ADVANCES IN

FERROELECTRICS

Edited by Aimé Peláiz Barranco

Advances in Ferroelectrics
http://dx.doi.org/10.5772/45744
Edited by Aimé Peláiz Barranco

Contributors
Takeo Sasaki, Jeffrey F. Webb, Hongyang Zhao, Shu-Tao Ai, Ashim Kumar Bain, Prem Chand, Ashok Kumar, Ram S.
Katiyar, M Correa, Nora Ortega, Shalini Kumari, Yuriy Garbovskiy, Anatoliy Glushchenko, Olena Zribi, Akira Onodera,
Desheng Fu, Hiroki Taniguchi, Mitsuru Itoh, Shigeo Mori, Amaury Suárez-Gómez, José-Manuel Saniger, Francisco
Calderón-Piñar, Junhao Chu, Zhigao Hu, Yawei Li, Kai Jiang, Ziqiang Zhu, Aimé Peláiz-Barranco, Osmany García-
Zaldívar, Yuslin González-Abreu, Dong Guo, Kai Cai, Hiroki Moriwake, Toshirou Yagi, Toshiro Kohmoto, Qiang Wan,
Changqing Chen, Yapeng Shen, Koukou Suu, Nicu Doinel Scarisoreanu, Ruxandra Birjega, Andreea Andrei, Maria
Dinescu, Carmen Galassi, Floriana Craciun, Kai-Huang Chen, Chien-Min Cheng, Sean Wu, Jen-Hwan Tsai, Kaoru Miura,
Funakubo Hiroshi, Martun Hovhannisyan, Matias Nunez

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Contents

Preface IX

Chapter 1 Electronic Structures of Tetragonal ABX3: Role of the B-X

Coulomb Repulsions for Ferroelectricity and
Piezoelectricity 1
Kaoru Miura and Hiroshi Funakubo

Chapter 2 Advances in Thermodynamics of Ferroelectric Phase

Transitions 25
Shu-Tao Ai

Chapter 3 Pb(Mg1/3Nb2/3)O3 (PMN) Relaxor: Dipole Glass or Nano-

Domain Ferroelectric? 51
Desheng Fu, Hiroki Taniguchi, Mitsuru Itoh and Shigeo Mori

Chapter 4 Self Assembled Nanoscale Relaxor Ferroelectrics 69

Ashok Kumar, Margarita Correa, Nora Ortega, Salini Kumari and R.
S. Katiyar

Chapter 5 Relaxor Behaviour in Ferroelectric Ceramics 85

A. Peláiz-Barranco, F. Calderón-Piñar, O. García-Zaldívar and Y.
González-Abreu

Chapter 6 Electronic Band Structures and Phase Transitions of

Ferroelectric and Multiferroic Oxides 109
Zhigao Hu, Junhao Chu, Yawei Li, Kai Jiang and Ziqiang Zhu

Chapter 7 Phase Diagram of The Ternary BaO-Bi2O3-B2O3 System: New

Compounds and Glass Ceramics Characterisation 127
Martun Hovhannisyan
VI Contents

Chapter 8 Optical Properties of Ferroelectrics and Measurement

Procedures 163
A.K. Bain and Prem Chand

Chapter 9 Ferroelectric Domain Imaging Multiferroic Films Using

Piezoresponse Force Microscopy 193
Hongyang Zhao, Hideo Kimura, Qiwen Yao, Lei Guo, Zhenxiang
Cheng and Xiaolin Wang

Chapter 10 Gelcasting of Ferroelectric Ceramics: Doping Effect and Further

Development 209
Dong Guo and Kai Cai

Chapter 11 Electronic Ferroelectricity in II-VI Semiconductor ZnO 231

Akira Onodera and Masaki Takesada

Chapter 12 Doping-Induced Ferroelectric Phase Transition and Ultraviolet-

Illumination Effect in a Quantum Paraelectric Material Studied
by Coherent Phonon Spectroscopy 257
Toshiro Kohmoto

Chapter 13 Raman Scattering Study on the Phase Transition Dynamics of

Ferroelectric Oxides 279
Hiroki Taniguchi, Hiroki Moriwake, Toshirou Yagi and Mitsuru Itoh

Chapter 14 Electromechanical Coupling Multiaxial Experimental and

Micro-Constitutive Model Study of Pb(Mg1/3Nb2/3)O3-
0.32PbTiO3 Ferroelectric Single Crystal 295
Wan Qiang, Chen Changqing and Shen Yapeng

Chapter 15 'Universal' Synthesis of PZT (1-X)/X Submicrometric Structures

Using Highly Stable Colloidal Dispersions: A Bottom-Up
Approach 323
A. Suárez-Gómez, J.M. Saniger-Blesa and F. Calderón-Piñar

Chapter 16 Phase Transitions, Dielectric and Ferroelectric Properties of

Lead-free NBT-BT Thin Films 351
N. D. Scarisoreanu, R. Birjega, A. Andrei, M. Dinescu, F. Craciun and
C. Galassi

Chapter 17 Thin-Film Process Technology for Ferroelectric

Application 369
Koukou Suu
 Contents VII

Chapter 18 Ferroelectrics at the Nanoscale: A First Principle

Approach 401
Matías Núñez

Chapter 19 The Influence of Vanadium Doping on the Physical and

Electrical Properties of Non-Volatile Random Access Memory
Using the BTV, BLTV, and BNTV Oxide Thin Films 429
Kai-Huang Chen, Chien-Min Cheng, Sean Wu, Chin-Hsiung Liao and
Jen-Hwan Tsai

Chapter 20 Nanoscale Ferroelectric Films, Strips and Boxes 449

Jeffrey F. Webb

Chapter 21 Emerging Applications of Ferroelectric Nanoparticles in

Materials Technologies, Biology and Medicine 475
Yuriy Garbovskiy, Olena Zribi and Anatoliy Glushchenko

Chapter 22 Photorefractive Effect in Ferroelectric Liquid Crystals 499

Takeo Sasaki
Preface

Since the discovery of the phenomenon of ferroelectricity, the continuous development of

materials and technology has provided an important number of applications. The
ferroelectricity has been the heart and soul of several industries to the development of
piezoelectric transducers, pyroelectric sensors, medical diagnostic transducers, radio and
communication filters, ultrasonic motors, electro-optical devices, ferroelectric memories, etc.
The most striking properties of the ferroelectric materials are strong coupling effects, strong
hysteresis in the field polarization response, and extremely high dielectric permittivity. For
the development of new technology by using ferroelectric materials, much research has been
carried out from the perspective of theory and of experiment. These have provided
revolutionary breakthroughs in the understanding of single crystals, ceramics, thin films
and composites. The advances in the studies of these materials at nanoscale have also
showed the potential applications of ferroelectric nanoparticles.
The purpose of this book is to offer an up-to-date view of ferroelectricity, covering a wide
range of theoretical and experimental topics. Several researches on ceramics, thin films,
ferroelectric liquids and ferroelectricity at nanoscale are included. The book is the result of
an important number of contributions of researchers from the international scientific
community, which work in different topics of ferroelectricity.
I would like to thank all the authors for their interesting contributions to this book and the
InTech team for the outstanding support.
We hope that this book will be of real value to students and researchers moving into the
ferroelectric field.

Dr. Aimé Peláiz Barranco

Applied Physics Department
Physics Faculty, Havana University
Cuba
 Chapter 1

Electronic Structures of Tetragonal ABX3:

Role of the B-X Coulomb Repulsions for
Ferroelectricity and Piezoelectricity

Kaoru Miura and Hiroshi Funakubo

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52187

1. Introduction

Since Cohen proposed an origin for ferroelectricity in perovskites (ABX3) [1], investigations
of ferroelectric materials using first-principles calculations have been extensively studied
[2-20]. Currently, using the pseudopotential (PP) methods, most of the crystal structures in
ferroelectric ABX3 can be precisely predicted. However, even in BaTiO3, which is a well-
known ferroelectric perovskite oxide with tetragonal structure at room temperature, the op‐
timized structure by the PP methods is strongly dependent on the choice of the Ti PPs as
illustrated in Fig. 1; preparation for Ti 3s and 3p semicore states in addition to Ti 3d, 4s, and
4p valence states is essential to the appearance of the tetragonal structure. This is an impor‐
tant problem for ferroelectricity, but it has been generally recognized for a long time that
this problem is within an empirical framework of the calculational techniques [21].

Unit cell
O Ti O
z- axis
Wave functions Wave functions
Ti 3d, 4s, 4p Valence states (FP)
(PP)
O 2s, 2p (PP)

Ti 3s, 3p ?
Atomic potentials
Ti 1s ～ 2p Core states
O 1s ～ charge density～

Figure 1. Illustration of the choice of Ti 3s and 3p states in pseudopotentials.

© 2012 Miura and Funakubo; licensee InTech. This is an open access article distributed under the terms of the
Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
2 Advances in Ferroelectrics

It is known that ferroelectric state appears when the long-range forces due to the dipole-di‐
pole interaction overcome the short-range forces due to the Coulomb repulsions. Investiga‐
tions about the relationship between the Ti-O Coulomb repulsions and the appearance of
ferroelectricity in ATiO3 (A = Ba, Pb) were reported both theoretically and experimentally.
Theoretically, Cohen first proposed the hybridization between Ti 3d state and O 2p state (Ti
3d-O 2p) as an origin for ferroelectricity in BaTiO3 and PbTiO3 [1]. On the other hand, we
investigated [20] the influence of the Ti-Oz Coulomb repulsions on Ti ion displacement in
tetragonal BaTiO3 and PbTiO3, where Oz denotes the O atom to the z-axis (Ti is displaced to
the z-axis). Whereas the hybridization between Ti 3d state and Oz 2pz state stabilize Ti ion
displacement, the strong Coulomb repulsions between Ti 3s and 3pz states and O 2pz states
do not favourably cause Ti ion displacement. Experimentally, on the other hand, Kuroiwa et
al. [22] showed that the appearance of ferroelectric state is closely related to the total charge
density of Ti-O bonding in BaTiO3. As discussed above, investigation about a role of Ti 3s
and 3p states is important in the appearance of the ferroelectric state in tetragonal BaTiO3, in
addition to the Ti 3d-O 2p hybridization as an origin of ferroelectricity [1].

It seems that the strong B-X Coulomb repulsions affect the most stable structure of ABX3. It has
been well known that the most stable structure of ABX3 is closely related to the tolerance factor t,

rA + rX
t= , (1)
2 (rB + rX )

where rA, rB, and rX denote the ionic radii of A, B, and X ions, respectively [23]. In general
ferroelectric ABX3, the most stable structure is tetragonal for t ≳ 1, cubic for t ≈ 1, and rhom‐
bohedral or orthorhombic for t ≲ 1. In fact, BaTiO3 with t = 1.062 shows tetragonal structure
in room temperature. However, recently, BiZn0.5Ti0.5O3 (BZT) with t = 0.935 was experimen‐
tally reported [24] to show a tetragonal PbTiO3-type structure with high c/a ratio (1.211).
This result is in contrast to that of BiZn0.5Mg0.5O3 (BMT) with t = 0.939, i.e., the most stable
structure was reported to be the orthorhombic or rhombohedral structure [25, 26]. Several
theoretical papers of BZT have been reported [4-6], but the role of the Zn-O Coulomb repul‐
sions in the appearance of the tetragonal structure has not been discussed sufficiently.

Piezoelectric properties in ABX3 are also closely related to the crystal structure. Investigations of
the relationship between piezoelectric properties and the crystal structure of ABX3 by first-prin‐
ciples calculations have been extensively studied [2-19]. Moreover, phenomenological investi‐
gations of the piezoelectric properties have been also performed [27, 28]. However, it seems that
the piezoelectric properties in the atomic level have not been sufficiently investigated. There‐
fore, further theoretical investigation of the relationship between piezoelectric properties and
the crystal structure of ABX3, especially the B-X Coulomb repulsions, should be needed.

Recently, we investigated the roles of the Ti-O Coulomb repulsions in the appearance of a
ferroelectric state in tetragonal BaTiO3 by the analysis of a first-principles PP method [11-15].
We investigated the structural properties of tetragonal and rhombohedral BaTiO3 with two
kinds of Ti PPs, and propose the role of Ti 3s and 3p states for ferroelectricity. We also inves‐
 Electronic Structures of Tetragonal ABX3: Role of the B-X Coulomb Repulsions for Ferroelectricity and Piezoelectricity 3
http://dx.doi.org/10.5772/52187

tigated the role of the Zn-O Coulomb repulsions in the appearance of a ferroelectric state in
tetragonal BZT [10, 13]. Moreover, we also investigated the structural, ferroelectric, and pie‐
zoelectric properties of tetragonal ABX3 and discussed the piezoelectric mechanisms based
on the B-X Coulomb repulsions [12, 14, 15, 18, 19].
In this chapter, based on our recent papers and patents [10-19], we discuss a general role of
B-X Coulomb repulsions for the appearance of the ferroelectric state in ABX3. Then, we also
discuss the relationship between the B-X Coulomb repulsions and the piezoelectric proper‐
ties of tetragonal ABX3.

2. Methodology

The calculations for ABX3 were performed using the ABINIT code [29], which is one of the norm-
conserving PP (NCPP) methods. Electron-electron interaction was treated in the local-density
approximation (LDA) [30]. Pseudopotentials were generated using the OPIUM code [31]:

i. In BaTiO3, 5s, 5p and 6s electrons for Ba PP, and 2s and 2p electrons for O PP were
treated as semicore or valence electrons, respectively. Moreover, in order to investi‐
gate the role of Ti 3s and 3p states, two kinds of Ti PPs were prepared: the Ti PP
with 3s, 3p, 3d and 4s electrons treated as semicore or valence electrons (Ti3spd4s
PP), and that with only 3d and 4s electrons treated as valence electrons (Ti3d4s PP).
In both PPs, the differences between the calculated result and experimental one are
within 1.5 % of the lattice constant and within 10 % of the bulk modulus in the opti‐
mized calculation of bulk Ti. The cutoff energy for plane-wave basis functions was
set to be 50 Hartree (Hr). The number of atoms in the unit cell was set to be five,
and a 6×6×6 Monkhorst-Pack k-point mesh was set in the Brillouin zone of the unit
cell. Positions of all the atoms were optimized within the framework of the tetrago‐
nal (P4mm) or rhombohedral (R3m) structure.
ii. In BZT and BMT, 5d, 6s, and 6p electrons for Bi PP, and 2s and 2p electrons for O
PP were treated as semicore or valence electrons, respectively. Moreover, in order
to investigate the roles of Zn and Ti 3s and 3p states, and Mg 2s and 2p states, two
types of PPs were prepared: the PPs with only Zn and Ti 3d and 4s states, and Mg
3s states, considered as valence electrons (Case I), Zn and Ti 3s, 3p, 3d, and 4s
states, and Mg 2s, 2p, and 3s states considered as semicore or valence electrons
(Case II). The cutoff energy for plane-wave basis functions was set to be 70 Hr for
Case I and 110 Hr for Case II. A 4×4×4 Monkhorst-Pack k-point mesh was set in the
Brillouin zone of the unit cell. The calculated results can be discussed within 0.02
eV per formula unit (f.u.) using the above conditions. The present calculations were
performed for the monoclinic, rhombohedral, and A-, C-, and G-type tetragonal
structures. The number of atoms in the unit cell was set to be 10 for the rhombohe‐
dral and monoclinic structures, and 20 for the A-, C-, and G-type tetragonal struc‐
tures. Positions of all the atoms were optimized within the framework of the
rhombohedral (R3), monoclinic (Pm), and tetragonal (P4mm) structures.
4 Advances in Ferroelectrics

iii. Relationship between the B-X Coulomb repulsions and the piezoelectric properties
in tetragonal ABX3 is investigated. The pseudopotentials were generated using the
opium code [31] with semicore and valence electrons (e.g., Ti3spd4s PP), and the
virtual crystal approximation [32] were applied to several ABX3.

Spontaneous polarizations and piezoelectric constants were also evaluated, due to the Born
effective charges [33]. The spontaneous polarization of tetragonal structures along the [001]
axis, P3, is defined as

ec *
P3 = å Z ( k ) u 3 ( k) , (2)
k
Ω 33

where e, c, and Ω denote the charge unit, lattice parameter of the unit cell along the [001]
axis, and the volume of the unit cell, respectively. u3(k) denotes the displacement along the
[001] axis of the kth atom, and Z33*(k) denotes the Born effective charges [33] which contrib‐
utes to the P3 from the u3(k).

The piezoelectric e33 constant is defined as

æ ¶P ö ec * ¶u ( k )
e3 j = çç 3 ÷÷ + å Z33
¶h Ω
( k ) ¶h3 ( j = 3,1) , (3)
è 3 øu k j

where e and Ω denote the charge unit and the volume of the unit cell. P3 and c denote the
spontaneous polarization of tetragonal structures and the lattice parameter of the unit cell
along the [001] axis, respectively. u3(k) denotes the displacement along the [001] axis of the
kth atom, and Z33*(k) denotes the Born effective charges which contributes to the P3 from the
u3(k). η3 denotes the strain of lattice along the [001] axis, which is defined as η3 ≡ (c – c0)/c0; c0
denotes the c lattice parameter with fully optimized structure. On the other hand, η1 denotes
the strain of lattice along the [100] axis, which is defined as η1 ≡ (a – a0)/a0; a0 denotes the a
lattice parameter with fully optimized structure. The first term of the right hand in Eq. (3)
denotes the clamped term evaluated at vanishing internal strain, and the second term de‐
notes the relaxed term that is due to the relative displacements.

The relationship between the piezoelectric d33 constant and the e33 one is

6
d33 º ås3Ej ´ T ( e3 j ) , (4)
j =1

where s3j denotes the elastic compliance, and ``T ” denotes the transposition of matrix ele‐
E

ments. The suffix j denotes the direction-indexes of the axis, i.e., 1 along the [100] axis, 2
along the [010] axis, 3 along the [001] axis, and 4 to 6 along the shear directions, respectively.
The relationship between the piezoelectric d33 constant and the e33 one is

6
d33  s3Ej  T ( e3 j ) , (4)
Electronic Structures of Tetragonal ABX3: Role of the
j 1B-X Coulomb Repulsions for Ferroelectricity and Piezoelectricity 5
http://dx.doi.org/10.5772/52187

where s3jE denotes the elastic compliance, and ``T ” denotes the transposition of matrix elements. The suffix j denotes the direction-
indexes of the 3. Results
axis, andthediscussion
i.e., 1 along [100] axis, 2 along the [010] axis, 3 along the [001] axis, and 4 to 6 along the shear directions,
respectively.
3.1. Ferroelectricity
3. Results and discussion
3.1.1. Role of Ti 3s and 3p states in ferroelectric BaTiO3

3.1. Ferroelectricity
Figures 2(a) and 2(b)show the optimized results for the ratio c/a of the lattice parameters
and the value of the Ti ion displacement (δTi) as a function of the a lattice parameter in
3.1.1. Role of tetragonal
Ti 3s and BaTiO 3p3, states
respectively. Results withBaTiO
in ferroelectric arrows3 are the fully optimized results, and
the others results are those with the c lattice parameters and all the inner coordination
Figures 2(a) andoptimized
2(b) show for fixed a. Note
the optimized resultsthat theratio
for the fully
c/a optimized
of the latticestructure
parametersofand BaTiO 3 is tetragonal
the value of the Ti ion displacement
with
(δTi) as a function of the
the aTi3spd4s PP, whereas
lattice parameter it is cubic
in tetragonal BaTiOwith the Ti3d4s
3, respectively. PP. with
Results Thisarrows
result are
suggests
the fullythat
optimized results,
and the others the explicit
results treatment
are those with the of Ti 3sparameters
c lattice and 3p semicore
and all thestates is essential optimized
inner coordination to the appearance of that the fully
for fixed a. Note
ferroelectric
optimized structure of BaTiOstates in BaTiO
3 is tetragonal with
3 . the Ti3spd4s PP, whereas it is cubic with the Ti3d4s PP. This result suggests that
the explicit treatment of Ti 3s and 3p semicore states is essential to the appearance of ferroelectric states in BaTiO3.

(a) (b)
1.5 0.6
1.4 0.5
Ti3spd4s
0.4
δTi (Å)

1.3
c/a

Ti3spd4s 0.3
1.2 0.2
1.1 Ti3d4s Ti3d4s
0.1
1 0
3.5 3.6 3.7 3.8 3.9 4 3.5 3.6 3.7 3.8 3.9 4
a (Å) a (Å)

Figure
Figure 2. Optimized 2. Optimized
calculated calculated
results resultsBaTiO
in tetragonal in tetragonal BaTiO
3. Results with3.arrows
Results are
withthe
arrows
fully are the fullyresults
optimized optimized
[11].results [11].

The calculatedThe calculated

results shown in results
Fig. 2shown
suggestinthat
Fig.the
2 suggest that the explicit
explicit treatment of Ti 3s treatment of Ti 3sstates
and 3p semicore and is3pessential to the
appearance of semicore states
ferroelectric statesisinessential to the
BaTiO3. In thefollowing,
appearance
we of ferroelectric
investigate states
the role in3sBaTiO
of Ti 3. In
and 3p the for
states follow‐
ferroelectricity from
ing, we investigate the role of Ti 3s and 3p states for ferroelectricity from two viewpoints.
two viewpoints.

One viewpointOne viewpoint

concerns concerns
hybridizations hybridizations
between between
Ti 3s and 3p Ti other
states and 3s and 3p states
states. Figure and other
3(a) and 3(b)states.
showsFig‐
the total density of
ure 3(a) and 3(b) shows the total density of states (DOS) of tetragonal BaTiO
states (DOS) of tetragonal BaTiO3 with two Ti PPs. Both results are in good agreement with previous calculated 3 with two results [7] by the
Ti PPs.
full-potential linear Both results
augmented are in
plane wave good agreement
(FLAPW) with
method. In the DOSprevious
with the calculated
Ti3spd4s PP,results [7] by
the energy the not bands, of
``levels",
full-potential
Ti 3s and 3p states, are locatedlinear
at -2.0 augmented
Hr and -1.2 Hr, plane wave (FLAPW)
respectively. method.that
This result suggests In the
theTiDOS
3s andwith the do not make
3p orbitals
Ti3spd4s
any hybridization but onlyPP,give
theCoulomb
energy repulsions
``levels", not
withbands, of Ti 3sasand
the O orbitals well3p states,
as the are located
Ba orbitals. In theatDOS
-2.0with
Hr the Ti3d4s PP,
and -1.2
on the other hand, Hr, respectively.
the energy levels of Ti This
3s andresult suggests
3p states that
are not the Ti
shown 3s and
because Ti 3p orbitals
3s and do not
3p states make
were treated as the core
any hybridization
charges. This result means that the Ti but
3s only
and 3pgive Coulomb
orbitals repulsions
cannot even with the
give Coulomb O orbitals
repulsions withas thewell as the
O orbitals as well as the Ba
orbitals.
Ba orbitals. In the DOS with the Ti3d4s PP, on the other hand, the energy levels of Ti 3s
and 3p states are not shown because Ti 3s and 3p states were treated as the core charg‐
es. This result means that the Ti 3s and 3p orbitals cannot even give Coulomb repulsions
with the O orbitals as well as the Ba orbitals.
6 Advances in Ferroelectrics

Density of States (/ Hr)

Ti 3s Ti 3p O 2p Ti 3d

～ Ti3spd4s
～ Ti3d4s

Figure 3. Total density of states (DOS) of fully optimized tetragonal BaTiO3 with the Ti3spd4s PP (solid line) and cubic
BaTiO3 with the Ti3d4s PP (red dashed line) [11].

Another viewpoint is about the Coulomb repulsions between Ti 3s and 3px (y) states and Ox (y) 2s
and 2px (y) states in tetragonal BaTiO3. Figure 4(a) and 4(b) show two-dimensional electron-den‐
sity contour map on the xz-plane. These are the optimized calculated results with a fixed to be 3.8
Å, and the electron density in Fig. 4(a) is quantitatively in good agreement with the experimen‐
tal result [22]. The electron density between Ti and Ox ions in Fig. 3(a) is larger than that in Fig.
4(b), which suggests that Ti ion displacement is closely related to the Coulomb repulsions be‐
tween Ti 3s and 3px (y) states and Ox (y) 2s and 2px (y) states; the Ti-O Coulomb repulsion is an impor‐
tant role in the appearance of the ferroelectric state in BaTiO3.

The present discussion of the Coulomb repulsions is consistent with the previous reports. A
recent soft mode investigation [8] of BaTiO3 shows that Ba ions contribute little to the ap‐
pearance of Ti ion displacement along the [001] axis. This result suggests that Ti ion dis‐
placement is closely related to the structural distortion of TiO6 octahedra. In the present
calculations, on the other hand, the only difference between BaTiO3 with the Ti3spd4s PP
and with the Ti3d4s PP is the difference in the expression for the Ti 3s and 3p states, i.e., the
explicit treatment and including core charges. However, our previous calculation [20] shows
that the strong Coulomb repulsions between Ti 3s and 3pz states and Oz 2s and 2pz states do
not favor Ti ion displacement along the [001] axis. This result suggests that the Coulomb re‐
pulsions between Ti 3s and 3px (y) states and Ox (y) 2s and 2px (y) states would contribute to Ti
ion displacement along the [001] axis, and the suggestion is consistent with a recent calcula‐
tion [9] for PbTiO3 indicating that the tetragonal and ferroelectric structure appears more fa‐
vorable as the a lattice constant decreases.
 Electronic Structures of Tetragonal ABX3: Role of the B-X Coulomb Repulsions for Ferroelectricity and Piezoelectricity 7
http://dx.doi.org/10.5772/52187

(a) (b)
Oz Oz

Ti Ox Ti Ox

Ti3spd4s Ti3d4s

Figure 4. Two-dimensional electron-density contour map on the xz-plane for tetragonal BaTiO3: (a) with the Ti3spd4s
PP, and (b) with the Ti3d4s PP. The optimized calculated results with a fixed to be 3.8 Å are shown in both figures. The
electron density increases as color changes from blue to red via white. Contour curves are drawn from 0.4 to 2.0 e/Å3
with increments of 0.2 e/Å3 [11].

Considering the above investigations, we propose the mechanism of Ti ion displacement as

follows: Ti ion displacement along the z-axis appears when the Coulomb repulsions be‐
tween Ti 3s and 3 px (y) states and Ox (y) 2s and 2 px (y) states, in addition to the dipole-dipole
interaction, overcome the Coulomb repulsions between Ti 3s and 3pz states and Oz 2s and
2pz states. An illustration of the Coulomb repulsions is shown in Fig. 5(a). In fully optimized
BaTiO3 with the Ti3spd4s PP, the Ti ion can be displaced due to the above mechanism. In
fully optimized BaTiO3 with the Ti3d4sPP, on the other hand, the Ti ion cannot be displaced
due to the weaker Coulomb repulsions between Ti and Ox (y) ions. However, since the Cou‐
lomb repulsion between Ti and Oz ions in BaTiO3 with the Ti3d4s PP is also weaker than that
in BaTiO3 with the Ti3spd4s PP, the Coulomb repulsions between Ti and Ox (y) ions in addi‐
tion to the log-range force become comparable to the Coulomb repulsions between Ti and Oz
ions both in Ti PPs, as the a lattice parameter becomes smaller. The above discussion sug‐
gests that the hybridization between Ti 3d and Oz 2s and 2pz stabilizes Ti ion displacement,
but contribute little to a driving force for the appearance of Ti ion displacement.
8 Advances in Ferroelectrics

It seems that the above proposed mechanism for tetragonal BaTiO3 can be applied to the
mechanism of Ti ion displacement in rhombohedral BaTiO3, as illustrated in Fig. 5(b). The
strong isotropic Coulomb repulsions between Ti 3s and 3px (y, z) states and Ox (y, z) 2s and
2px (y, z) states yield Ti ion displacement along the [111] axis. On the other hand, when the
isotropic Coulomb repulsions are weaker or stronger, the Ti ion cannot be displaced and
therefore it is favoured for the crystal structure to be cubic.

(a) z (b) z

2s

2pz Oz
Oz
3pz 2s 2s
3s 3s
Ox 3px Ox
Ti
x x
Ti 3px 2px
2 2px
Coulomb 3pz
Coulomb repulsion
repulsion

Figure 5. Illustrations of the proposed mechanisms for the Coulomb repulsions between Ti 3s and 3p states and O 2s
and 2p states in BaTiO3: (a) anisotropic Coulomb repulsions between Ti 3s and 3px (y) states and Ox (y) 2s and 2px (y)
states, and between Ti 3s and 3pz states and Oz 2s and 2pz states, in the tetragonal structure. (b) isotropic Coulomb
repulsions between Ti 3s and 3px (y, z) states and Ox (y, z) 2s and 2px (y, z) states, in the rhombohedral structure [11].

Let us investigate the structural properties of rhombohedral BaTiO3. Figures 6(a) and 6(b)
show the optimized results of the 90-α degree and δTi as a function of fixed volumes of the
unit cells in rhombohedral BaTiO3, respectively, where α denotes the angle between two lat‐
tice vectors. In these figures, α denotes the angle between two crystal axes of rhombohedral
BaTiO3, and δTi denotes the value of the Ti ion displacement along the [111] axis. Results
with arrows are the fully optimized results; Vopt denote the volume of the fully optimized
unit cell with the Ti3spd4s PP. The other results are those with all the inner coordination op‐
timized with fixed volumes of the unit cells. The proposal mechanisms about the Coulomb
repulsions seem to be consistent with the calculated results shown in Fig.6: For V/Vopt ≲ 0.9
or ≳ 1.3, the isotropic Coulomb repulsions are weaker or stronger, and the Ti ion cannot be
displaced along the [111] axis and therefore the crystal structure is cubic for both Ti PPs. For
0.9 ≲ V/Vopt ≲ 1.3, on the other hand, the isotropic Coulomb repulsions are strong enough to
yield Ti ion displacement for both Ti PPs. However, since the magnitude of the isotropic
Coulomb repulsion is different in the two Ti PPs, the properties of the 90-α degree and δTi
are different quantitatively.
the value of the Ti ion displacement along the [111] axis. Results with arrows are the fully optimized results; Vopt denote the volume
of the fully optimized unit cell with the Ti3spd4s PP. The other results are those with all the inner coordination optimized with
fixed volumes of the unit cells. The proposal mechanisms about the Coulomb repulsions seem to be consistent with the calculated
results shown in Fig.6: For V/Vopt ≲ 0.9 or ≳ 1.3, the isotropic Coulomb repulsions are weaker or stronger, and the Ti ion cannot be
displaced alongElectronic
the [111]Structures
axis andoftherefore
Tetragonalthe
ABX3: Role structure
crystal of the B-X Coulomb
is cubic Repulsions
for both TiforPPs.
Ferroelectricity
For 0.9 ≲ V/Vand opt ≲ 1.3, on the 9other hand,
Piezoelectricity
the isotropic Coulomb repulsions are strong enough to yield Ti ion displacement for both http://dx.doi.org/10.5772/52187
Ti PPs. However, since the magnitude of
the isotropic Coulomb repulsion is different in the two Ti PPs, the properties of the 90-α degree and δTi are different quantitatively.

(a) (b)
1.2 0.4
1 Ti3spd4s
90 - α(deg.)

Ti3spd4s 0.3
0.8

δ Ti (Å)
Ti3d4s
0.6 0.2
0.4
0.2 0.1
0 Ti3d4s
0
0.8 0.9 1 1.1 1.2 1.3 1.4 0.8 0.9 1 1.1 1.2 1.3 1.4
V/Vopt V/Vopt

6. Optimized
Figure calculated
Figure 6. Optimized calculated
results results of
as a function as the
a function of the fixed
fixed volumes of thevolumes ofin
unit cells the unit cells in rhombohedral
rhombohedral BaTiO
BaTiO3: (a) 90-α 3: (a)
degree and (b) δTi to the
[111] axis. Blue90-α
linesdegree and (b)
correspond to δthe
Ti to the [111]
results withaxis. Blue lines PP,
the Ti3spd4s correspond to thecorrespond
and red lines results withtothe Ti3spd4s
those PP,Ti3d4s
with the and red
PP.lines
Voptcorre‐
denote the volume of
spondunit
the fully optimized to those withthe
cell with theTi3spd4s
Ti3d4s PP.PP. denotewith
VoptResults the volume of the
arrows are thefully
fullyoptimized
optimized unit cell with
results, andthe
theTi3spd4s PP. Results
other results are those with all the
with optimized
inner coordination arrows areforthefixed
fullyvolumes
optimized results,
of the unitand
cellsthe other results are those with all the inner coordination optimized
[11].
for fixed volumes of the unit cells [11].

3.1.2. Role of Zn 3s, 3p and 3d states in ferroelectric BiZn0.5Ti0.5O3

3.1.2. Role of Zn 3s, 3p and 3d states in ferroelectric BiZn0.5Ti0.5O3
As discussed in Sec. 3.1.1, the Coulomb repulsions between Ti 3s and 3px (y) states and Ox (y) 2s and 2px (y) states have an important
As discussed
role in the appearance of theinferroelectric
Sec. 3.1.1,state
the Coulomb repulsions
in tetragonal BaTiO3. Inbetween Ti 3s and
this subsection, 3px (y) states
we discuss the roleand Ox 3d
of Zn (y) (d10) states in
2s and 2p x (y) states have an important role in
addition to 3s and 3p states for ferroelectricity in tetragonal BZT. the appearance of the ferroelectric state in tet‐
ragonal BaTiO3. In this subsection, we discuss the role of Zn 3d (d10) states in addition to 3s
and
Table 1 shows 3p states of
a summary forthe
ferroelectricity in tetragonal
optimized results BZT.I and II. ΔEtotal denotes the difference in total energy per f.u.
of BZT in Cases
between the rhombohedral and other structures. Although the lattice constant in each structure except the rhombohedral one
Table 1 shows
seems to be quantitatively a summary
similar of the
in both cases, optimized
properties of Δresults
Etotal are of BZT inInCases
different. Case I,I the
andrhombohedral
II. ΔEtotal denotes
structure is the most
the difference in total energy per f.u. between the rhombohedral and other structures. Al‐
though the lattice constant in each structure except the rhombohedral one seems to be quan‐
titatively similar in both cases, properties of ΔEtotal are different. In Case I, the rhombohedral
structure is the most stable, which is in disagreement with the experimental result [24]. In
Case II, on the other hand, the monoclinic structure, which is the ``pseudo-C-type-tetrago‐
nal'' structure, is the most stable. Unfortunately, this result seems to be in disagreement with
the experimental result [24], but is in good agreement with the recent calculated result [6].
Note that the magnitude of ΔEtotal in Case II is markedly smaller than that in Case I. In con‐
trast to BZT, the rhombohedral structure is the most stable structure in both cases in BMT,
which is consistent with the experimental result [26].

Figures 7(a) and 7(b) show two-dimensional electron density contour maps of the C-type tet‐
ragonal BZT in Cases I and II, respectively. The Coulomb repulsion of Zn-Ox in Case II is
larger than that in Case I, and the Coulomb repulsion favorably causes Zn ion displacement
to O z in Case II. This result is consistent with Sec. 3.1.1. In contrast to the properties of Zn-O
bonding, the inner coordination of the Ti ion is similar in both cases, although the electron
densities are markedly different. This result suggests that the Coulomb repulsion magnitude
of Ti-Oz is the same as that of Ti-Ox in small Ti-O bonding (≈ 1.8 Å), in both Cases I and II.
Figures 7(c) and 7(d) show two-dimensional electron density contour maps of the C-type tet‐
10 Advances in Ferroelectrics

ragonal BMT in Cases I and II, respectively. Although the electron densities in both cases are
markedly different, the inner coordination of the Mg ion are similar. This result suggests
that the Coulomb repulsion between Mg and O is not strong sufficiently for inducing Mg
ion displacement even in Case II.

Structure a (Å) c (Å) c/a α (deg.) ΔEtotal (eV/f.u.)

A-type Tetra. 3.748 4.579 1.222 90 0.316

C-type Tetra. 3.681 4.784 1.299 90 0.240

G-type Tetra. 3.725 4.574 1.228 90 0.158

Monoclinic 3.735 4.741 1.269 β = 91.5 0.193

Rhombohedral 5.560 1 59.93 0

Experiment [24] 3.822 4.628 1.211 90 ---

(a)

Structure a (Å) c (Å) c/a α (deg.) ΔEtotal (eV/f.u.)

A-type Tetra. 3.711 4.662 1.256 90 0.135

C-type Tetra. 3.670 4.789 1.305 90 0.091

G-type Tetra. 3.684 4.698 1.275 90 0.047

Monoclinic 3.726 4.740 1.272 β = 91.1 -0.021

Rhombohedral 5.590 1 59.90 0

Experiment [24] 3.822 4.628 1.211 90 ---

(b)

Table 1. Summary of the optimized results of BZT in (a) Case I and (b) Case II. a and c denote the lattice parameters,
and α and β denote angles between two lattice axes. ΔEtotal denotes the difference in total energy per f.u. between the
rhombohedral and other structures [10].

Finally in this subsection, we discuss the difference in the electronic structures between the
C-type tetragonal and the monoclinic BZT. Figures 8(a) and 8(b) show the electron density
contour maps of the C-type tetragonal BZT and that of the monoclinic BZT in Case II, re‐
spectively. This result suggests that the strong Coulomb repulsion between Zn and Oz caus‐
es the small Zn ion displacement in the [110] direction in the monoclinic BZT, which makes
the Coulomb repulsion of Zn-Oz weaker than that in the C-type tetragonal BZT. As a result,
this small Zn ion displacement makes the monoclinic BZT more stable than the C-type tet‐
ragonal structure.
 Electronic Structures of Tetragonal ABX3: Role of the B-X Coulomb Repulsions for Ferroelectricity and Piezoelectricity 11
http://dx.doi.org/10.5772/52187

(a) ～ b～

Ox Ox
Zn Ti Zn Ti

Oz Oz Oz Oz

(c) ～ d～

Ox Ox
Mg Ti Mg Ti
[001]
Oz Oz Oz Oz

[110]

Figure 7. Two-dimensional electron density contour maps of monoclinic (a) BZT in Case I, (b) BZT in Case II, (c) BMT in
Case I, and (d) BMT in Case II. The electron density increases as color changes from blue to red via white. Contour
curves are drawn from 0.2 to 2.0 e/Å3 with increments of 0.2 e/Å3 [10].

(a) ～ b～

Bi
Bi
Ti Zn Ti Zn
[001]
Oz Oz Oz Oz [110] [110]
Bi Bi

Figure 8. Two-dimensional electron density contour maps of BZT in Case II (a) C-type tetragonal and (b) monoclinic.
The electron density increases as color changes from blue to red via white. Contour curves are drawn from 0.2 to 2.0
e/Å3 with increments of 0.2 e/Å3 [10].
 12 Advances in Ferroelectrics

3.2. Piezoelectricity

3.2.1. Role of the Ti-O Coulomb repulsions in tetragonal piezoelectric SrTiO3 and BaTiO3

As discussed in Sec. 3.1, the Coulomb repulsions between Ti 3s and 3px (y) states and Ox (y) 2s
and 2px (y) states have an important role in the appearance of the ferroelectric state in tetrago‐
nal BaTiO3. In this subsection, we discuss the role of the Ti-O Coulomb repulsions for piezo‐
electric SrTiO3 and BaTiO3.

Figures 9(a) shows the optimized results for c – ccub as a function of the a lattice parameters
in tetragonal SrTiO3 and BaTiO3, where ccub denotes the c lattice parameter in cubic SrTiO3
and BaTiO3, respectively. These results are the fully optimized results and the results with
the c lattice parameters and all the inner coordination optimized for fixed a. The fully opti‐
mized parameters of SrTiO3 (a = 3.84 Å: cubic) and BaTiO3 (a = 3.91 Å and c = 4.00 Å: tetrago‐
nal) are within 2.0 % in agreement with the experimental results in room temperature.
Figure 9(b) shows the evaluated results for P3 as a function of the a lattice parameters in tet‐
ragonal SrTiO3 and BaTiO3, where P3, which is evaluated by Eq. (2), denotes the spontane‐
ous polarization along the [001] axis. Note that the tetragonal and ferroelectric structures
appear even in SrTiO3 when the fixed a lattice parameter is compressed to be smaller than
the fully-optimized a lattice parameter. As shown in Figs. 9(a) and 9(b), the tetragonal and
ferroelectric structure appears more favorable as the fixed a lattice parameter decreases,
which is consistent with previous calculated results [9, 11]. The results would be due to the
suggestion discussed in the previous section that the large Coulomb repulsion of Ti-O bond‐
ing along the [100] axis (and the [010] axis) is a driving force of the displacement of Ti ions
suggestionalong the [001]
discussed in the axis, i.e.,section
previous the large
that Coulomb repulsion
the large Coulomb alongofthe
repulsion [100]
Ti-O axis along
bonding (and the [010]axis
the [100] axis)
(and the [010]
is essential for the appearance of the tetragonal structure.
axis) is a driving force of the displacement of Ti ions along the [001] axis, i.e., the large Coulomb repulsion along the [100] axis (and
the [010] axis) is essential for the appearance of the tetragonal structure.

(a) （b）
1.0 1.0

0.8 0.8
(A)

(C/m^2)

BaTiO 3 BaTiO 3
cub (Å)

2)
3 (C/m

0.6 0.6
cc -- cc_cub

0.4 0.4
PP3

SrTiO 3
0.2 0.2
SrTiO 3
0.0 0.0
3.6 3.7 3.8 3.9 4.0 3.6 3.7 3.8 3.9 4.0

a a(Å)
(A) aa (Å)
(A)

Figure 9. Optimized calculated results as a function of a lattice parameters in compressive tetragonal SrTiO3 and BaTiO3: (a) c – ccub and (b) P3, i.e.,
Figure 9. Optimized calculated results as a function of a lattice parameters in compressive tetragonal SrTiO3 and Ba‐
spontaneous polarization along the [001] axis [12].
TiO3: (a) c – ccub and (b) P3, i.e., spontaneous polarization along the [001] axis [12].

In the following, we use c – ccub as a functional parameter, because c – ccub is closely related to η3. Figures 10(a) and 10(b) shows the
In the following, we use c – ccub as a functional parameter, because c – ccub is closely related to
piezoelectric properties of e33 and e31 as a function of c – ccub in tetragonal SrTiO3 and BaTiO3. The value c – ccub is optimized value as
shown in ηFig.
3. Figures
9(a) and10(a) and
e33 and e31 10(b) shows the
are evaluated values piezoelectric properties
in their optimized of e33Note
structures. and that
e31 ase33abecome
function of cat– c – ccub ≈ 0,
larger
c in tetragonal SrTiO and BaTiO
cubSrTiO3. These properties3 seem to be similar
especially in 3 . The value c – c is optimized value as shown in Fig.
cub arond the Curie temperatures in piezoelectric
to the properties ABO3;
Damjanovic 9(a) and e33 and
emphasized e31 are evaluated
the importance values inextension
of the polarization their optimized structures.
as a mechanism Note
of larger that e33 become
piezoelectric constants in a recent
paper [28]. Contrary to e33, on the other hand, the changes in e31 are much smaller than the changes in e33, but note that e31 shows
negative in SrTiO3 while positive in BaTiO3.

(a) （b）
16.0 1.0
BaTiO 3
12.0
m2 )

0.5
2)
m^2)

SrTiO 3
^2)
 cc -- cc_c
cu
0.4

3 ((
0.4

PP3
SrTiO 3
0.2 0.2
SrTiO 3
0.0 0.0
Electronic Structures
3.6 of Tetragonal
3.7 ABX3: 3.9
3.8 Role of 4.0
the B-X Coulomb Repulsions
3.6 for
3.7Ferroelectricity
3.8 3.9and Piezoelectricity
4.0 13
http://dx.doi.org/10.5772/52187
aa (Å)
(A)
a a(Å)
(A)

larger atcalculated
Figure 9. Optimized c – ccubresults
≈ 0, especially
as a function in
of aSrTiO
3. These properties seem to be similar to the proper‐
lattice parameters in compressive tetragonal SrTiO3 and BaTiO3: (a) c – ccub and (b) P3, i.e.,
spontaneous polarization along the [001] axis [12].
ties arond the Curie temperatures in piezoelectric ABO3; Damjanovic emphasized the impor‐
tance
In the following, weof use
thec polarization extension
– ccub as a functional as abecause
parameter, mechanism ofclosely
c – ccub is largerrelated
piezoelectric constants
to η3. Figures 10(a) andin a shows the
10(b)
recent
piezoelectric paperof[28].
properties e33 andContrary to e33, on
e31 as a function of c the
– ccubother hand, the
in tetragonal SrTiOchanges in e331. The
3 and BaTiO are value
muchc –smaller than value as
ccub is optimized
the changes
shown in Fig. 9(a) and ein e33, but note that e31 shows negative in SrTiO3 while positive in BaTiO3.
33 and e31 are evaluated values in their optimized structures. Note that e33 become larger at c – ccub ≈ 0,

especially in SrTiO3. These properties seem to be similar to the properties arond the Curie temperatures in piezoelectric ABO3;
Damjanovic emphasized the importance of the polarization extension as a mechanism of larger piezoelectric constants in a recent
paper [28]. Contrary to e33, on the other hand, the changes in e31 are much smaller than the changes in e33, but note that e31 shows
negative in SrTiO3 while positive in BaTiO3.

(a) （b）
16.0 1.0
BaTiO 3
12.0

(C/m2 )
0.5
2)
(C/m^2)

SrTiO 3

e 31(C/m^2)
e 33 (C/m

8.0 0.0
BaTiO 3
e33

e31
4.0 -0.5
SrTiO 3
0.0 -1.0
0.00 0.20 0.40 0.60 0.80 1.00 0.00 0.20 0.40 0.60 0.80 1.00

cc--c_cub
c cub (Å)
(Å)
c-c - c cub
c_cub (Å)(Å)

Figure 10. Evaluated piezoelectric constants as a function of c – ccub in optimized tetragonal SrTiO3 and BaTiO3: (a) e33 and (b) e31 [12].

As expressed in 10.
Eq. Evaluated
(3), e3j is piezoelectric
the sum of constants
the contributions from
as a function of the
c – cclamped term and the relaxed term. However, it has been
Figure cub in optimized tetragonal SrTiO3 and BaTiO3: (a) e33
generally known
and (b) ethat the contribution to e3j from the clamped term is much smaller than that from the relaxed term; in fact, the
31 [12].
absolute values of the e33 clamped terms are less than 1 C/m2 in both SrTiO3 and BaTiO3. We therefore investigate the contributions
As expressed
to the relaxed term of e33 and in Eq. (3),detail.
e31 in e3j isAstheexpressed
sum of in theEq.contributions
(3), the relaxedfrom termsthe
of eclamped term and the
3j are proportional to the sum of the

products between the Z33* (k) and ∂u3 (k)/∂ηj (j = 3 or 1) values. Let us show the evaluated results of Z33* (k), ∂u3(k)/∂η3, and ∂u3(k)/∂η1
relaxed term. However, it has been* generally known that the contribution to e3j from the *
in the following. Figures 11(a) and 11(b) show the Z33 (k) values in SrTiO3 and BaTiO3, respectively. Properties of the Z33 (k) values
clamped
are quantitatively terminisboth
similar much SrTiOsmaller than that from the relaxed term; in fact, the absolute values of
3 and BaTiO3. Therefore, the difference in the properties of e33 and e31 between SrTiO3 and
the
BaTiO3 must be 33 e clamped terms are less
due to the difference in the properties than 1 of
C/m 2
in both
∂u3(k)/∂η SrTiO
j. Figures 3 and
12(a) andBaTiO 3. We
12(b) show thetherefore investi‐
∂u3(k)/∂η3 values in SrTiO3 and
gate the contributions
BaTiO3, respectively. In these figures, toOthe
x andrelaxed term
Oz denote of e33 atoms
oxygen and ealong
31 in detail.
the As
[100] expressed
and [001] in
axes, Eq. (3), theClearly, the
respectively.
relaxed
absolute values terms
of ∂u of e3j are proportional to the sum of the products between the Z33* (k) and
3(k)/∂η3 are different in between SrTiO3 and BaTiO3. On the other hand, Figs. 13(a)
∂u3 show the
and 13(b)
∂u3(k)/∂η1 values in SrTiO3 and BaTiO3, respectively. The absolute values of ∂u3(k)/∂η1, especially for Ti, Ox, and Oz are different in
(k)/∂ηj (j = 3 or 1) values. Let us show the evaluated results of Z33* (k), ∂u3(k)/∂η3, and ∂u3(k)/
between SrTiO3 and BaTiO3. As a result, the quantitative differences in e33 and e31 between SrTiO3 and BaTiO3 are due to the
differences∂η in contribution
in1the the following. of theFigures
∂u3(k)/∂η11(a) and 11(b) show the Z33* (k) values in SrTiO3 and BaTiO3,
3 and ∂u3(k)/∂η1 values, respectively.
respectively. Properties of the Z33* (k) values are quantitatively similar in both SrTiO3 and Ba‐
TiO3. Therefore, the difference in the properties of e33 and e31 between SrTiO3 and BaTiO3
must be due to the difference in the properties of ∂u3(k)/∂ηj. Figures 12(a) and 12(b) show the
∂u3(k)/∂η3 values in SrTiO3 and BaTiO3, respectively. In these figures, Ox and Oz denote oxy‐
gen atoms along the [100] and [001] axes, respectively. Clearly, the absolute values of ∂u3(k)/
∂η3 are different in between SrTiO3 and BaTiO3. On the other hand, Figs. 13(a) and 13(b)
show the ∂u3(k)/∂η1 values in SrTiO3 and BaTiO3, respectively. The absolute values of ∂u3(k)/
∂η1, especially for Ti, Ox, and Oz are different in between SrTiO3 and BaTiO3. As a result, the
quantitative differences in e33 and e31 between SrTiO3 and BaTiO3 are due to the differences
in the contribution of the ∂u3(k)/∂η3 and ∂u3(k)/∂η1 values, respectively.
 14 Advances in Ferroelectrics

(a) STO （b） BTO

8.0 8.0
(a) 6.0 STO （b） 6.0 BTO
Ti
4.0
Ti 4.0
8.0
8.0 Sr Ba

Z*33
（b） 2.0

*
(a) 6.0 Ti
33 Z*33

2.0 BTO
* Z 33 *

33
6.0 STO
Ti 0.0

* Z
0.0
4.0 4.0 OBa
8.0 x
8.0 OSr -2.0

Z*33
-2.0 x 2.0
Z*33

2.0 6.0 Ti

33
6.0
-4.0 -4.0
0.0 O
OOzTi
z

Z
0.0 4.0 O
Z

4.0
-6.0 -6.0
-2.0 Bax
-2.0 Srx

Z*33
2.00.00 0.20 0.40 0.60 0.80 1.00

*
Z*33

2.00.00 0.20 0.40 0.60 0.80 1.00

*

33
-4.0 Oz
33

-4.0 0.0

Z
0.0 Oz -6.0 Ox
Z

-6.0
-2.0 O
cc-x -c_cub
c 0.60(Å)0.80 1.00
(A)
-2.0 c - c_cub (A)
-4.0 0.00 0.20 0.40 cub -4.0 0.00 0.20 c 0.40
- c cub0.60
(Å) 0.80
Oz
1.00

-6.0
Oz -6.0
cc- -c_cub
c 0.60(A)
(Å) c - c_cub (A)
0.00 0.20 * 0.40 cub 0.80 1.00 c - c cub
0.00 0.20 0.40 0.60(Å)
0.80 1.00
Figure 11. Evaluated Born effective charges Z33 (k) as a function of c – ccub: (a) SrTiO3 and (b) BaTiO3. Ox and Oz denote oxygen atoms along the [100]
axis and the Figure Evaluated Born
11.respectively
[001] axis, [12]. effective charges Z33* (k) as a function of c – ccub: (a) SrTiO and (b)
c -3 c_cub (A)BaTiO 3. Ox and Oz denote
cc- -c_cub
c cub (Å)
(A) c - c cub (Å)
oxygen atoms along the [100] axis and the [001] axis, respectively [12].
Figure 11. Evaluated Born effective charges Z33* (k) as a function of c – ccub: (a) SrTiO3 and (b) BaTiO3. Ox and Oz denote oxygen atoms along the [100]
axis and the [001] axis, respectively [12].
STO
Figure 11. Evaluated Born(a)effective charges Z33* (k) as a function of c – ccub: (a) （b）
SrTiO3 and (b) BaTiO3BTO
. Ox and Oz denote oxygen atoms along the [100]
axis and the [001] axis, respectively1.0[12]. 1.0
(a) 0.8 Ti STO
（b） BTO
0.8
0.6
∂u3/∂η3

0.6
3

∂u 3 /∂η3
1.0 Sr STO Ti
3 ∂u3/∂η3
3 /∂η

0.4 Ti 1.0
0.4 Ba
(a) 0.8
0.2 （b） 0.8 BTO
0.6 0.2
∂u3/∂η3

0.6
3

1.0
0.0 Sr Ti
∂u3/∂η3
3 /∂η

∂u 3 /∂η

0.0
1.0 OBa
0.4 Ti O x 0.4 x
∂u

0.8
-0.2 -0.2
0.8
0.2 0.2
0.6
-0.4
∂u3/∂η3

OSr -0.4
0.6 O
3

0.0 Ti
∂u3/∂η3

z z
3 /∂η

3 /∂η

0.4
-0.6 Ox 0.0
-0.6
0.4 BaOx
∂u

-0.2 -0.2
0.20.00 0.20 0.40 0.60 0.80 1.00 0.20.00 0.20 0.40 0.60 0.80 1.00
-0.4 O -0.4 O
0.0
-0.6 ccx-z-c_cub
O c cub (A)
(Å) 0.0
-0.6 c c- - c cub(A)
c_cub (Å) O xz
∂u

∂u

-0.2 -0.2
-0.4 0.00 0.20 0.40 0.60 0.80 1.00
Oz -0.4 0.00 0.20 0.40 0.60 0.80
Oz 1.00
-0.6 cc--c_cub
c cub (A)
(Å) -0.6 c c- - c cub(A)
c_cub (Å)
Figure 12. Evaluated values of ∂u3(k)/∂η 3 as a0.20
0.00 function
0.40 of 0.60
c – ccub0.80
: (a) SrTiO
1.00 3 and (b) BaTiO30.00
[12]. 0.20 0.40 0.60 0.80 1.00
cc--c_cub
c cub (A)
(Å)
c c- - c cub(A)
c_cub (Å)
Figure 12. Evaluated values of ∂u3(k)/∂η3 as a function of c – ccub: (a) SrTiO3 and (b) BaTiO3 [12].
Figure 12. Evaluated
(a) values of ∂u3(k)/∂η
STO 3 as a function of c – ccub:（b）
(a) SrTiO3 and (b) BaTiO
BTO 3 [12].

Figure 12. Evaluated values of ∂u3(k)/∂η

0.1 3 as a function of c – ccub: (a) SrTiO3 and (b) BaTiO
0.1 3 [12].
(a) Sr STO （b） Ti BTO Ba
0.0 0.0
Oz
1 ∂u3/∂η1
∂u 3 /∂η1

3 /∂η1

Oz
∂u3/∂η1

(a) 0.1
-0.1 （b）-0.10.1
TiSr Ti
STO BTO
0.0
-0.2 0.0
-0.2
Ba
Oz
∂u3/∂η1 1

0.1 0.1 Oz
∂u3/∂η1
3 /∂η

3 /∂η

-0.3
-0.1 Sr -0.1
-0.3 Ti
∂u

0.0 OTix 0.0

Ba
Ox
-0.4
-0.2 Oz -0.4
-0.2
∂u3/∂η1

Oz
∂u3/∂η1
3 /∂η

3 /∂η

-0.1
-0.5
-0.3 -0.1
Ti -0.5
-0.3
∂u

∂u

-0.2
0.00 O
0.20 x0.40 0.60 0.80 1.00 -0.2
0.00 0.20 0.40 0.60
Ox
0.80 1.00
-0.4 -0.4
-0.3 -0.3
∂u

∂u

-0.5 O -0.5 c - c_cub (A)

-0.4 0.00 ccx--0.40
0.20
cc_cub
cub (Å)
(A)
0.60 0.80 1.00 -0.4 0.00 0.20 c - c cub (Å) O x
0.40 0.60 0.80 1.00
-0.5 -0.5
c - c_cub (A)
0.20cc-0.40
- cc_cub(Å)
(A) 0.80 1.00
cub 0.60 0.00 c - c cub
0.00 0.20 0.40 0.60(Å)
0.80 1.00
Figure 13. Evaluated values of ∂u3(k)/∂η1 as a function of c – ccub: (a) SrTiO3 and (b) BaTiO3 [12].
c - c_cub (A)
cc-- cc_cub
cub (Å)
(A) c - c cub (Å)
Let us 13.
Figure discuss
Evaluated the values
reasons of3(k)/∂η
of ∂u the quantitative
1 as a function differences
of c – ccub: (a) in SrTiOe33 3between
and (b) BaTiO SrTiO 3 and BaTiO3. Figure 14(a) shows the difference
3 [12].

between the Ti-Oz distance (RTi-Oz) and the sum of the rTi and rOz (rTi + rOz) along the [001] axis as a function of c – ccub. Note that RTi-Oz
Figure
is
Letsmaller Figure
us13.discuss
Evaluated
than rTi 13.
the Evaluated
+values in of
rreasons
Oz ∂uof
both values
3(k)/∂η
SrTiO 3of
as a∂u
and
the1 quantitative (k)/∂ηof
function
3BaTiO .as –a cfunction
cHowever,
13differences of ecdifference
cub: (a) SrTiO
the
in 3–and
33 cub: (a) SrTiO
cbetween
(b) BaTiO 3 and
3 [12].
inSrTiO
absolute3 (b)
and BaTiO
value
BaTiO [12].
3between
3. Figure RTi-Oz andshows
14(a) rTi + rOzthein SrTiO 3 is
difference
smaller than the difference in BaTiO for 0 ≲ c – c
between the Ti-Oz distance (RTi-Oz) and the sum of the rTi and rOz (rTi + rOz) along the
3 cub ≲ 0.20. This result suggests that the axis
[001] Ti-Oas z Coulomb
a functionrepulsion
of c – ccubalong
. Notethe that[001]
RTi-Oz
Let
axis us
in SrTiO
is smaller Let
discuss3 isus
than rthe discuss
smaller
Ti +
reasons
rOz inthan the
ofthat
both thereasons
SrTiO 3 and 3of
inquantitative
BaTiO and
BaTiOthethat
3.quantitative
differences
therefore
However, inthe
the differences
e33difference
between
Ti SrTiO
ion of SrTiO in3 3can
eand
in absolute 33 between
BaTiO
bevalue
displaced SrTiO
between more and
easily
R3Ti-Oz andBaTiO
3. Figure 14(a) shows the difference
along r3Oz. in
rTi + the [001] axis
SrTiO 3 is
between the Ti-O z distance (RTi-Oz) and the sum of the rTi and rOz (rTi + rOz) along the [001] axis as a function of c – ccub. Note that RTi-Oz
than that
smaller than
is smaller
ofFigure
than
BaTiO 14(a)
. This
the difference
3
rTismaller
+ rshows
shows
wouldin BaTiObe the
a difference
reason
3 for why
0 ≲ c – ccubthe between
absolute
≲ 0.20. This the
values Ti-O
of
result ∂u
z distance
(k)/∂η
suggests
3 3 of (R
Ti
that and O)
the Ti-O
Oz in both SrTiO3 and BaTiO3. However, the difference in absolute value between RTi-Oz and rTi + rOz in SrTiO3 is
Ti-Oz
z
and
ions the sum
in SrTiO
z Coulomb of the
3 are larger
repulsion r thanthe
along
Ti
that[001]
in
BaTiO
axis in3.SrTiO
Figure 14(b)
3 is thethat
than difference
in BaTiO between
3 and that thetherefore
A-Ox distance the Ti(R ion ) and
A-Oxof SrTiO the3 can
sumbe ofdisplaced
rA and rOxmore (rA + reasily
Ox) on along
the (100)the plane as
[001] axis
smaller
athan
function than
that of the
of BaTiO difference
c – ccub3,. where
This would in BaTiO
the values 3 for 0 ≲ c – ccub ≲ 0.20. This result suggests that the Ti-Oz Coulomb repulsion along the [001]
of the ionic
be a reason why radii are defined
the absolute values as Shannon's
of ∂u3(k)/∂ηones 3 of Ti[23].
andNoteOz ionsthat inRA-Ox is smaller
SrTiO thanthan
3 are larger rA + rthat
Ox inin
axis
both
BaTiOin SrTiO
SrTiO
3. Figure
3 is smaller
3 and BaTiO
14(b) 3.than
shows However,
thethat intheBaTiO
difference 3 and that
difference
between inthe therefore
absolute the Tibetween
value
A-Ox distance ion of )SrTiO
(RA-Ox 3 can
RA-Oxthe
and andsumbe
rA displaced
+ rrOx
of rmore
in SrTiO
A and
easily
Ox (r3A is
+ rmuch along
the the
Ox) onsmaller (100) [001]
than axis
theas
plane
than that of
difference BaTiO3.3 This 0would cbe
cuba≲ reason why result
the absolute values thatasof ∂uSr-O
3(k)/∂η 3 of Ti and Oz ions in SrTiO 3 are plane
largerin than that in
a functionin of BaTiO
c – ccub, for where ≲thec –values 0.20.
of theThis
ionic radii suggests are defined the
Shannon's x Coulomb
ones [23]. repulsion
Note that onR the
A-Ox (100)
is smaller thanSrTiOrA + r3Oxisin
BaTiOsmaller
much 3. Figure 14(b)
than the shows
Ba-O the difference
Coulomb between
repulsion in the
BaTiO A-O x distance
and that (RA-Ox) and
therefore Sr the sum
and O of rof
ions A andSrTiO rOx3 (rA +be
can rOxdisplaced
) on the (100) more plane
easilyas
both SrTiO3 and BaTiO3. However, the difference in absolute value between RA-Ox and rA + rOx in SrTiO3 is much smaller than the
x 3 x
a function
along of c –axis
the [001] ccub, where the values of the ionic3. radii are defined as Shannon's ones [23]. Note that
of R∂uA-Ox is smaller thanOrxA ions
+ rOx in
difference in BaTiOthan 3 for Ba 0≲ and c –Ocxcub ions≲ of BaTiO
0.20. This would
This result suggests be athat reasonthe why
Sr-Othe absolute
x Coulomb values
repulsion on 3(k)/∂η
the (100)3 of Sr and
plane in SrTiOin 3 is
both SrTiO
SrTiO are 3 and than
larger BaTiO 3. However,
those of Ba and theO difference
ions in BaTiOin absolute
. value between RA-Ox and rA + rOx in SrTiO3 is much smaller than the
much smaller than the Ba-Ox Coulomb repulsion in BaTiO3 and that therefore Sr and Ox ions of SrTiO3 can be displaced more easily
3 x 3
difference in BaTiO3 for 0 ≲ c – ccub ≲ 0.20. This result suggests that the Sr-Ox Coulomb repulsion on the (100) plane in SrTiO3 is
along the [001] axis than Ba and Ox ions of BaTiO3. This would be a reason why the absolute values of ∂u3(k)/∂η3 of Sr and Ox ions in
much smaller than the Ba-Ox Coulomb repulsion in BaTiO3 and that therefore Sr and Ox ions of SrTiO3 can be displaced more easily
 Electronic Structures of Tetragonal ABX3: Role of the B-X Coulomb Repulsions for Ferroelectricity and Piezoelectricity 15
http://dx.doi.org/10.5772/52187

and rOz (rTi + rOz) along the [001] axis as a function of c – ccub. Note that RTi-Oz is smaller than rTi
+ rOz in both SrTiO3 and BaTiO3. However, the difference in absolute value between RTi-Oz
and rTi + rOz in SrTiO3 is smaller than the difference in BaTiO3 for 0 ≲ c – ccub ≲ 0.20. This
result suggests that the Ti-Oz Coulomb repulsion along the [001] axis in SrTiO3 is smaller
than that in BaTiO3 and that therefore the Ti ion of SrTiO3 can be displaced more easily
along the [001] axis than that of BaTiO3. This would be a reason why the absolute values of
∂u3(k)/∂η3 of Ti and Oz ions in SrTiO3 are larger than that in BaTiO3. Figure 14(b) shows the
difference between the A-Ox distance (RA-Ox) and the sum of rA and rOx (rA + rOx) on the (100)
plane as a function of c – ccub, where the values of the ionic radii are defined as Shannon's
ones [23]. Note that RA-Ox is smaller than rA + rOx in both SrTiO3 and BaTiO3. However, the
difference in absolute value between RA-Ox and rA + rOx in SrTiO3 is much smaller than the
difference in BaTiO3 for 0 ≲ c – ccub ≲ 0.20. This result suggests that the Sr-Ox Coulomb re‐
pulsion on the (100) plane in SrTiO3 is much smaller than the Ba-Ox Coulomb repulsion in
BaTiO3 and that therefore Sr and Ox ions of SrTiO3 can be displaced more easily along the
[001] axis than Ba and Ox ions of BaTiO3. This would be a reason why the absolute values of
∂u3(k)/∂η3 of Sr and Ox ions in SrTiO3 are larger than those of Ba and Ox ions in BaTiO3.

(a) （b）
(Å)
(Å)

0.0 -0.1
O ) (A)
O ) (A)

SrTiO 3
B ++rr_O)

-0.2
A ++rr_O)

-0.1
SrTiO 3 -0.3
B -Oz - -(r(r_B

A -Ox - -(r(r_A

-0.2 BaTiO 3
-0.4
RR_A-O1
RR_B-O3

-0.3
BaTiO 3 -0.5
0.00 0.20 0.40 0.60 0.80 1.00 0.00 0.20 0.40 0.60 0.80 1.00

cc- -c_cub
c cub(Å)
(Å) c -c c_cub
- c cub(Å)
(Å)

Figure 14. Evaluated values as a function of c – ccub in optimized tetragonal SrTiO3 and BaTiO3: (a) difference between the Ti-Oz distance (RTi-Oz) and
Figure 14.
rTi + rOz. (b) difference Evaluated
between values
the A-O as a function of c – ccub+inrOxoptimized
x distance (RA-Ox) and rA . RA-Ox andtetragonal SrTiO33 are
RTi-Oz in ATiO andalso
BaTiO 3: (a) difference
illustrated. between
Note that all the ionic radii are
much larger and the Ti-O
that distance
A zand Ti ions(Rare
Ti-Oz)displaced
and rTi + along
rOz. (b)the
difference
[001] axisbetween
in actualthe A-O
ATiO distance (RA-Ox) and rA + rOx. RA-Ox and RTi-Oz in
3 x[12].
ATiO3 are also illustrated. Note that all the ionic radii are much larger and that A and Ti ions are displaced along the
[001] axis in actual ATiO3 [12].
Finally, in this subsection, we discuss the relationship between ∂u3(k)/∂η3 and c – ccub in detail. Figure 15(a) shows the differences in
the total energy (ΔEtotalin) as
Finally, a function
this of u3we
subsection, (Ti).discuss
In this figure, the properties
the relationship of SrTiO
between ∂u3 3with
(k)/∂ηη33 =and
0.011,
c –SrTiO 3 with η3 = 0.053 and
ccub in de‐
fully optimized BaTiO3 as a reference, are shown. Calculations of Etotal were performed with the fixed crystal structures of
tail. Figure 15(a) shows the differences in the total energy (ΔEtotal ) as a function of u3(Ti). In
previously optimized structures except Ti ions. Clearly, the magnitude of u3(Ti) at the minimum points of the ΔEtotal and the depth
of the potential are closely related to the spontaneous polarization P3 and the Curie temperature (TC), respectively. On the other
hand, e33 seems to be closely related to the deviation at the minimum points of the ΔEtotal. Figure 15(b) shows illustrations of ΔEtotal
curves with deviations at the minimum points of the ΔEtotal values, corresponding to the ΔEtotal curves of SrTiO3 in Fig. 15(a).
Clearly, as η3 becomes smaller, the deviated value at the minimum point of the ΔEtotal values becomes smaller, i.e., the Ti ion can be
displaced more favourably. On the other hand, as shown in Fig. 12(a), the absolute value of ∂u3(Ti)/∂η3 becomes larger as η3
becomes smaller.
 16 Advances in Ferroelectrics

this figure, the properties of SrTiO3 with η3 = 0.011, SrTiO3 with η3 = 0.053 and fully opti‐
mized BaTiO
Figure 14. Evaluated values as as
3 a reference,
a function of c – ccubare shown.tetragonal
in optimized Calculations of EBaTiO
SrTiO3 and
total were performed with the fixed
3: (a) difference between the Ti-Oz distance (RTi-Oz) and

rTi + rOz. (b) difference between the A-Ox distance (RA-Ox) and rA + rOx. RA-Ox and RTi-Oz in ATiO3 are also illustrated. Note that all the ionic radii are
crystal structures of previously optimized structures except Ti ions. Clearly, the magnitude
much larger and that A and Ti ions are displaced along the [001] axis in actual ATiO3 [12].
of u3(Ti) at the minimum points of the ΔEtotal and the depth of the potential are closely relat‐
Finally, in ed
thisto the spontaneous
subsection, we discusspolarization
the relationship P3between
and the∂uCurie
3(k)/∂η3 temperature (TC), Figure
and c – ccub in detail. respectively. On the
15(a) shows thedifferences in
other (ΔE
the total energy hand,
total ) eas aseems
33 to
function be
of u closely
3(Ti). In related
this figure,to the
the deviation
properties of at
SrTiO the minimum
3 with η 3 = 0.011,points
SrTiO 3 of
withtheη3 = 0.053 and
ΔEtotal.BaTiO
fully optimized Figure 15(b) shows illustrations of ΔEtotal curves with deviations at the minimum
3 as a reference, are shown. Calculations of Etotal were performed with the fixed crystal structures of

previously optimized structures except Ti ions. Clearly, the magnitude of u3(Ti) at the minimum points of the ΔEtotal and the depth
points of the ΔEtotal values, corresponding to the ΔEtotal curves of SrTiO3 in Fig. 15(a). Clearly,
of the potential are closely related to the spontaneous polarization P3 and the Curie temperature (TC), respectively. On the other
as η becomes smaller, the deviated value at the minimum point of the ΔE 15(b)
hand, e33 seems3 to be closely related to the deviation at the minimum points of the ΔEtotal. Figuretotal
values becomes
shows illustrations of ΔEtotal
curves with deviations at the minimum points of the ΔEtotal values, corresponding to the ΔEtotal curves of SrTiOin
smaller, i.e., the Ti ion can be displaced more favourably. On the other hand, as shown 3 in Fig. 15(a).

Clearly, asFig. 12(a), the

η3 becomes absolute
smaller, value of
the deviated ∂u3at
value (Ti)/∂η 3 becomes
the minimum larger
point of theasΔE
ηtotal
3 becomes smaller.
values becomes smaller, i.e., the Ti ion can be
displaced more favourably. On the other hand, as shown in Fig. 12(a), the absolute value of ∂u3(Ti)/∂η3 becomes larger as η3
Therefore, the Ti ion can be displaced more favourably as the deviated value at the mini‐
becomes smaller.
mum point of the ΔEtotal values becomes smaller. The relationship between e33 and ∂u3(Ti)/∂η3
Therefore,isthe
discussed
Ti ion canin
beSec. 3.2.3. more favourably as the deviated value at the minimum point of the ΔEtotal values becomes
displaced
smaller. The relationship between e33 and ∂u3(Ti)/∂η3 is discussed in Sec. 3.2.3.

(a) (b)
⊿E
⊿Etotal v.s.
total v.s.
⊿u ⊿u
3 (Ti)
Ti ⊿E total v.s. ⊿u3 (Ti)
0.006
SrTiO3 (η3 = 0.011)
⊿E total (arb. unit)

0.004
BaTiO3
(eV)
total (eV)

⊿Etot (eV)

0.002
0
⊿Etot

0.000
⊿E

-0.002
-0.004 SrTiO3
(η 3 = 0.053) -0.006
-0.006
0.0 0.1 0.2 0.3 0
0.0
⊿uu_Ti (A) ⊿u 3u_Ti
(Ti ) (A)
(arb. unit)
3 (Ti ) (Å)

Figure 15. (a) ΔEtotal as a function of u3(Ti) in tetragonal SrTiO3 and BaTiO3. (b) Illustration of the ΔEtotal curves in tetragonal SrTiO3 with η3 = 0.011
Figure 15. a) ΔEtotal as a function of u3(Ti) in tetragonal SrTiO3 and BaTiO3. (b) Illustration of the ΔEtotal curves in tetrago‐
and SrTiO3 with η3 = 0.053 with deviations at the minimum point of ΔEtotal [14].
nal SrTiO3 with η3 = 0.011 and SrTiO3 with η3 = 0.053 with deviations at the minimum point of ΔEtotal [14].

3.2.2. Proposal of new piezoelectric materials

3.2.2. Proposal of new piezoelectric materials
The previous discussion in Sec. 3.2.1 suggests that the piezoelectric properties of e33 are closely related to the B-X Coulomb
The previous discussion in Sec. 3.2.1 suggests that the piezoelectric properties of e33 are
repulsions in tegtragonal ABX3. In the viewpoint of the change of the B-X Coulomb repulsions, we recently proposed new
closely related
piezoelectric materials to i.e.,
[16, 17], the BaTi
B-X1-xCoulomb repulsions
NixO3 and Ba(Ti in tegtragonal ABX3. In the viewpoint of the
1-3zNb3z)(O1-zNz)3.

change of the B-X Coulomb repulsions, we recently proposed new piezoelectric materials
It has been[16, 17],that
known i.e., BaNiO
BaTi1-x3 Ni xO3 and Ba(Ti1-3zNb3z)(O1-zNz)3.
shows the 2H hexagonal structure as the most stable structure in room temperature. Moreover, the
ionic radius of Ni4+ (d6) with the low-spin state in 2H BaNiO3 is 0.48 Å, which is much smaller than that of Ti4+ (d0), 0.605 Å, in
It has been known that BaNiO3 shows the 2H hexagonal structure as the most stable struc‐
ture in room temperature. Moreover, the ionic radius of Ni4+ (d6) with the low-spin state in
2H BaNiO3 is 0.48 Å, which is much smaller than that of Ti4+ (d0), 0.605 Å, in BaTiO3. There‐
fore, due to the drastic change in the (Ti1-xNix)-O Coulomb repulsions in tetragonal BaTi1-
xNixO3, the e33 piezoelectric values are expected to be larger than that in tetragonal BaTiO3,
especially around the morphotropic phase boundary (MPB). Figure 16(a) shows the total-en‐
 Electronic Structures of Tetragonal ABX3: Role of the B-X Coulomb Repulsions for Ferroelectricity and Piezoelectricity 17
http://dx.doi.org/10.5772/52187

ergy difference ΔEtotal between 2H and tetragonal structures of BaTi1-xNixO3 as a function of

x. The most stable structure changes at x ≈ 0.26. Figure 16(b) shows c – ccub as a function of x.
The c – ccub value shows 0 around x = 0.26, which suggests the appearance of the MPB, i.e.,
the e33 piezoelectric value shows a maximum at x ≈ 0.26.

(a) ～ b～

Figure 16. a) ΔEtotal (total-energy difference between 2H and tetragonal structures), and (b) c – ccub of the tetragonal
structure, as a function of x in BaTi1-xNixO3 [16]. For or 0.26 ≤ x ≦ 1, the tetragonal structure is not the most stable one.

Figure 17. (a) ΔEtotal (total-energy difference between cubic and tetragonal structures), and (b) c – ccub, as a function of
x in Ba(Ti1-3zNb3z)(O1-zNz)3 [17].

Another proposal is tetragonal Ba(Ti1-3zNb3z)(O1-zNz)3, which consists of BaTiO3 and BaN‐

bO2N [17]. Due to the change of (Ti1-3zNb3z)-(O1-zNz) Coulomb repulsions, the e33 piezoelectric
values are expected to be larger than that in tetragonal BaTiO3. Recent experimental paper
reported that the most stable structure of BaNbO2N is cubic in room temperature [34]. Con‐
trary to the experimental result, however, our calculations suggest that the tetragonal struc‐
ture will be more stable than the cubic one, as shown in Fig. 17(a). Figure 17(b) shows c – ccub
 18 Advances in Ferroelectrics

as a function of x. The c – ccub value shows almost 0 at x ≈ 0.12. Although the MPB does not
appear in tetragonal Ba(Ti1-3zNb3z)(O1-zNz)3, the e33 piezoelectric values are expected to show a
maximum at x ≈ 0.12.

3.2.3. Piezoelectric properties of in tetragonal ABX3

In the following, we discuss the role of the B-X Coulomb repulsions in piezoelectric ABX3.

Figures 18(a) and 18(b) show the piezoelectric properties of e33 as a function of the value c –
ccub in tetragonal ABX3, where ccub denotes the c lattice parameter in cubic ABX3; c – ccub is a
closely related parameter to η3. For ABX3, SrTiO3, BaTiO3 and PbTiO3 with the c lattice pa‐
rameter and all the inner coordination optimized for fixed a, and BaTi1-xNixO3 (0 ≦ x ≦ 0.05),
Ba(Ti1-3zNb3z)(O1-zNz)3 (0 ≦ z ≦ 0.125), Ba1-ySryTiO3 (0 ≦ y ≦ 0.5), BaTi1-xZrxO3 (0 ≦ x ≦ 0.06),
and BiM’O3 (M’ = Al, Sc) with fully optimized, were prepared [15]. Note that e33 becomes
larger as c – ccub becomes smaller and that the trend of e33 is almost independent of the kind
of A ions. Moreover, note also that e33 of BaTi1-xNixO3 and that of Ba(Ti1-3zNb3z)(O1-zNz)3 show
much larger values than the other ABX3.

(a) (b)
60 20
x = 0.05 BaTi1-xNixO 3
50
15
x = 0.04
(C/m 2 )

2 )2)
e 33 (C/m^2)

(C/m^2)

40
(C/m

BaTi1-xNixO 3 Ba(Ti1-3zNb3z)(O1-zNz)3 Bi M O3
e 33(C/m

30 10
SrTiO3
e33

e e33

Ba(Ti1-3zNb3z)(O1-zNz)3 PbTiO3
33

20 Ba 1-ySryTiO3
x = 0.04 5
10 BaTi1-xZrxO3
x=0 BaTiO3
0 x=0 0
0.00 0.20 0.40 0.60 0.80 1.00 0.00 0.05 0.10 0.15 0.20

cc -- c_cub
c cub (Å)
(Å) c -- c_cub
c cub (Å)
(Å)

Figure 18. e33 as a function of c – ccub for different scales [15].

Figure 18. e33 as a function of c – ccub for different scales [15].
Let us discuss the relationship between ∂u3(k)/∂η3 and c – ccub in BaTi1-xNixO3 and BaTiO3 in
Let us discuss thethefollowing.
relationshipFigures
between 19(a) and 319(b)
∂u3(k)/∂η and cshow theBaTi
– ccub in ∂u31-x(k)/∂η values.
NixO33 and BaTiOIn3 these
in the figures,
following. OxFigures
and O19(a)
z
and 19(b)
denote oxygen atoms along the [100] and [001] axes, respectively. Clearly, the absolute val‐
show the ∂u3(k)/∂η 3 values. In these figures, Ox and Oz denote oxygen atoms along the [100] and [001] axes, respectively. Clearly, the

absolute values of ∂u3(k)/∂η3 in BaTi1-xNixO3 are much larger than those in BaTiO3. Moreover, in comparison with Fig.18, properties
ues of ∂u3(k)/∂η3 in BaTi1-xNixO3 are much larger than those in BaTiO3. Moreover, in compari‐
of e33 are closely related to those of ∂u3(k)/∂η3. Figure 20(a) shows the difference between RB-Oz and rB + rOz along the [001] axis, and
son with Fig.18, properties of e33 are closely related to those of ∂u3(k)/∂η3. Figure 20(a) shows
Fig. 20(b) shows the difference between RA-Ox and rA + rOx on the (100) plane for several ABO3, as a function of c – ccub. Clearly, the
the difference between RB-Oz and rB + rOz along the [001] axis, and Fig. 20(b) shows the differ‐
difference between RB-Oz and rB + rOz is closely related to e33 shown in Fig. 18, rather than the difference between RA-Ox and rA + rOx.
Moreover, note encethatbetween RA-Ox and
the difference rA + rOxvalue
in absolute on the (100)Rplane
between for several ABO , as a function of c – ccub.that in BaTiO3.
B-Oz and rB + rOz in BaTi1-x3NixO3 is much smaller than
Clearly,that
This result suggests thethe
difference between
(Ti1-xNix)-O R repulsion
z CoulombB-Oz
and rB along
+ rOz the is closely
[001] axisrelated
in BaTito1-xNi
e33xO
shown in Fig. 18,
3 is much smaller than the Ti-Oz
rather in
Coulomb repulsion than the3 and
BaTiO difference between
that therefore RxA-Ox
Ti1-xNi ionand rA 1-x+Ni
of BaTi rOx . 3Moreover,
xO note more
can be displaced that the difference
easily in axis than Ti
along the [001]
ion of BaTiO3absolute
. This mustvalue
be a between
reason why RB-Oz
the and rB + value
absolute rOz in of
BaTi
∂u31-x NixO
(k)/∂η 3 is
3 of Timuch smaller
1-xNix and Oz ions than that1-xin
in BaTi NixBaTiO 3.
O3 is larger than those
in BaTiO3. This result suggests that the (Ti1-xNix)-Oz Coulomb repulsion along the [001] axis in BaTi1-
x NixO3 is much smaller than the Ti-Oz Coulomb repulsion in BaTiO3 and that therefore Ti1-
xNi x ion of BaTi1-xNixO3 can be displaced more easily along the [001] axis than Ti ion of

(a) (b)
2.0 1.0
1.6 0.8
∂u 3 (k)/∂η3

x = 0.04
∂u 3 (k)/∂η3

1.2 0.6
0.8
Ti 1-xNi x Ba
0.4
0.4
x=0
0.2
0.0
Ba Ti
0.0
Ox Ox
-0.4 -0.2
-0.8 -0.4
 absolute values of ∂u3(k)/∂η3 in BaTi1-xNixO3 are much larger than those in BaTiO3. Moreover, in comparison with Fig.18, properties
of e33 are closely related to those of ∂u3(k)/∂η3. Figure 20(a) shows the difference between RB-Oz and rB + rOz along the [001] axis, and
Fig. 20(b) shows the difference between RA-Ox and rA + rOx on the (100) plane for several ABO3, as a function of c – ccub. Clearly, the
difference between
ElectronicRStructures
B-Oz and rBof+Tetragonal
rOz is closely
ABX3:related tothe
Role of e33 B-X
shown in Fig.
Coulomb 18, ratherforthan
Repulsions the difference
Ferroelectricity between RA-Ox and
and Piezoelectricity 19 rA + rOx.
Moreover, note that the difference in absolute value between RB-Oz and rB + rOz in BaTi1-x http://dx.doi.org/10.5772/52187
NixO3 is much smaller than that in BaTiO3.
This result suggests that the (Ti1-xNix)-Oz Coulomb repulsion along the [001] axis in BaTi1-xNixO3 is much smaller than the Ti-Oz
Coulomb repulsion in BaTiO3 and that therefore Ti1-xNix ion of BaTi1-xNixO3 can be displaced more easily along the [001] axis than Ti
BaTiO
ion of BaTiO 3. This
3. This must must be a why
be a reason reason
the why thevalue
absolute absolute
of ∂u3value ofTi∂u
(k)/∂η3 of (k)/∂η of Ti1-xin
1-x3Nix and3 Oz ions
NiBaTi
x and O ions in
1-xNixzO3 is larger than those

in BaTiO3. BaTi 1-x Ni O

x 3 is larger than those in BaTiO 3 .

(a) (b)
2.0 1.0
1.6 0.8
∂u 3 (k)/∂η3

x = 0.04

∂u 3 (k)/∂η3
1.2 0.6
0.8
Ti 1-xNi x Ba
0.4
0.4
x=0
0.2
0.0
Ba Ti
0.0
Ox Ox
-0.4 -0.2
-0.8 -0.4
Oz Oz
-1.2 -0.6
0.00 0.20 0.40 0.60 0.80 1.00 0.00 0.20 0.40 0.60 0.80 1.00

c - c cub (Å) c - c cub (Å)

Figure 19. ∂u3(k)/∂η3 as a function of c – ccub : (a) BaTi1-xNixO3 and (b) BaTiO3 [15].
Figure 19. ∂u3(k)/∂η3 as a function of c – ccub : (a) BaTi1-xNixO3 and (b) BaTiO3 [15].

(a) （b）
) (Å)

) (Å)

0.0 -0.1
BaTi1-xNixO3
(A)
(A)

x = 0.05 SrTiO3
+ r+Or_O)

+ r+Or_O)

-0.2
-0.1
BiAlO BaTiO3
x = 0.04 3
- (r-A(r_A
- (r-B(r_B

-0.3BaTi1-xNixO 3
SrTiO3 BiScO3
-0.2 x = 0 BiAlO3
R_A-O1
R_B-O3

-0.4
BaTiO3 PbTiO3
R A-Ox
R B-Oz

BiScO3
PbTiO3 -0.5
-0.3
0.00 0.20 0.40 0.60 0.80 1.00 0.00 0.20 0.40 0.60 0.80 1.00

c -c c_cub c - c_cub (Å)

- c cub (Å)
(Å) c - c cub (Å)

20. Evaluated
Figurevalues
Figure 20. Evaluated values of
of in optimized in optimized
tetragonal tetragonal
BaTi1-x BaTi31-x
NixO3, BaTiO NixOseveral
, and 3, BaTiO3, and several ABO3, as a function of c – ccub:
ABO3, as a function of c – ccub: (a) RB-Oz - (rB + rOz), and (b) RA-
(a) RB-Oz - (rB + rOz), and (b) RA-Ox – (rA + rOx) [15].
Ox – (rA + rOx) [15].

Figure
Figure 21(a) shows ΔE21(a)
total as shows ΔEof
a function the
total asdisplacement
a function of of the
theTidisplacement
1-xNix ions with of thecrystal
fixed Ti1-xNi x ions with
structures fixed
of fully-optimized BaTi1-
crystalofstructures
xNixO3. Calculations of fully-optimized
Etotal were performed with the fixedBaTi crystal
1-x Ni O . Calculations
structures
x 3 of of
previously E
optimized
total were performed
structures except Ti 1-xNi x ions.
The deviated with thethefixed
value at crystal
minimum structures
point of previously
of ΔEtotal, i.e., optimized
∂(ΔEtotal)/∂u3(Ti structures
1-xNix), becomes smallerexcept Ti1-xNilarger.
as x becomes x ions.Moreover, both
The
e33 and ∂u3(Ti1-x deviated
Nix)/∂η value at the minimum point of ΔEtotal, i.e., ∂(ΔEtotal)/∂u3(Ti1-xNix), becomes
3 become larger as x becomes larger, as shown in Figs. 18 and 19. This result is consistent with the result of

SrTiO3 shown in Fig. 15(a).

Let us discuss the above reasons in the following. ∂(⊿Etotal)/∂u3(Ti1-xNix) can be written as

1
  Etotal    Etotal   u3 (Ti1 x Ni x ) 
        . (5)
 u3 (Ti1 x Ni x )   3   3 
 20 Advances in Ferroelectrics

smaller as x becomes larger. Moreover, both e33 and ∂u3(Ti1-xNix)/∂η3 become larger as x
becomes
Figure 20. Evaluated larger,
values as shown
of in optimized in Figs.
tetragonal 18xOand
BaTi1-xNi 19.3, and
3, BaTiO This result
several ABOis consistent
3, as a function of with
c – ccub: the result
(a) RB-Oz - (rB +of
rOz), and (b) RA-
SrTiO shown in Fig. 15(a).
Ox – (rA + rOx) [15].
3

Figure 21(a) Let

showsus ΔE
discuss the
total as a aboveofreasons
function in the following.
the displacement ∂(⊿E
of the Ti1-xNi total)/∂u3(Ti1-xNix) can be written as
x ions with fixed crystal structures of fully-optimized BaTi1-
xNixO3. Calculations of Etotal were performed with the fixed crystal structures of previously optimized structures except Ti1-xNix ions.

The deviated value at the minimum point of ΔEtotal, i.e., ∂(ΔEtotal)/∂u3(Ti1-xNix), becomes smaller as x becomes larger. Moreover, both
-1 This result is consistent with the result of
e33 and ∂u3(Ti1-xNix)/∂η3 become largeræ as x becomesö larger,
¶ΔE æ ¶ΔEastotal ö æ ¶inu3Figs.
shown
(Ti1-18 and ö19.
x Ni x )
SrTiO3 shown in Fig. 15(a). ç total
÷ =ç ÷´ç ÷ . (5)
ç ¶u (Ti Ni ) ÷ ç ¶h3 ÷ ç ¶h3 ÷
è 3 1- x x ø è ø è ø
Let us discuss the above reasons in the following. ∂(⊿Etotal)/∂u3(Ti1-xNix) can be written as

As shown in Fig. 21(b), ∂(ΔEtotal)/ ∂η3 is almost constant, and therefore, 1 ∂(ΔEtotal)/∂u3(Ti1-xNix)
 ⊿ Etotal   ⊿ -1 Etotal   u3 (Ti1 x Ni x ) 
is almost proportional to (∂u 3(Ti1-xNix)/∂η
  3) , i.e.,   . (5)
 u (Ti Ni )   3   3 
 3 1 x x     

-1
æ almost
As shown in Fig. 21(b), ∂(ΔEtotal)/ ∂η3 is ¶ΔEtotal ö and
constant, æ ¶utherefore,
÷ .
(
∂(ΔEötotal)/∂u3(Ti1-xNix) is almost proportional to (∂u3(Ti1-
3 Ti1- x Ni x
(6)
)
Nix)/∂η3)-1, i.e.,
x çç ÷÷ µ ç ç ÷
è ¶u3 (Ti1- x Ni x ) ø è ¶h3 ø
1
 ⊿ Etotal   u3  Ti1 x Ni x  
     . (6)
On the other hand, according to Eq.
u3 (Ti Ni x )e33 becomes
1 x(3), 
 as ∂u (Ti Ni )/∂η becomes larg‐
 3 larger
 3 1-x x 3
er. This is a reason why e33 becomes larger as ∂(ΔEtotal)/∂u3(Ti1-xNix) becomes smaller. This re‐
On the othersult
hand,is consistent
according to with
Eq. the
(3), result of SrTiO
e33 becomes 3 discussed in Sec. 3.2.1.
larger as ∂u3(Ti1-xNix)/∂η3 becomes larger. This is a reason why e33 becomes
larger as ∂(ΔEtotal)/∂u3(Ti1-xNix) becomes smaller. This result is consistent with the result of SrTiO3 discussed in Sec. 3.2.1.

(a) (b)
BaTi1-xNixO3 ⊿E v.s. η3
3.0
x=0.05 0.0
x=0.04
Hr)

Hr)

-10.0
(×10 -3Hr)

2.0
BaTiO3
(×10-3Hr)

larger e33
x=0
E total(×10^-3

-20.0
total(×10^-3

1.0
-30.0
0.0
-40.0
BaTi1-xNixO3
⊿⊿Etot

⊿Etot

smaller e33
-1.0
⊿E

-50.0
∂(⊿E)/∂η3 ≒(const.)
-2.0 -60.0
0.0 0.1 0.2 0.3 -0.05 0.00 0.05 0.10 0.15 0.20

u TiNi (Å) η3
η
u_Ti 1-xNix (A) 3

Figure 21. (a) Figure

ΔEtotal as
21.a (a)
function
ΔEtotal of
as ua3(Ti1-xNix) in BaTi1-xNixO3. Results with x = 0.05, 0.04, and 0 are shown. Dashed lines denote guidelines of
function of u3(Ti1-xNix) in BaTi1-xNixO3. Results with x = 0.05, 0.04, and 0 are shown. Dashed
∂(ΔEtotal)/∂u3(Ti1-xNix) for each x. (b) ΔEtotal as a function of η3 for BaTi1-xNixO3 and BaTiO3 [15].
lines denote guidelines of ∂(ΔE )/∂u (Ti Ni ) for each x. (b) ΔE as a function of η for BaTi Ni O and BaTiO [15].
total 3 1-x x total 3 1-x x 3 3

Finally, we comment on the difference in the properties between e33 and d33 in tetragonal ABX3. Figures 22(a) and 22(b) show the
Finally, we comment on the difference in the properties between e33 and d33 in tetragonal
piezoelectric properties of d33 as a function of c – ccub. Note that the trend of d33 is closely dependent on the kind of A ions. This
ABX3. Figures 22(a) and 22(b) show the piezoelectric properties of d33 as a function of c – ccub.
Note that the trend of d33 is closely dependent on the kind of A ions. This result is in contrast
with the trend of e33 as shown in Fig. 18. As expressed in Eq. (4), d33 is closely related to the
elastic compliance s3jE as well as e3 . In fact, the absolute value of s3jE in BiBX3 or PbBX3 is gen‐
j

erally larger than that in ABX3 with alkaline-earth A ions. This result must be due to the
larger Coulomb repulsion of Bi-X or Pb-X derived from 6s electrons in Bi (Pb) ion.
result is in contrast
Electronicwith the trend
Structures of e33 as shown
of Tetragonal ABX3: in Fig.
Role 18. B-X
of the As Coulomb
expressed in Eq. (4),
Repulsions fordFerroelectricity
33 is closely related to the elastic compliance
and Piezoelectricity 21
s3jE as well as e3j. In fact, the absolute value of s3jE in BiBX3 or PbBX3 is generally larger than http://dx.doi.org/10.5772/52187
that in ABX3 with alkaline-earth A ions.
result is in contrast with the trend of e33 as shown in Fig. 18. As expressed in Eq. (4), d33 is closely related to the elastic compliance
This result must be due to the larger Coulomb repulsion of Bi-X or Pb-X derived from 6s electrons in Bi (Pb) ion.
s3jE as well as e3j. In fact, the absolute value of s3jE in BiBX3 or PbBX3 is generally larger than that in ABX3 with alkaline-earth A ions.
This result must be due to the larger Coulomb repulsion of Bi-X or Pb-X derived from 6s electrons in Bi (Pb) ion.
(a) （b）
(a) 320.0 （b） 160.0
BaTi1-xNixO 3
320.0
160.0 Ba(Ti
240.0
120.0 1-3z Nb3z )(O1-zNz )3
d33 (pC/N)

BaTi Ni O

d33 (pC/N)
(pC/N)

Ba 1-xSryxTiO3
PbTiO3

d33 (pC/N)
240.0
120.0 Ba(Ti1-y 3
1-3z Nb3z )(O1-zNz )3
d33 (pC/N)

160.0

d33 (pC/N)
80.0
(pC/N)

Ba 1-ySryTiO3 PbTiO3

d33 (pC/N)
PbTiO3 Bi M O3
d33

160.0
80.0 80.0 BaTiO3
PbTiO 40.0 Bi M O3
d33

BiAlO3 3 BiScO3
80.0 BaTi1-xZrxO3 BaTiO3
0.0 40.0
BiAlO3 BiScO3 0.0
0.00 0.20 0.40 0.60 0.80 1.00 BaTi1-xZrxO3
0.0 0.00 0.05 0.10 0.15 0.20
0.0
0.00 0.20 0.40 0.60 0.80 1.00
cc -- c_cub
c cub (Å) 0.00 0.05 0.10 0.15 0.20
(Å) cc--c_cub
c cub(Å)
(Å)
cc -- c_cub
c cub (Å)
(Å) cc--c_cub
c cub(Å)
(Å)

Figure 22. d33 Figure 22. d33ofasc a– function

as a function of c – ccub
ccub for different for different
scales [15]. scales [15].
Figure 22. d33 as a function of c – ccub for different scales [15].

Figure 23. (a) Illustration of the relationship between the B-X Coulomb repulsions and the ferroelectric and piezoelectric states in tetragonal ABX3.
(b) Figure 23. (a)ofIllustration
Illustration of the relationship
the relationship between e33between
and thethe B-X Coulomb
deviation. repulsions
P3 and andthe
TC denote thespontaneous
ferroelectric and piezoelectric
polarization and states in tetragonal
the Curie ABX3.
temperature,
respectively. Figureof23.
(b) Illustration the(a) Illustration between
relationship of the relationship
e33 and thebetween thePB-X
deviation. Coulomb
3 and repulsions
TC denote and the ferroelectric
the spontaneous and
polarization andpiezoelec‐
the Curie temperature,
tric states in tetragonal ABX3. (b) Illustration of the relationship between e33 and the deviation. P3 and TC denote the
respectively.
spontaneous polarization and the Curie temperature, respectively.
4. Conclusion
4. Conclusion
We have discussed a general role of the B-X Coulomb repulsions for ferroelectric and piezoelectric properties of tetragonal ABX3,
We on
based have
our4. Conclusion
discussed
recent a general
papers role of the
and patents. WeB-X Coulomb
have found thatrepulsions for ferroelectric
both ferroelectric and piezoelectric
state and piezoelectric state
properties of tetragonal
are closely ABX
related to the3,
based on our recent papers and patents. We have found that both ferroelectric state and piezoelectric state are closely
B-Xz Coulomb repulsions as well as the B-Xx ones, as illustrated in Fig. 23(a). Moreover, as illustrated in Fig. 23(b), we have also related to the
Coulomb
B-Xzthat eWe repulsions as to
well as the B-Xxatones, as illustrated inof
Fig. 23(a).
ΔEtotalMoreover, as illustrated in Fig. 23(b), we have also
found have
33 is closelydiscussed
related a general
the rolethe
deviation of minimum
the B-X Coulomb
point therepulsions
. for ferroelectric and piezo‐
found that e33 is closely related to the deviation at the minimum point of the ΔEtotal.
electric properties of tetragonal ABX , based on our recent papers and patents. We have
3

found
Acknowledgements that both ferroelectric state and piezoelectric state are closely related to the B-X Cou‐ z
Acknowledgements
lomb repulsions as well as the B-X ones, as illustrated in Fig. 23(a). Moreover, as illustrated
x

in Fig. 23(b),
We thank Professor we have
M. Azuma also Institute
in Tokyo found that e is closely
of Technology for related to the deviation
useful discussion. at theT.minimum
We also thank
33
Furuta, M. Kubota, H.
We thank Professor M. Azuma in Tokyo Institute of Technology for useful discussion. We also thank T. Furuta, M. Kubota, H.
Yabuta, andpoint of the ΔEfor. useful discussion and computational support. The present work was partly supported by the
T. Watanabe
Yabuta, and T. Watanabe for useful discussion and computational support. The present work was partly supported by the
total

Elements Science and Technology Project from the Ministry of Education, Culture, Sports, Science and Technology.
Elements Science and Technology Project from the Ministry of Education, Culture, Sports, Science and Technology.

5. 5.
References
References
[1] Cohen R E. Origin of ferroelectricity in perovskite oxides. Nature 1992; 451 (6382) : 136-8.
[1] Cohen R E. Origin of ferroelectricity in perovskite oxides. Nature 1992; 451 (6382) : 136-8.
[2] Wu Z, Cohen R E. Pressure-induced anomalous phase transitions and colossal enhancement of piezoelectricity in PbTiO3.
[2] Wu Z, Cohen R E. Pressure-induced anomalous phase transitions and colossal enhancement of piezoelectricity in PbTiO3.
Phys. Rev. Lett. 2005; 95 (3): 037601, and related references therein.
Phys. Rev. Lett. 2005; 95 (3): 037601, and related references therein.
22 Advances in Ferroelectrics

Acknowledgements

We thank Professor M. Azuma in Tokyo Institute of Technology for useful discussion.

We also thank T. Furuta, M. Kubota, H. Yabuta, and T. Watanabe for useful discussion
and computational support. The present work was partly supported by the Elements Sci‐
ence and Technology Project from the Ministry of Education, Culture, Sports, Science
and Technology.

Author details

Kaoru Miura1 and Hiroshi Funakubo2

1 Canon Inc., Tokyo, Japan

2 Tokyo Institute of Technology, Yokohama, Japan

References

[1] Cohen R E. Origin of ferroelectricity in perovskite oxides. Nature 1992; 451 (6382) :
136-8.

[2] Wu Z, Cohen R E. Pressure-induced anomalous phase transitions and colossal en‐

hancement of piezoelectricity in PbTiO3. Phys. Rev. Lett. 2005; 95 (3): 037601, and re‐
lated references therein.

[3] Deguez O, Rabe K M, Vanderbilt D. First-principles study of epitaxial strain in per‐

ovskites. Phys. Rev. B 2005; 72 (14): 144101, and related references therein.

[4] Qi T, Grinberg I, Rappe A M. First-principles investigation of the high tetragonal fer‐

roelectric material BiZn1/2Ti1/2O3. Phys. Rev. B 2010; 79 (13): 134113, and related refer‐
ences therein.

[5] Wang H, Huang H, Lu W, Chan H L W, Wang B, Woo C H. Theoretical prediction on

the structural, electronic, and polarization properties of tetragonal Bi2ZnTiO6. J.
Appl. Phys. 2009; 105 (5): 053713.

[6] Dai J Q, Fang Z. Structural, electronic, and polarization properties of Bi2ZnTiO6 su‐
percell from first-principles. J. Appl. Phys. 2012; 111 (11): 114101.

[7] Khenata R, Sahnoun M, Baltache H, Rerat M, Rashek A H, Illes N, Bouhafs B. First-

principle calculations of structural, electronic and optical properties of BaTiO3 and
BaZrO3 under hydrostatic pressure. Solid State Commun. 2005; 136 (2): 120-125.
Electronic Structures of Tetragonal ABX3: Role of the B-X Coulomb Repulsions for Ferroelectricity and Piezoelectricity 23
http://dx.doi.org/10.5772/52187

[8] Oguchi T, Ishii F, Uratani Y. New method for calculating physical properties from
first principles-piezoelectric and multiferroics. Butsuri 2009; 64 (4): 270-6 [in Japa‐
nese].
[9] Uratani Y, Shishidou T, Oguchi T. First-principles calculations of colossal piezoelec‐
tric response in thin film PbTiO3. Jpn. Soc. Appl. Phys. 2008: conference proceedings,
27-30 March 2008, Funabashi, Japan [in Japanese].
[10] Miura K, Kubota M, Azuma M, and Funakubo H. Electronic and structural proper‐
ties of BiZn0.5Ti0.5O3. Jpn. J. Appl. Phys. 2009; 48 (9): 09KF05.
[11] Miura K, Furuta T, Funakubo H. Electronic and structural properties of BaTiO3: A
proposal about the role of Ti 3s and 3p states for ferroelectricity. Solid State Com‐
mun. 2010; 150 (3-4): 205-8.
[12] Furuta T, Miura K. First-principles study of ferroelectric and piezoelectric properties
of tetragonal SrTiO3 and BaTiO3 with in-plane compressive structures. Solid State
Commun. 2010; 150 (47-48): 2350-3.
[13] Miura K, Azuma M, Funakubo H. Electronic and structural properties of ABO3: Role
of the B-O Coulomb repulsions for ferroelectricity. Materials 2011; 4 (1): 260-73.
http://www.mdpi.com/1996-1944/4/1/260 (accessed 20 July 2012).
[14] Miura K. First-principles study of ABO3: Role of the B-O Coulomb repulsions for fer‐
roelectricity and piezoelectricity. Lallart M. (ed.) Ferroelectrics - Characterization and
Modeling. Rijeka: InTech; 2012. p395-410. Available from http://www.intechop‐
en.com/books/ferroelectrics-characterization-and-modeling/first-principles-study-of-
abo3-role-of-the-b-o-coulomb-repulsions-for-ferroelectricity-and-piezoelec (accessed
20 July 2012).
[15] Miura K, Funakubo H. First-principles analysis of tetragonal ABO3: Role of the B-O
Coulomb repulsions for ferroelectricity and piezoelectricity. Proceedings of 15th US-
Japan Seminar on Dielectric and Piezoelectric Ceramics, 6-9 November 2011, Kagosh‐
ima, Japan.
[16] Miura K, Ifuku T, Kubota M, Hayashi J. Piezoelectric Material. Japan Patent
2011-001257 [in Japanese].
[17] Miura K, Kubota M, Hayashi J, Watanabe T. Piezoelectric Material. submitted to Ja‐
pan Patent [in Japanese].
[18] Miura K, Furuta T. First-principles study of structural trend of BiMO3 and BaMO3:
Relationship between tetragonal and rhombohedral structure and the tolerance fac‐
tors. Jpn. J. Appl. Phys. 2010; 49 (3): 031501 (2010).
[19] Miura K, Kubota M, Azuma M, and Funakubo H. Electronic, structural, and piezo‐
electric properties of BiFe1-xCoxO3. Jpn. J. Appl. Phys. 2010; 49 (9): 09ME07.
[20] Miura K, Tanaka M. Electronic structures of PbTiO3: I. Covalent interaction between
Ti and O ions. Jpn. J. Appl. Phys. 1998; 37 (12A): 6451-9.
24 Advances in Ferroelectrics

[21] LDA_TM_psp1_data: ABINIT. http://www.abinit.org/downloads/psp-links/

lda_tm_psp1_data/ (accessed 20 July 2012).

[22] Kuroiwa Y, Aoyagi S, Sawada A, Harada J, Nishibori E, Tanaka M, and Sakata M.

Evidence for Pb-O covalency in tetragonal PbTiO3. Phys. Rev. Lett. 2001; 87 (21):
217601.

[23] Shannon R D. Revised effective ionic radii and systematic studies of interatomic dis‐
tances in halides and chalcogenides. Acta Crystallogr. Sect. A. 1976; 32 (5): 751-67.

[24] Suchomel M R, Fogg A M, Allix M, Niu H, Claridge J B, Rosseinsky M J. Bi2ZnTiO6:

A lead-free closed-shell polar perovskite with a calculated ionic polarization of 150
μC cm-2. Chem. Mater. 2006; 18 (21), 4987-9.

[25] Khalyavin D D, Salak A N, Vyshatko N P, Lopes A B, Olekhnovich N M, Pushkarev

A V, Maroz I I, Radyush T V. Crystal structure of metastable perovskite
Bi(Mg1/2Ti1/2)O3: Bi-based structural analogue of antiferroelectric PbZrO3. Chem. Ma‐
ter. 2006; 18 (21), 5104-10.

[26] Randall C A, Eitel R, Jones B, Shrout T R, Woodward D I, Reaney I M, Investigation

of a high TC piezoelectric system: (1-x)Bi(Mg1/2Ti1/2)O3-(x)PbTiO3. J. Appl. Phys. 2004;
95 (7): 3633-9.

[27] Rossetti Jr G A, Khachaturyan A G. Concepts of morphotropism in ferroelectric solid

solutions. Proceedings of 13th US-Japan Seminar on Dielectric and Piezoelectric Ce‐
ramics, 4-7 November 2007, Awaji, Japan, and related references therein.

[28] Damjanovic D. A morphotropic phase boundary system based on polarization rota‐

tion and polarization extension. Appl. Phys. Lett. 2010; 97 (6): 062906, and related ref‐
erences therein.

[29] Gonze X, Beuken J-M, Caracas R, Detraux F, Fuchs M, Rignanese G-M, Sindic L, Ver‐
straete M, Zerah G, Jollet F, Torrent M, Roy A, Mikami M, Ghosez P, Raty J-Y, Allan
D C. First-principles computation of material properties: the ABINIT software
project. Comput. Mater. Sci. 2002; 25 (3), 478-92.

[30] Hohenberg P, Kohn W. Inhomogeneous electron gas. Phys. Rev. 1964; 136 (3B):
B864-71.

[31] Opium - pseudopotential generation project. http://opium.sourceforge.net/

index.html (accessed 20 July 2012).

[32] Ramer N J, Rappe A M. Application of a new virtual crystal approach for the study
of disordered perovskites. J. Phys. Chem. Solids. 2000; 61 (2): 315-20.

[33] Resta R. Macroscopic polarization in crystalline dielectrics: the geometric phase ap‐
proach. Rev. Mod. Phys. 1994; 66 (3): 899-915.

[34] Kim Y-I, Lee E. Constant-wavelength neutron diffraction study of cubic perovskites
BaTaO2N and BaNbO2N. J. Ceram. Soc. Jpn. 2011; 119 (5): 371-4.
 Chapter 2

Advances in Thermodynamics
of Ferroelectric Phase Transitions

Shu-Tao Ai

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52089

1. Introduction

The thermodynamics of ferroelectric phase transitions is an important constituent part of the

phenomenological theories of them, as well as the interface dynamics of them. In particular,
if we confine the thermodynamics to the equilibrium range, we can say that the Landau-
Devonshire theory is a milestone in the process of the development of ferroelectric phase
transition theories. This can be found in many classical books such as [1,2]. Many studies
centering on it, especially the size-effects and surface-effects of ferroelectric phase transitions,
have been carried out. For the reason of simplicity, we just cite a few [3,4]. But we think these
are a kind of technical but not fundamental progress.

Why we think so is based on that the Landau-Devonshire theory is confined to the equilibrium
range in essene so it can’t deal with the outstanding irreversible phenomonon of first-order
ferroelectric phase transitions strictly, which is the „thermal hysteresis“. The Landau-Devon‐
shire theory attributes the phenomenon to a series of metastable states existing around the
Curie temperature T C . In principle, the metastable states are not the equilibrium ones and can
not be processed by using the equilibrium thermodynamics. Therefore, we believe the Landau-
Devonshire theory is problematic though it is successful in mathematics. The real processes of
phase transition were distorted. In this contribution, the Landau-Devonshire theory will be
reviewed critically, then the latest phenomenological theory of ferroelectric phase transitions
will be established on the basis of non-equilibrium or irreversible thermodynamics.

This contribution are organized as the follows. In Section 2, we will show the unpleasant
consequence caused by the metastable states hypothesis, and the evidence for the non-
existence of metastable states, i.e. the logical conflict. Then in Section 3 and 4, we will give the
non-equilibrium ( or irreversible ) thermodynamic description of ferroelectric phase transi‐

© 2012 Ai; licensee InTech. This is an open access article distributed under the terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
26 Advances in Ferroelectrics

tions, which eliminates the unpleasant consequence caused by the metastable states hypoth‐
esis. In Section 5, we will give the non-equilibrium thermodynamic explanation of the
irreversibility of ferroelectric phase transitions, i.e. the thermal hysteresis and the domain
occurrences in ferroelectrics. At last, in Section 6 we will make some concluding remarks and
look forward to some possible developments.

2. Limitations of Landau-Devonshire theory and demonstration of new

approach

The most outstanding merit of Landau-Devonshire theory is that the Curie temperature and
the spontaneous polarization at Curie temperature can be determined simply. However, in
the Landau-Devonshire theory, the path of a first-order ferroelectric phase transition is
believed to consist of a series of metastable states existing around the Curie temperature. This
is too difficult to believe because of the difficulties encounted ( just see the follows) T C .

2.1. Unpleasant consequence caused by metastable states hypothesis

Basing on the Landau-Devonshire theory, we make the following inference. Because of the
thermal hysteresis, a first-order ferroelectric phase transition must occur at another tempera‐
ture, which is different from the Curie temperature [5]. The state corresponding to the
mentioned temperature ( i.e. actural phase transition temperature ) is a metastable one. Since
the unified temperature and spontanous polarization can be said about the metastable state,
we neglect the heterogeneity of system actually. In other words, every part of the system, i.e.
either the surface or the inner part, is of equal value physically. When the phase transition
occurs at the certain temperature, every part of the system absorbs or releases the latent heat
simultaneously by a kind of action at a distance. ( The concept arose in the electromagnetism
first. Here it maybe a kind of heat transfer. ) Otherwise, the heat transfer in system, with a finite
rate, must destroy the homogeneity of system and lead to a non-equilibrium thermodynamic
approach. The unpleasant consequence, i.e. the action at a distance should be eliminated and
the lifeforce should be bestowed on the non-equilibrium thermodynamic approach.
In fact, a first-order phase transition process is always accompanied with the fundamental
characteristics, called the co-existence of phases and the moving interface ( i.e. phase boun‐
dary ). The fact reveals that the phase transition at various sites can not occur at the same time.
Yet, the phase transition is induced by the external actions ( i.e. absorption or release of latent
heat ). It conflicts sharply with the action at a distance.

2.2. Evidence for non-existence of metastable states: logical conflict

In the Landau-Devonshire theory, if we neglect the influence of stress, the elastic Gibbs energy
G1 can be expressed with a binary function of variables, namely the temperature T and the
electric displacement D ( As G1 is independent of the orientation of D , here we are interested
in the magnitude of D only )
 Advances in Thermodynamics of Ferroelectric Phase Transitions 27
http://dx.doi.org/10.5772/52089

G1 = g1 (T , D ) (1)

The long-standing, close correlation between analytical dynamics and thermodynamics

implies that Equation (1) can be taken as a scleronomic constraint equation

f1 ( G1 ,T , D ) = G1 - g1 (T , D ) = 0 (2)

where G1, T , D are the generalized displacements. The possible displacements dG1, dT and
dD satisfy the following equation

¶g1 ¶g
dG1 - dT - 1 dD = 0 (3)
¶T ¶D

In the Landau-Devonshire theory, the scleronomic constraint equation, i.e. Equation (1) is
expressed in the form of the power series of D ( For simplicity, only the powers whose orders
are not more than six are considered )

1 1 1
G1 = G10 + a D 2 + b D 4 + g D 6 (4)
2 4 6

where α, β, γ are the functions of T , and G10 is the elastic Gibbs energy of paraelectric phase.
The relation between G1 and D at various temperature, which belongs to first-order phase
transition ferroelectrics is represented graphically in Figure 1. The electric displacements
which correspond to the bilateral minima of G1 are identified as ±D *, and the electric displace‐
ment which corresponds to the middle minimum of G1 equals zero. The possible electric
displacements should be the above ones which correspond to the minima of G1.

Equivalently, imposed on the generalized displacements G1, T , D is a constraint, which is

¶G1
=0 (5)
¶D

So, the possible displacement dD should be the follows

dD *, − dD *, 0 − (±D *) = ∓ D *, ± D * − 0 = ± D *, 0. After all, if our discussion are limited in the
equilibrium thermodynamics strictly, there must be the third constraint, i.e. the equilibrium
D and T should satisfy

h ( D ,T ) = 0 (6)
28 Advances in Ferroelectrics

Figure 1. The relation between elastic Gibbs energy G1 and zero field electric displacement D belongs to the ferroelec‐
trics at various temperature, which undergoes a first-order phase transition [5]. T 0 :the lowest temperature at which
the paraelectric phase may exist, i.e. the Curie-Weiss temperature; T C :the phase transition temperature, i.e. the Curie
temperature; T 1 : the highest temperature at which the ferroelectric phase may exist; T 2 : the highest temperature at
which the ferroelectric phase may be induced by the external electric field.

where h is a binary function of the variables D and T . It can be determined by the principle
of minimum energy

G1 = min (7)

for certain T . Then, the metastable states are excluded. Thus, the thermal hysteresis does not
come into being. The corollary conflicts with the fact sharply. This reveals that the first-order
ferroelectric phase transition processes must not be reversible at all so as not to be dealt with
by using the equilibrium thermodynamics.
How can this difficulty be overcome? An expedient measure adopted by Devonshire is that
the metastable states are considered. However, do they really exist?
Because the metastable states are not the equilibrium ones, the relevant thermodynamic
variables or functions should be dependent on the time t . In addition, the metastable states are
close to equilibrium, so the heterogeneity of system can be neglected. Here, the elastic Gibbs
energy G ′1 should be

G1¢ = g2 (T , D , t ) (8)

For the same reason as was mentioned above, Equation (8) can be regarded as a rheonomic
constraint on the generalized displacements G ′1, T , D
 Advances in Thermodynamics of Ferroelectric Phase Transitions 29
http://dx.doi.org/10.5772/52089

f2 ( G1¢ ,T , D , t ) = G1¢ - g2 (T , D , t ) = 0 (9)

In this case, the possible displacements dG ′1, dT and dD satisfy the following equation

¶g2 ¶g ¶g
dG1¢ - dT - 2 dD - 2 dt = 0 (10)
¶T ¶D ¶t

Comparing Equation (3) with Equation (10), we may find that the possible displacements here
are not the same as those in the former case which characterize the metastable states for they
satisfy the different constraint equations, respectively. ( In the latter case, the possible dis‐
placements are time-dependent, whereas in the former case they are not. ) Yet, the integral of
possible displacement dD is the possible electric displacement in every case. The possible
electric displacements which characterize one certain metastable state vary with the cases. A
self-contradiction arises. So the metastable states can not come into being.

What are the real states among a phase transition process? In fact, both the evolution with time
and the spatial heterogeneity need to be considered when the system is out of equilibrium
[6-9]. Just as what will be shown in Section 2.3, the real states should be the stationary ones,
which do not vary with the time but may be not metastable.

2.3. Real path: Existence of stationary states

The real path of a first-order ferroelectric phase transition is believed by us to consist of a series
of stationary states. At first, this was conjectured according to the experimental results, then
was demonstrated reliable with the aid of non-equilibrium variational principles.

Because in the experiments the ferroelectric phase transitions are often achieved by the quasi-
static heating or cooling, we conjetured that they are stationary states processes [8]. The results
on the motion of interface in ferroelectrics and antiferroelectrics support our opinion [10-12].
From Figure 2, we may find that the motion of interface is jerky especially when the average
velocity va is small. A sequence of segments of time corresponding to the states of rest may be
found. The experimental results about other materials such as PbTiO3 are alike [11]. This
reveals that in these segments of time ( i.e. characteristic time of phase transition ) the stationary
distributions of temperature, heat flux, stress, etc. may be established. Otherwise, if the motion
of interface is continuous and smooth, with the unceasing moving of interface ( where the
temperature is T C ) to the inner part, the local temperature of outer part must change to keep
the temperature gradient ∇ T of this region unchanged for it is determined by
±lρv ′ = J qdiff = − κ∇ T , where l is the latent heat ( per unit mass ), ρ is the mass density, v ′ is the
velocity of interface ( where the phase transition is occurring ), J qdiff is the diffusion of heat, i.e.
heat conduction, κ is the thermal conductivity ( and maybe a tensor. ) Then, the states are not
stationary.
30 Advances in Ferroelectrics

Figure 2. The position of phase boundary as a function of time for NaNbO3 single crystal for the various values of aver‐
age velocity va (the values in μm/s given against the curves) [12].

The non-equilibrium variational principles are just the analogue and generalization of the
variational principles in analytical dynamics. The principle of least dissipation of energy, the
Gauss’s principle of least constraint and the Hamiltonian principle etc., in non-equilibrium
thermodynamics play the fundamental roles as those in analytical dynamics. They describe
the characteristics of stationary states or determine the real path of a non-equilibrium process.
For the basic characteristics of non-equilibrium processes is the dissipation of energy, the
dissipation function φ is defined as

j = ss -p (11)

where σs is the rate of local entropy production and π is the external power supply ( per unit
volume and temperature ). After the rather lengthy deducing and utilizing the thermodynamic
Gauss’s principle of least constraint which makes the system choose a real path [13], the
evolution with time t of the deviation from a given non-equilibrium stationary state,
ξ (t ) = {ξi (t )}, was obtained in two cases. If no external power supply,
 Advances in Thermodynamics of Ferroelectric Phase Transitions 31
http://dx.doi.org/10.5772/52089

2Si
t
(12)
xi ( t ) = xi ( 0 ) e Ri

where ξi (0) is the initial value of ξi (t ), Si is the coefficient between the linear variation in the
( )
thermodynamic force χTi1 (ξ ) and the deviation of the extensive pseudo-thermodynamic
variable from a given non-equilibrium stationary state ξi , Ri is the coefficient between the linear
( )
variation in the dissipative force χDi1 (ξ̇ ) and the time-derivative of the deviation of the
extensive pseudo-thermodynamic variable from a given non-equilibrium stationary state ξ̇ i .
Equation (12) define the real path with the addition that Ri should be a suitable value Ri*. If
the external power supply exists, similarly the evolution of deviation ξi can be obtained

2 ( Si - Vi )
t
(13)
xi ( t ) = xi ( 0 ) e Ri

where V i is the coefficient between the linear variation in the force related to the external power
( )
χEi1 and the deviation of the extensive pseudo-thermodynamic variable from a given non-
equilibrium stationary state ξi . If the coefficients V i , Ri assume the suitable values V i**, Ri**,
the system choose a real path.

Figure 3. Three types of regions and their interfaces in the ferroelectric-paraelectric system in which a first-order
phase transition is occurring [13].
32 Advances in Ferroelectrics

Both the real paths in the two cases reveal that the deviations decrease exponentially when the
system regresses to the stationary states. Stationary states are a king of attractors to non-
equilibrium states. The decreases are steep. So the regressions are quick. It should be noted
that we are interested in calculating the change in the generalized displacements during a
macroscopically small time interval. In other words, we are concerned with the determination
of the path of an irreversible process which is described in terms of a finite difference equation.
In the limit as the time interval is allowed to approach zero, we obtain the variational equation
of thermodynamic path.

So, if the irreversible process is not quick enough, it can be regarded as the one that consists
of a series of stationary states. The ferroelectric phase transitions are usually achieved by the
quasi-static heating or cooling in the experiments. So, the processes are not quick enough to
make the states deviate from the corresponding stationary states in all the time. In Figure 3,
three types of regions and their interfaces are marked with I, II, III, 1, 2 respectively. The region
III where the phase transition will occur is in equilibrium and has no dissipation. In the region
I where the phase transition has occurred, there is no external power supply, and in the region
II ( i.e. the paraelectric-ferroelectric interface as a region with finite thickness instead of a
geometrical plane ) where the phase transition is occurring, there exists the external power
supply, i.e. the latent heat ( per unit volume and temperature ). According to the former
analysis in two cases, we may conclude that they are in stationary states except for the very
narrow intervals of time after the sudden lose of phase stability.

3. Thermo-electric coupling

In the paraelectric-ferroelectric interface dynamics induced by the latent heat transfer [6,7], the
normal velocity of interface vn was obtained

1 é
vn = k ( ÑT ) fer - k par ( ÑT ) par ù × n (14)
lr ëê fer ûú

where l is the latent heat ( per unit mass ), ρ is the density of metastable phase (paraelectric
phase ), k fer is the thermal conductivity coefficient of ferroelectric phase, k par is the thermal
conductivity coefficient of paraelectric phase, (∇ T ) fer is the temperature gradient in ferro‐
electric phase part, (∇ T ) par is the temperature gradient in paraelectric phase part, n is the unit
vector in normal direction and directs from the ferroelectric phase part to the paraelectric phase
part. The temperature gradients can be studied from the point of view that a ferroelectric phase
transition is a stationary, thermo-electric coupled transport process [8].

3.1. Local entropy production

In the thermo-electric coupling case, the Gibbs equation was given as the following [8]
 Advances in Thermodynamics of Ferroelectric Phase Transitions 33
http://dx.doi.org/10.5772/52089

Tds = du - E × dD - å midni (15)

i

where T , E , D is the temperature, the electric field intensity and the electric displacement
within a random small volume, respectively; s, u, μi , ni is the entropy density, the internal
energy density, the chemical potential and the molar quantity density in the small volume,
respectively. And there, it was assumed that the crystal system is mechanically-free ( i.e. no
force is exerted on it ). Differentiating Equation (15) and using the following relations

¶u
+ Ñ × Ju = 0 (16)
¶t

¶D ¶ ( e 0 E + P )
= = JP (17)
¶t ¶t

¶ni
+ Ñ × J ni = 0 (18)
¶t

we have

¶s 1 E m
= - Ñ × J u - × J P + å i Ñ × J ni (19)
¶t T T i T

where J u , J P , J ni is the energy flux, the polarization current and the matter flux; P is the
polarization. J u should consist of three parts: the energy flux caused by the heat conduction,
the energy flux caused by the charge transport and the energy flux caused by the matter
transport

J u = J q + j J P + å mi J ni (20)
i

where J q is the heat flux, φ is the electrical potential and satisfies

E = -Ñj (21)

Then we deduce the following

34 Advances in Ferroelectrics

¶s æ Jq + jJ P ö æ1ö æj ö J
= -Ñ × ç ÷ + J q × Ñ ç ÷ + J P × Ñ ç ÷ - å ni × Ñmi (22)
¶t ç T ÷ è T ø è T ø T
è ø i

If we define a entropy flux J s and a rate of local entropy production σs as

Jq + jJP
Js = (23)
T

æ1ö æj ö J
s s = J q × Ñ ç ÷ + J P × Ñ ç ÷ - å ni × Ñmi (24)
èT ø èT ø i T

Equation (22) can be written as

¶s
+ Ñ × Js = s s (25)
¶t

This is the local entropy balance equation. We know, the system is in the crystalline states
before and after a phase transition so that there is no diffusion of any kind of particles in the
system. So, J ni = 0. The local entropy production can be reduced as

æ1ö æj ö
s s = Jq × Ñ ç ÷ + J P × Ñ ç ÷ (26)
T
è ø èT ø

We know the existence of ferroics is due to the molecular field. It is an internal field. So we
must take it into account. Here, the electric field should be the sum of the external electric field
Ee and the internal electric field Ei

E = E e + Ei (27)

Correspondingly, there are the external electrical potential φe and the internal electrical
potential φi and they satisfy

Ee = -Ñje (28)

Ei = -Ñji (29)
 Advances in Thermodynamics of Ferroelectric Phase Transitions 35
http://dx.doi.org/10.5772/52089

If the external electric field is not applied, φe can be a random constant. There is no harm in
letting the constant equal zero. Then the entropy production equals

æ1ö æj ö
s s = Jq × Ñ ç ÷ + J P × Ñ ç i ÷ (30)
T
è ø èT ø

According to the crystal structures of ferroelectrics [2], we know the polarization current J P
originates from the displacement or ordering of ions in ferroelectrics. We may consider it as
the transport of charges influenced by the internal electric field.

3.2. Description of phase transitions and verification of interface dynamics

Assume the external electric field is not applied. Here are the thermodynamic fluxex J q , J P and
the corresponding thermodynamic forces X q , X P

æ1ö
Xq = Ñç ÷ (31)
èT ø

æj ö
XP = Ñç i ÷ (32)
èT ø

J i can be expanded linearly with X j (i, j = q, P )

J q = Lqq × X q + LqP × X P (33)

J P = LPq × X q + LPP × X P (34)

where L qq , L qP , L Pq and L PP are the transport coefficients, which are four second-order
tensors. They should satisfy the generalized Onsager relations [14]
T T
L qq = L qq , L qP = L Pq ,

LPP = LTPP (35)

Because to a first-order ferroelectric phase transition the electric displacement changes

suddenly and so does the internal electrical potential, the force X P of the region where the
phase transition is occurring can be regarded as a large constant roughly in the characteristic
36 Advances in Ferroelectrics

times of phase transition ( i.e. the times in which the interface keeps rest ). For the ferroelectric
phase transition may be regarded as a stationary states process, the principle of minimum
entropy production must be satisfied [15].

According to Equations (30)-(35), we have

s s = Lqq : X q X q + 2LqP : X q X P + LPP : X P X P (36)

If there is no any restriction on X q and X P , according to the conditions on which the entropy
production is a minimum

æ ¶s ö
ç s ÷ = 2Lqq × X q + 2LqP × X P = 2J q = 0 (37)
ç ¶X q ÷
è øXP

æ ¶s s ö
çç ÷÷ = 2LPq × X q + 2LPP × X P = 2J P = 0 (38)
è ¶X P ø X q

We know the stationary states are equilibrium ones actually. If we let X q ( or X P ) be a constant,
according to Equation (38) ( or (37) ) we know J P ( or J q ) which is corresponded to another
force X P ( or X q ) should be zero.

Then, a first-order ferroelectric phase transition can be described by the second paradigm.
Since the force X P of the region where the phase transition is occurring is a large constant, the
flux J q of this region should be zero ( but J P ≠ 0 ). This states clearly that the pure heat conduction
and the heat conduction induced by the thermo-electric coupling cancel out each other so as
to release or absorb the latent heat. It is certain that the latent heat passes through the region
where the phase transition has occurred ( at the outside of the region where the phase transition
is occurring ) and exchanges itself with the thermal bath. Accompanied with the change of the
surface’s temperature and the unceasing jerky moving of the region where the phase transition
is occurring, a constant temperature gradient is kept in the region where the phase transition
has occurred, i.e. the force X q is a constant. So, the flux J P = 0 ( but J q ≠ 0 ). This states clearly
that the electric displacement of the region where the phase transition has occurred will not
change but keep the value at Curie temperature or zero until the phase transition finishes.
Differently, the region where the phase transition will occur should be described by the first
paradigm for there is no restriction on the two forces X P , X q . The states of this region are
equilibrium ones. So the temperature gradient ∇ T should be zero.

Considering that (∇ T ) par ≈ 0 for the region where the phase transition will occur ( i.e. the
paraelectric phase part ) can be regarded as an equilibrium system, we modify Equation (14) as
 Advances in Thermodynamics of Ferroelectric Phase Transitions 37
http://dx.doi.org/10.5772/52089

k fer ( ÑT ) fer × n
vn = (39)
lr

In order to compare it with the experiments, we make use of the following values which are
about PbTiO3 crystal: ρ =7.1g/cm3 [16], l =900cal/mol [17], k fer =8.8 × 105erg/cm﹒s ﹒K [18]. The
value of the velocity of the interface’s fast motion, which has been measured in the experiments,
is 0.5mm/s [11]. According to Equation (39), we calculate the corresponding temperature
gradient to be 57.35K/cm. However, in [19] it is reported that the experimental temperature
gradient varies from 1.5 to 3.5K/mm while the experimental velocity of the interface’s motion
varies from 732 to 843μm/s. Considering the model is rather rough, we may conclude that the
theory coincides with the experiments.

3.3. Relation between latent heat and spontaneous polarization

In the experiments, the latent heat and the spotaneous polarization are measured often for
first-order ferroelectric phase transitions. So in the follows, we will establish the relation
between latent heat and spontaneous polarization in the realm of non-equilibrium thermody‐
namics.

All the quantities of the region where the phase transition has occurred are marked with the
superscript “I”; all the quantities of the region where the phase transition is occurring are
marked with the superscript “II”; and all the quantities of the region where the phase transition
will occur are marked with the superscript “III”. Let’s consider the heating processes of phase
transition firstly. In the region where the phase transition has occurred,

J qI - para = LIqq- para × X qI - para = lr va (40)

where we have ignored the difference between the mass density of ferroelectric phase and that
of paraelectric phase ( almost the same ) and denote them as ρ , va is the average velocity of
interface. In the region where the phase transition is occurring,

J qII = LIIqq × X qII + LIIqP × X PII = 0 (41)

J PII = LIIPq × X qII + LIIPP × X PII (42)

The heat which is transferred to the region where the phase transition is occurring is absorbed
as the latent heat because the pure heat conduction and the heat conduction induced by the
thermo-electric coupling cancel out each other. So,
38 Advances in Ferroelectrics

lr va = LIIqq × X qII (43)

According to Eqations (41)-(43), we work out

é
( ) ( )
-1 -1 ù
J PII = lr ê LIIPq × LIIqq - LIIPP × LIIqP ú × va (44)
ë û

where the superscript “-1” means reverse. While

spon
II
ò J P dt = - D = e 0ÑjiIII - P spon - III = - P spon - III (45)

where we utilized the boundary condition of D and considered the region where the phase
transition will occur is in equilibrium, the superscript “spon” means spontaneous. So,

P spon = P spon - III = - ò J PII dt (46)

The relation between latent heat and spontaneous polarization are obtained. In the cooling
processes of phase transition,

-lr va = LIqq- ferr × X qI - ferr + LIqP- ferr × X PI - ferr = LIIqq × X qII (47)

II ¢ spon - I
ò J P dt = D = -e 0ÑjiI + P spon - I (48)

Repeating the above steps, we obtain

P spon - I = ò J PII ¢dt + e 0ÑjiI (49)

With

é
( ) ( )
-1 -1 ù
J PII ¢ = -lr ê LIIPq × LIIqq - LIIPP × LIIqP II
ú × va = - J P (50)
ë û

Then we find that P spon−III ( serves as the equilibrium polarization ) is not equal P spon−I ( serves
as the non-equilibrium polarization ). For the region where the phase transition will occur is
 Advances in Thermodynamics of Ferroelectric Phase Transitions 39
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stressed [9], there is some difference between P spon ( = P spon−III ) and the equilibrium spontane‐
ous polarization without the affects of stress P spon ′ because of the piezoelectric effect.

4. Thermo-electro-mechanical coupling

The comprehensive thermo-electro-mechanical coupling may be found in ferroelectric phase

transition processes. Because there exists not only the change of polarization but also the
changes of the system’s volume and shape when a ferroelectric phase transition occurs in it,
the mechanics can not be ignored even if it is mechanically-free, i.e. no external force is exerted
on it. To a first-order ferroelectric phase transition, it occurs at the surface layer of system firstly,
then in the inner part. So, the stress may be found in the system.

Since one aspect of the nature of ferroelectric phase transitions is the thermo-electro-mechan‐
ical coupling, we take the mechanics into account on the basis of Section 3, where only the
thermo-electric coupling has been considered. This may lead to a complete description in the
sense of continuum physics.

4.1. Deformation mechanics

For a continuum, the momentum equation in differential form can be written as

Ñ × σ + r f = ra (51)

where σ, f , a, ρ is the stress, the volume force exerted on unit mass, the acceleration and the
1
mass density, respectively. Let k = v 2 be the local kinetic energy density (per unit mass), with
2
v is the velocity. Then

dk
= v ×a (52)
dt

where t is the time. In terms of

∇ ⋅ (v ⋅ σ ) = v ⋅ (∇ ⋅ σ ) + (∇ v ) : σ (53)

σ : ( Ñv ) = σ : d (54)

we can deduce the following balance equation of mechanical energy basing on Equations
(51) (52)
40 Advances in Ferroelectrics

dk
ρ − ∇ ⋅ (v ⋅ σ ) = ρv ⋅ f − σ : d (55)
dt

which is in differential form and in Lagrangian form. Or in Eulerian form

∂ (ρk )
+ ∇ ⋅ (ρkv − v ⋅ σ ) = ρv ⋅ f − σ : d (56)
∂t

1 1
where d = (∇ v + v∇ ) = ∇ v + (∇ v )T is the rate of deformation or strain rate ( the super‐
2 2
script “T” means transposition ).

To a ferroelectric phase transition, f and σ may be the nominal volume force and stress, which
are the embodiments of the actions of thermo-electro-mechanical coupling and are two internal
fields. Generally, they are the sums of real and nominal volume force or stress

f = f real + f nom (57)

σ = σ real + σ nom (58)

The nominal volume force and stress are not zero until the eigen ( or free ) deformation of
system finishes in phase transitions. If they are zero, the eigen ( or free ) deformation finishes.

4.2. Local entropy production and description of phase transitions

The Gibbs equation was given as the following [9]

1 1
T ds + ∑ μi dni + E ⋅ dD + f ⋅ dr + ∇ ⋅ (v ⋅ σ )dt = du + dk (59)
i
ρ ρ

where T , E , D is the local temperature, the local electric field intensity and the local electric
displacement, respectively; s, u, ni , μi is the local entropy density ( per unit mass ), the local
internal energy density ( per unit mass ), the local molar quantity density ( per unit mass ) and
the chemical potential, respectively; r is the displacement vector. If the external electric field
is not applied, the quantity E is the internal electric field Ei only [8].

Make the material derivative of Equation (59) with t , then obtain

ds ρ dni 1 dD ρ dr 1 ρ de
ρ +
dt T
∑ μi dt
+ Ei ⋅
T dt
+
T
f⋅ + ∇ ⋅ (v ⋅ σ ) =
dt T T dt
(60)
i
 Advances in Thermodynamics of Ferroelectric Phase Transitions 41
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where e is the total energy with e = u + k . We know, the system is in the crystalline states before
and after a phase transition so that there is no diffusion of any kind of particles in the system.
d ni dD
So, ni as the local molar quantity ( per unit mass ) does not change with t , i.e. = 0. stands
dt dt
dr
for the polarization current J P , while stands for the velocity v , Ei = − ∇ φi ( φi stands for the
dt
internal electric potential ).

After the lengthy and troublesome deduction [9], the local entropy balance equation in
Lagrangian form can be obtained

ds
r = -Ñ × J s + s s (61)
dt

with the entropy flux J s

J qdiff + φi J P − v ⋅ σ
Js = (62)
T

and the rate of local entropy production σs

σs = J qdiff ⋅ ∇ ( T1 ) + J P ⋅∇
( φT ) − σ : v∇ ( T1 ) − ρf ⋅ Tv
i
(63)

where J qdiff is the diffusion of heat, i.e. heat conduction.

Here are the thermodynamic fluxes J qdiff ( = J q ), J P , σ ( = J σ ), ρf ( = J f ) and the corresponding

thermodynamic forces X q , X P , X σ , X f

æ1ö
Xq = Ñç ÷ (64)
èT ø

æj ö
XP = Ñç i ÷ (65)
èT ø

æ1ö
X s = - vÑ ç ÷ (66)
èT ø
42 Advances in Ferroelectrics

v
Xf =- (67)
T

J i (i = q, P, σ, f ) can be expanded linearly with X j ( j = q, P, σ, f )

J q = Lqq × X q + LqP × X P + Lqs : X s + Lqf × X f (68)

J P = LPq × X q + LPP × X P + LPs : X s + LPf × X f (69)

Js = Ls q × X q + Ls P × X P + Lss : X s + Ls f × X f (70)

J f = L fq × X q + L fP × X P + L f s : X s + L ff × X f (71)

where L qq , L PP , L ff ,L qP , L Pq , L qf ,L fq , L Pf ,L fP are nine second-order tensors,

L qσ , L σq , L Pσ , L σP , L σf , L fσ are six third-order tensors, L σσ is a fourth-order tensor. They
should satisfy the generalized Onsager relations [14]
T
L αα = L αα

(a = q , P , s , f ) (72)

T
L αβ = L βα

(a , b = q , P , s ,f , and a ¹ b ) (73)

So the rate of local entropy production can be written as

s s = Lqq : X q X q + LqP × × X P X q + Lqs L X sT X q + Lqf × × X f X q

+ LPq × × X q X P + LPP : X P X P + LPs L X sT X P + LPf × × X f X P
(74)
+ Ls q L X q X sT + Ls P L X P X sT + Lss L × X sT X sT + Ls f L X f X sT
+ L fq × × X q X f + L fP × × X P X f + L f s L X sT X f + L ff : X f X f

According to the condition on which the local entropy production is a minimum, from
Equation (74) we can deduce the following
 Advances in Thermodynamics of Ferroelectric Phase Transitions 43
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æ ¶s ö
ç s÷ = 2 Lqq × X q + LqP × X P + Lqs : X s + Lqf × X f
ç ¶X q ÷
è ø X P , Xs , X f
+ LTPq × X P + LTs q : X s + LTfq × X f
(75)
(
= 2 Lqq × X q + LqP × X P + Lqs : X s + Lqf × X f )
= 2J q
=0

æ ¶s s ö
çç ÷÷ = LTqP × X q + LPq × X q + 2 LPP × X P + LPs : X s
è ¶X P ø X q , Xs , X f
+ LPf × X f + LTs P : X s + LTfP × X f
(76)
(
= 2 LPq × X q + LPP × X P + LPs : X s + LPf × X f )
= 2J P
=0

æ ¶s s ö
çç ÷÷ = LTqs × X q + LTPs × X P + Ls q × X q + Ls P × X P
è ¶X s ø Xq , XP , X f
+ 2 Lss : X s + Ls f × X f + LTf s × X f
(77)
(
= 2 Ls q × X q + Ls P × X P + Lss : X s + Ls f × X f )
= 2 Js
=0

æ ¶s ö
ç s ÷ = LTqf × X q + LTPf × X P + LTs f : X s + L fq × X q
ç ¶X f ÷
è ø X q , X P , Xs
+ L fP × X P + L f s : X s + 2 L ff × X f
(78)
(
= 2 L fq × X q + L fP × X P + L f s : X s + L ff × X f )
= 2J f
=0

This reveals that if the k forces among those are kept constant, i.e.
X i = const (i = 1, 2, ⋅ ⋅ ⋅ , k, k < 4), the fluxes corresponding to the left 4 − k forces are zero. Of
course, if there are no restrictions on X i (i = 1, 2, 3, 4), all the flues are zero. ( For convenience,
we have modified the superscripts q, P, σ, f to be 1,2,3,4 ).
44 Advances in Ferroelectrics

We may describe a ferroelectric phase transition by using the two paradigms above similarly
as we have done in Section 3. To a first-order ferroelectric phase transition, the forces
X P , X σ , X f of the region where the phase transition is occurring can be regarded as three large
constants roughly in the characteristic times of phase transition ( i.e. the times in which the
interface keeps rest ) because the electric displacement, the volume and the shape change
suddenly. So, the flux J qdiff of the region should be zero (but J P ≠ 0, σ ≠ 0, ρf ≠ 0 ). This states
clearly that the pure heat conduction and the heat conduction induced by the thermo-electric
coupling and the thermo-mechanical coupling cancel out each other so as to release or absorb
the latent heat. The phase transition occurs at the surface layer firstly, which is mechanically-
free. So, when the phase transition occurs in this region, the flux σ maybe the nominal stress
σ nom only, which does work to realize the transformation from internal energy to kinetic
energy. When the phase transition occurs in the inner part, the flux σ should be the sum of
σ real and σ nom because the sudden changes of the inner part’s volume and shape have to
overcome the bound of outer part then σ real arises. The region where the phase transition is
occurring, i.e. the phase boundary is accompanied with the real stress σ real usually, which does
work to realize the transformation from kinetic energy to internal energy. This has been
predicted and described with a propagating stress wave [20].

It is certain that the latent heat passes through the region where the phase transition has
occurred ( at the outside of the region where the phase transition is occurring ) and exchange
itself with the thermal bath. For ±lρva = J qdiff = − κ ⋅ ∇ T , a constant temperature gradient ∇ T is
kept in the region where the phase transition has occurrd, i.e. the force X q at every site is a
constant ( which does not change with the time but may vary with the position ). So, the fluxes
J P = σ = ρf = 0 ( but the flux J qdiff ≠ 0 ). This states clearly that the electric displacement D will not
change but keep the value at Curie temperature or zero until the phase transition finishes and
σ real = − σ nom in this region. Because the electric displacement D and the strain ( or deformation )
are all determined by the crystal structure of system, J P = 0 reveals that D of this region does
not change so does not the crystal structure then does not the strain ( or deformation ).
According to [20], we know the region where the phase transition has occurred is unstressed,
i.e. σ real = 0, then σ nom = 0. This reveals that the eigen ( or free ) strain ( or deformation ) of system
induced by the thermo-electro-mechanical coupling of phase transition is complete and the
change of it terminates before the phase transition finishes. The two deductions coincide with
each other. σ real may relaxes via the free surface.

The region where the phase transition will occur should be in equilibrium because there are
no restrictions on the forces X q , X P , X σ , X f . Whereas, according to [20], the region is stressed,
i.e. σ real ≠ 0. To the heating process of phase transition, this may lead to a change of the
spontaneous polarization of this region because of the electro-mechanical coupling ( piezo‐
electric effect ).

An immediate result of the above irreversible thermodynamic description is that the action at
a distance, which is the kind of heat transfer at phase transitions, is removed absolutely. The
 Advances in Thermodynamics of Ferroelectric Phase Transitions 45
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latent heat is transferred within a finite time so the occurrence of phase transition in the inner
part is delayed. ( Of course, another cause is the stress, just see Section 5 ) In other words, the
various parts absorb or release the latent heat at the various times. The action at a distance
does not affect the phase transition necessarily.

5. Irreversibility: Thermal hysteresis and occurrences of domain structure

5.1. Thermal hysteresis

The “thermal hysteresis” of first-order ferroelectric phase transitions is an irreversible

phenomenon obviously. But it was treated by using the equilibrium thermodynamics for
ferroelectric phase transitions, the well-known Landau-Devonshire theory [2]. So, there is an
inherent contradiction in this case. The system in which a first-order ferroelectric phase
transition occurs is heterogeneous. The occurrences of phase transition in different parts are
not at the same time. The phase transition occurs at the surface layer then in the inner part of
system. According to the description above, we know a constant temperature gradient is kept
in the region where the phase transition has occurred. The temperature of surface layer, which
is usually regarded as the temperature of the whole system in experiments, must be higher
( or lower ) than the Curie temperature. This may lead to the thermal hysteresis.

No doubt that the shape and the area of surface can greatly affect the above processes. We may
conclude that the thermal hysteresis can be reduced if the system has a larger specific surface
and, the thermal hysteresis can be neglected if a finite system has an extremely-large specific
surface. So, the thermal hysteresis is not an intrinsic property of the system.

The region where the phase transition will occur can be regarded as an equilibrium system for
there are no restrictions on the forces X q , X P , X σ , X f . In other words, the forces and the
corresponding fluxes are zero in this region. To a system where a second-order ferroelectric
phase transition occurs, the case is somewhat like that of the region where a first-order
ferroelectric phase transition will occur. The spontaneous polarization, the volume and the
shape of system are continuous at the Curie temperature and change with the infinitesimal
magnitudes. This means X q , X P , X σ , X f and J qdiff , J P , σ, ρf can be arbitrary infinitesimal
magnitudes. The second-order phase transition occurs in every part of the system simultane‐
ously, i.e. there is no the co-existence of two phases ( ferroelectric and paraelectric ). So, there
is no the latent heat and stress. The thermal hysteresis disappears.

The region where a first-order ferroelectric phase transition will occur is stressed. This reveals
that the occurrences of phase transition in the inner part have to overcome the bound of outer
part, where the phase transition occurs earlier. This may lead to the delay of phase transition
in the inner part.

5.2. Occurrences of domain structure

Though the rationalization of the existence of domain structures can be explained by the
equilibrium thermodynamics, the evolving characteristics of domain occurrences in
46 Advances in Ferroelectrics

ferroelectrics can not be explained by it, but can be explained by the non-equilibrium
thermodynamics.

In the region where the phase transition is occurring, the thermodynamic forces X P (= ∇ ( φT ) ),
i

X σ (= − v∇ ( T1 ) ), X f (= −
v
T
) can be regarded as three large constants in the characteristic

times of transition and the thermodynamic flux J qdiff = 0 (but J P ≠ 0, σ ≠ 0, ρf ≠ 0 ). The local
entropy production (cf. Equation (63)) reduces to

æj ö é æ 1 öù v
ss = JP × Ñç i ÷ - : ê vÑ ç ÷ ú - r f × (79)
èT ø ë è T ø û T

Now, we are facing a set of complicated fields of T , v and φi , respectively. Assume that the
phase transition front is denoted by S . The points included in S stand for the locations where
the transition is occurring. Because the transition occurs along all directions from the outer

part to the inner part, we may infer that the orientations of ∇

φi
T
, or of − v∇ ( )
1
T
( )
and or of
v
− vary continuously such that they are differently oriented at different locations.
T

There are always several ( at least two ) symmetry equivalent orientations in the prototype
phase ( in most cases it is the high temperature phase ), which are the possible orientations for
spontaneous polarization ( or spontaneous deformation or spontaneous displacement ).
Therefore, the spontaneous polarization, the spontaneous deformation and the spontaneous
displacement must take an appropriate orientation respectively to ensure σs is a positive
minimum when the system transforms from the prototype ( paraelectric ) phase to the
ferroelectric ( low temperature ) phase. The underlying reasons are that

dD d ( e 0 Ei + P )
JP = = (80)
dt dt

= L:ε (81)

dv
rf =r -Ñ× (82)
dt

where L , ε, and ε0 are the modulus of rigidity, the strain and the permittivity of vacuum,
respectively. Therefore, P, ε at different locations will be differently oriented. The domain
structures in ferroelectrics thus occur.
 Advances in Thermodynamics of Ferroelectric Phase Transitions 47
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It seems that the picture of domain occurrences for first-order ferroelectric phase transition
systems should disappear when we face second-order ferroelectric phase transition systems.
This is true if the transition processes proceed infinitely slowly as expounded by the equili‐
brium thermodynamics. But any actual process proceeds with finite rate, so it is irreversible.
Then the above picture revives.
In [21], the domain occurrences in ferromagnetics can be described parallelly by analogy. And
the case of ferroelastic domain occurrences is a reduced, simpler one compared with that of
ferroelectrics or ferromagnetics.
It is well known that the Landau theory or the Curie principle tells us how to determine the
symmetry change at a phase transition. A concise statement is as follows [22]: for a crystal
undergoing a phase transition with a space-group symmetry reduction from G0 to G , whereas
G determines the symmetry of transition parameter ( or vice versa ), it is the symmetry
operations lost in going from G0 to G that determine the domain structure in the low-symmetry
phase. The ferroic phase transitions are the ones accompanied by a change of point group
symmetry [23]. Therefore, the substitution of “point group” for the “space group” in the above
statement will be adequate for ferroic phase transitions. From the above statement, the domain
structure is a manifestation of the symmetry operations lost at the phase transition. In our
treatment of the domain occurrences in ferroics, we took into account the finiteness of system
( i.e. existence of surface ) and the irreversibility of process ( asymmetry of time ). The finiteness

of system make the thermodynamic forces such as ∇ ( )φi

T
, − v∇
1
T
( )
, −
v
T
have infinite
space symmetry. The infinite space symmetry, combined with the asymmetry of time,
reproduces the symmetry operations lost at the phase transition in the ferroic phase. It can be
viewed as an embodiment of time-space symmetry.
After all, for the domain structures can exist in equilibrium systems, they are the equilibrium
structures but not the dissipative ones, for the latter can only exist in systems far from
equilibrium [24].

6. Concluding remarks

In order to overcome the shortcoming of Landau-Devonshire theory, the non-equilibrium

thermodynamics was applied to study the ferroelectric phase transitions. The essence of
transitions is the thermo-electro-mechanical coupling. Moreover, the irreversibility, namely
thermal hysteresis and domain occurrences can be explained well in the realm of non-
equilibrium thermodynamics.
The non-equilibrium thermodynamic approach utilized here is the linear thermodynamic one
actully. In order to get the more adequate approaches, we should pay attention to the new
developments of non-equilibrium thermodynamics. The thermodynamics with internal
variables [25] and the extended ( irreversible ) thermodynamics [26] are two current ones. They
all expand the fundamental variables spaces to describe the irreversible processes more
48 Advances in Ferroelectrics

adequately. Whereas, the relevant theoretical processing must be more complicated undoubt‐
ly. This situation needs very much effort.

Acknowledgements

The work is supported by the Natural Science Foundation Program of Shandong Province,
China ( Grant No. ZR2011AM019 ).

Author details

Shu-Tao Ai*

School of Science, Linyi University, Linyi, People’s Republic of China

References

[1] Grindlay, I. An Introduction to the Phenomenological Theory of Ferroelectricity.

Oxford: Pergamon; (1970).

[2] Lines, M E, & Glass, A M. Principles and Applications of Ferroelectrics and Related
Materials. Oxford: Clarendon; (1977).

[3] Tilley, D R, & Zeks, B. Landau Theory of Phase Transitions in Thick Films. Solid State
Communications (1984). , 49(8), 823-828.

[4] Scott, J F, Duiker, H M, Beale, P D, Pouligny, B, Dimmler, K, Parris, M, Butler, D, &

Eaton, S. Properties of Ceramic KNO3 Thin-Film Memories. Physica B+C (1988).

[5] Zhong, W L. Physics of Ferroelectrics ( in Chinese ). Beijing: Science Press; (1996).

[6] Gordon, A. Finite-Size Effects in Dynamics of Paraelectric-Ferroelectric Interfaces

Induced by Latent Heat Transfer. Physics Letters A (2001).

[7] Gordon, A, Dorfman, S, & Fuks, D. Temperature-Induced Motion of Interface Boun‐

daries in Confined Ferroelectrics. Philosophical Magazine B (2002). , 82(1), 63-71.

[8] Ai, S T. Paraelectric-Ferroelectric Interface Dynamics Induced by Latent Heat Transfer

and Irreversible Thermodynamics of Ferroelectric Phase Transitions. Ferroelectrics
(2006). , 345(1), 59-66.

[9] Ai, S T. Mechanical-Thermal-Electric Coupling and Irreversibility of Ferroelectric Phase

Transitions. Ferroelectrics (2007). , 350(1), 81-92.
 Advances in Thermodynamics of Ferroelectric Phase Transitions 49
http://dx.doi.org/10.5772/52089

[10] Yufatova, S M, Sindeyev, Y G, Garilyatchenko, V G, & Fesenko, E G. Different Kinetics

Types of Phase Transformations in Lead Titanate. Ferroelectrics (1980). , 26(1), 809-812.

[11] Dec, J. Jerky Phase Front Motion in PbTiO3 Crystal. Journal of Physics C (1988). , 21(7),
1257-1263.

[12] Dec, J, & Yurkevich, J. The Antiferroelectric Phase Boundary as a Kink. Ferroelectrics
(1990). , 110(1), 77-83.

[13] Ai, S T, Xu, C T, Wang, Y L, Zhang, S Y, Ning, X F, & Noll, E. Comparison of and
Comments on Two Thermodynamic Approaches ( Reversible and Irreversible ) to
Ferroelectric Phase Transitions. Phase Transitions (2008). , 81(5), 479-490.

[14] Ai, S T, Zhang, S Y, Jiang, J S, & Wang, C C. On Transport Coefficients of Ferroelectrics

and Onsager Reciprocal Relations. Ferroelectrics (2011). , 423(1), 54-62.

[15] Lavenda, B H. Thermodynamics of Irreversible Processes. London and Basingstoke:

Macmillan; (1978).

[16] Chewasatn, S, & Milne, S T. Synthesis and Characterization of PbTiO3 and Ca and Mn
Modified PbTiO3 Fibres Produced by Extrusion of Diol Based Gels. Journal of Material
Science (1994). , 29(14), 3621-3629.

[17] Nomura, S, & Sawada, S. Dielectric Properties of Lead-Strontium Titanate. Journal of

the Physical Society of Japan (1955). , 10(2), 108-111.

[18] Mante, A, & Volger, H. J. The Thermal Conductivity of PbTiO3 in the Neighbourhood
of Its Ferroelectric Transition Temperature. Physics Letters A (1967). , 24(3), 139-140.

[19] Dec, J. The Phase Boundary as a Kink. Ferroelectrics (1989). , 89(1), 193-200.

[20] Gordon, A. Propagation of Solitary Stress Wave at First-Order Ferroelectric Phase

Transitions. Physics Letters A (1991).

[21] Ai, S T, Zhang, S Y, Ning, X F, Wang, Y L, & Xu, C T. Non-Equilibrium Thermodynamic

Explanation of Domain Occurrences in Ferroics. Ferroelectrics Letters Section (2010). ,
37(2), 30-34.

[22] Janovec, V. A Symmetry Approach to Domain Structures. Ferroelectrics (1976). , 12(1),

43-53.

[23] Wadhawan, V K. Ferroelasticity and Related Properties of Crystals. Phase Transitions

(1982). , 3(1), 3-103.

[24] Glansdoff, P, & Prigogine, I. Thermodynamic Theory of Structure, Stability and

Fluctuation. New York: Wiley-Interscience; (1971).

[25] Maugin, G A, & Muschik, W. Thermodynamics with Internal Variables (I) General
Concepts, (II) Applications. Journal of Non-Equilibrium Thermodynamics (1994).

[26] Jou, D, Casas-vázquez, J, & Lebon, G. Extended Irreversible Thermodynamics ( 3rd

edition ). Berlin: Springer; (2001).
 Chapter 3

Pb(Mg1/3Nb2/3)O3 (PMN) Relaxor: Dipole Glass or Nano-

Domain Ferroelectric?

Desheng Fu, Hiroki Taniguchi, Mitsuru Itoh and

Shigeo Mori

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52139

1. Introduction

In sharp contrast to normal ferroelectric (for example BaTiO3), relaxors show unusually
large dielectric constant over a large temperature range (~100 K) (Fig. 1 (a)) [1,2]. Such large
dielectric response is strongly dependent on the frequency. Its origin has been the focus of
interest in the solid-state physics. Unlike the dielectric anomaly in BaTiO3, which is associat‐
ed with a ferroelectric phase transition, the maximum of dielectric response in relaxor does
not indicate the occurrence of a ferroelectric phase transition. Such huge dielectric response
suggests that local polarization might occur in the crystal. This was envisioned by Burns and
Dacol from the deviation from linearity of refractive index n(T) (Fig. 1(c)) around the so-
called Burns temperature (TBurns) [3] because the deviation Δn is proportional to polarization
Ps. The local polarization is suggested to occur in a nano-region, and is generally called as
polar nano-region (PNR). The existence of PNR in relaxor is well confirmed from the neu‐
tron scattering measurements [4] and transition electron microscopy (TEM) observation.
However, it is still unknown how PNRs contribute to the large dielectric response. More re‐
cently, it is also suggested that a strong coupling between zone-center and zone-boundary
soft-modes may play a key role in understanding the relaxor behaviors [5]. Clearly, the
question “what is the origin of the giant dielectric constant over a broad temperature
range?”is still unclear [6,7].
Another longstanding issue on relaxors is how PNRs interact at low temperature. There are
two acceptable models: (1) dipole glass model [2,8-11], and (2) random-field model [12,13].
In spherical random-bond–random-field (SRBRF) model, Pirc and Blinc assumed that PNRs
are spherical and interact randomly and proposed a frozen dipole glass state for relaxor
(Fig. 2(a)) [10,11]. It predicts that the scaled third-order nonlinear susceptibility a3=-ε3/ε14 will

© 2012 Fu et al.; licensee InTech. This is an open access article distributed under the terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
52 Advances in Ferroelectrics

shows a nearly divergent behavior at the freezing temperature Tf of the spherical glass
phase. In sharp contrast, the random field model of Fisch [13], which assumes non-random
two-spin exchange, predicts a ferroelectric or ferroelectric domain state in relaxor (Fig. 2(b)).
This random Potts field model also predicts a broadening specific heat peak for the glass
phase and shows that the latent heat at ferroelectric transition Tc is so small that it may be
difficult to be detected, which reasonably explains the data reported by Moriya et al. [14].
Combining our recent results [15] from the electrical polarization, Raman scattering, TEM
measurements and those reported in the literature, here, we propose a physical picture to
understand the dielectric behaviors of Pb(Mg1/3Nb2/3)O3 (PMN) relaxor.

Figure 1. Temperature dependence of (a) linear dielectric constant [9], (b) cold [35] & thermal [4] neutrons diffuse
intensities, and (c) refractive index [3] for PMN relaxor crystal.

2. Multiple inhomogeneities in relaxors

PMN is a prototypical relaxor with A(B’,B”)O3 perovskite structure (Fig. 3), in which B-sites
are occupied by two kinds of heterovalent cations. Such chemical inhomogeneity is a com‐
mon feature of relaxor crystals. Although it remains an average centrosymmetric cubic struc‐
ture down to 5 K [16], local structural inhomogeneity has been detected in PMN relaxor. In
addition to PNR mentioned above, chemically ordering region (COR) [17-19] with size of sev‐
 Pb(Mg1/3Nb2/3)O3 (PMN) Relaxor: Dipole Glass or Nano-Domain Ferroelectric? 53
http://dx.doi.org/10.5772/52139

eral nm has been observed in PMN crystal by TEM. It should be noticed that PNR and COR
belong to different symmetry groups and are considered to have non-centrosymmetry ofR3m
and centrosymmetryofFm3̄m, respectively. Therefore, there is spontaneous polarization Ps
along the <111>c direction of pseudocubic structure in PNRs [20,21], but none of Ps exists in
CORs. In addition to chemical and structural inhomogeneities, we will show that PMN relax‐
or also has inhomogeneity of ferroelectric domain structure. Multiple inhomogeneities are
thus considered to play a crucial role in inducing the intriguing behaviors in relaxors.

(a) dipole glass model 3.0 (b) random field model

~
D=0 2.5
paraelectric paraelectric
2.0

1 1.5
T/J
T/J

paraelectric glass
1.0
spherical ferroelectric ?
dipole glass
~/
D=0 0.5 [1,0]
[1,1]
domain ferroelectric
ferroelectric
0 0.0
0 1 0 2 4 6 8 10
J0/J h/J

Figure 2. Two phase diagrams proposed for relaxor by (a) a dipole glass model [10], and (b) a random field model [13].

Figure 3. (a) ABO3perovskite structure. (b) Model for relaxor structure. PNR and COR represent the polar nano-region
and chemically order region, respectively. (c) &(d) show two models of atom arrangement for COR. To maintain the
electric neutrality, a Nb-rich layer is required for case (c).
54 Advances in Ferroelectrics

3. Evolution of the electrical polarization and origin of the huge dielectric

responses

In order to understand the nature of the huge dielectric response and the ground state of the
electrical polarization in PMN, it is essential to know the polarization hysteresis of all states
including virgin state in PMN crystal. Although there are many reports on the polarization
hysteresis of PMN crystal, there is a lack of understanding of the polarization hysteresis of
the virgin state. In our polarization measurements, in order to access the virgin state of the
crystal at a temperature, it was firstly annealed at 360 K and then cooled to the desired tem‐
perature for the measurements.

Figure 4 shows the D-E hysteresis at three typical temperatures observed for (110)c-cut PMN
crystal At T=360 K that is greatly higher than the freezing temperature Tf=224 K assumed for
PMN crystal [9],there is no remnant polarization within the experimental time scale of τ~10
ms (one cycle of the D–E loop) and the polarization is history-independent, indicating that
the crystal is macroscopically paraelectric at this temperature. When temperature is lower
than room temperature (for example, T=250 K), remnant polarization was observed but it
generally disappears after removing the electric field.

Upon further cooling to temperatures lower than ~220 K,PMN shows polarization hysteresis
similar to that of normal ferroelectric [22]. Fig. 4(a) shows an example of the characteristic
hysteresis loop in this temperature range. In the virgin state as indicated by the thick red
line, it appears that there is no remnant polarization in the crystal at zero electric field. How‐
ever, as increasing the electric field, we can see the gradual growth of the polarization. This
is a characteristic behavior of the polarization reversal (switching) in ferroelectric. When the
applied field is larger than the coercive field Ec, ferroelectric domains are aligned along the
direction of the electric field, leading to a stable macroscopic polarization in the crystal. This
is evident from the fact that the remnant polarization is identical to the saturation polariza‐
tion. These results clearly indicate that PMN is a ferroelectric rather than a dipole glass at
temperature lower than 220 K.

There are many reports on the electric-field induced phase transition in PMN. On the basis
of the change of dielectric constant under the application of a DC electric field, Colla et al.
proposed an E-T phase diagram for PMN [8], which suggests a phase transition from a glass
phase to a ferroelectric phase at a critical field of Et=1. 5kV/cm in the temperature range of
160 K - 200 K. However, from our polarization results, we cannot find such a critical field
except the coercive field Ec. If we assume that Ec is the critical field, then its value completely
disagrees with the reported value. We observed that Ec increases rapidly with lowering the
temperature, for example, Ec can reach a value of ~11 kV/cm at 180 K, which is about 7 times
of Et. Moreover, Ec is strongly dependent on frequency (Fig. 4b), and has an exponential
form(1/f∝ exp (α/Ec) (Fig. 4c), which will result in an undefined critical field if we assume
Ec=Et because Ec is dependent on the measurement time-scale.
 Pb(Mg1/3Nb2/3)O3 (PMN) Relaxor: Dipole Glass or Nano-Domain Ferroelectric? 55
http://dx.doi.org/10.5772/52139

Figure 4. (a) Polarization hysteresis in PMN crystal at 190 K, 250 K, 360K. (b) Frequency dependence of polarization
hysteresis. (c) Relationship between frequency and coercive field determined from the peak of switching currents. Su‐
perscript i denotes the value observed for the virgin state.

As discussed in following, ferroelectric micro-domain and soft-mode behaviors have also

been observed at zero field in PMN in our measurements. Also, lowering of symmetry of
local structure at zero field was also revealed around 210 K by a NMR study [21]. All these
results direct to the fact of occurrence of a ferroelectric state at zero field in PMN crystal. We
therefore consider that it is more rational to attribute Ec to the coercive field required for the
domain switching rather than the critical field for a field-induced phase transition. In fact,
the exponential relationship of coercive field with frequency is well-known as Merz’s law
(f=1/τ∝exp(-α/Ec), τ=switching time, α=activation field) [23-28] in the normal ferroelectrics
(for example, BaTiO3,TGS) [23,24]. Using this relationship, the activation field is estimated to
be 83. 5 kV/cm for PMN crystal at 200 K (Fig. 4c), which is one order of magnitude greater
than that of the BaTiO3 crystal. This indicates that the domain switching in PMN become
more and more difficult as lowering temperatures. For example, when an electric field of 1
kV/cm is applied to the crystal at 200 K, an unpractical time of 2. 3×1029s (~7. 3×1021 years) is
required for the domain switching. Actually, it is impossible to observe the spontaneous po‐
larization by this weak field within a limit time at this temperature.
56 Advances in Ferroelectrics

The high-resolution data of the polarization obtained by a 14-bit oscilloscope allow us to cal‐
culate the linear and nonlinear dielectric susceptibilities (defined by the expansion P=ε0(χ1E
+χ3E3+ )) directly from the D-E hysteresis by differentiating the polarization with respective
to the electric field. The calculated results are summarized in Fig. 5 for various electric fields
in the virgin state and the zero electric field after the polarization reversal. These results al‐
low us to have a deep insight into the nature of abnormal dielectric behaviors and the phase
transition in PMN relaxor. Fig. 5(a) shows the linear dielectric response for the virgin state in
various electric fields. When comparing the response obtained at zero field with that ob‐
tained by LCR meter at the frequency corresponding to the sampling rate used in D-E hyste‐
resis measurements, one might find that they both behavior in the same way with the
temperature. As mentioned above that the polarization response under the electric field in
the virgin state is essentially due to the polarization reorientation, we therefore can reasona‐
bly attribute the dielectric anomaly usually observed in PMN relaxor to the polarization re‐
orientation. This indicates that the reorientation of the PNRs dominates the huge dielectric
response in PMN relaxor. Fig. 5 (a) also shows that the peak of dielectric response shifts to
lower temperature at a higher electric field. This means that the activation field required for
domain switching increases with lowering the temperature.

The nonlinear dielectric susceptibility ε3v and its scaled value a3v for the virgin state are given
in Fig. 5(c) and (d), respectively. ε3vshows a broad peak around 255 K, which is in good agree‐
ment with those obtained by Levstik et al. using a lock-in to wave analyzer technique for vari‐
ous frequencies [9]. Levstik et al. attributed this behavior to the freezing of dipole glass at
Tf=224 K in PMN. However, this picture is inconsistent with the results shown in the above
polarization measurements, which indicates that PMN relaxor is ferroelectric but not glass at
T<Tf. Such dipole glass picture is also excluded by the results of the scaled susceptibility a3
shown in Fig. 5(d), and those reported in the previous studies [29, 30]. We can see that there is
no divergent behavior of a3 in PMN relaxor. This result again suggests that there is no freez‐
ing of dipole glass in PMN as predicted for the dipole glass model. The observed anomaly of
nonlinear dielectric susceptibility around 255 K is more consistent with the phase diagram of
the random field model proposed by Fisch [13], in which a glass phase occurs between the
paraelectric phase and the ferroelectric phase in relaxors. Such anomaly of nonlinear dielec‐
tric susceptibility may be a manifestation of spherical dipole glass with random interaction
used in SRBRF model, and its nature requires further theoretical investigations.

In the random field model, the ferroelectric phase transition is suggested to be smeared due
to the quenched random fields, but it may be visible if the random fields are overcome by an
external electric field [12]. This ferroelectric phase transition has been convincingly shown
by the sharp peak of the linear dielectric susceptibility ε1p (Fig. 5(b)) and the anomaly of its
nonlinear components ε3p and a3p (solid circles in Fig. 5(c) and (d)) when ferroelectric do‐
mains are aligned by an external field. The sharp peak of linear susceptibility indicates that
the ferroelectric phase transition occurs at T=Tc=225 K, around which Curie-Weise law was
observed. The value of Curie constant is estimated to be C = 2. 05 *105 K, which is character‐
istic of that of the displacive-type phase transition, suggesting a soft mode-driven phase
transition in this system. This conclusion is supported by the occurrence of soft–mode in the
crystal observed by neutron [31] and Raman scattering measurements [32].
 Pb(Mg1/3Nb2/3)O3 (PMN) Relaxor: Dipole Glass or Nano-Domain Ferroelectric? 57
http://dx.doi.org/10.5772/52139

Figure 5. Dielectric responses in PMN crystal. (a) Chang of linear dielectric responses (ε1=∂D/∂E|E) with the electric field
for the virgin state. Inset shows an example of the polarization and dielectric responses, in which the thick lines indicate
the virgin state. Dielectric constant obtained by LCR impedance measurements at an ac level of 1 V/cm (red solid line) is
also shown for comparison. (b) Linear dielectric response (ε1p=∂D/∂E|E=0) at zero field after the polarization reversal (indi‐
cated by the square in inset of (a)), and its inverse. (c) Nonlinear dielectric constant(ε3=∂3D/∂3E|E=0) at zero field for the vir‐
gin state, and the state after the polarization reversal. (d) The corresponding a3=ε3/ε14|E=0 for these two states.
58 Advances in Ferroelectrics

Here, we can see that there are two characteristic temperatures in relaxors: Burns tempera‐
ture TBurns and ferroelectric phase transition temperature Tc. AtTBurns, local polarizations
(PNRs) begin to occur. Before the ferroelectric transition occurs, PNRs are dynamic, and more
importantly, interactions among them are random. Consequently, the existence of PNRs be‐
tween Tc and TBurns can be considered as precursor phenomenon in a phase transition [33]. Ac‐
tually, such precursor phenomenon has also been observed in the normal ferroelectric
BaTiO3at temperatures far above Tc[34]. A difference between BaTiO3 and PMN relaxor is that
the temperate region of precursor existence in PMN is greatly lager than in BaTiO3. To probe
the precursor behavior, one has to consider the time scale used. For example, we cannot de‐
tect a spontaneous polarization at ms scale by D-E measurements for PMN at room tempera‐
ture, but at the probe time scale of 2 ns, cold neutron high-flux backscattering spectrometer
can detect PNRs up to ~400K [35] (Fig. 1b). In contrast, due to a shorter probe time scale of ~6
ps [4], thermal neutron scattering can probe PNRs up to 600 K, which is close to TBurns deter‐
mined by the optical measurements that have the shortest probe time scale.

4. Soft mode behaviors in PMN relaxor

In the displacive-type ferroelectrics, soft-modes should occur in the lattice dynamics of the
crystal. Actually, in a study of neutron inelastic scattering, a FE soft mode was revealed to re‐
covers, i. e., becomes underdamped, below 220 K, and from there its energy squared (ħωs)2 in‐
creases linearly with decreasing T as for normal FEs below Tc(see also Fig. 6(e)) [31]. This has
long been a puzzle for PMN relaxor: how can this be, since it has been thought that PMN re‐
mains cubic to at least 5 K [16]? However, such soft-mode behavior is exactly consistent with
our results from polarization measurements shown in previous section, which show a ferro‐
electric phase transition at Tc~225 K. Our Raman scattering measurements also support the oc‐
currence of FE softmode in PMN relaxor [32].

In Raman scattering studies for relaxors, the multiple inhomogeneities due to the coexistence
of different symmetry regions such as the PNR and COR has been a tremendous barrier to
clarify the dynamical aspect of relaxor behavior in PMN. In particular, the intense tempera‐
ture-independent peak at 45 cm−1 (indicated by↓in Fig. 6(a)), which stems from the COR with
Fm3̄m [32], always precludes a detailed investigation of low-wave number spectra of PMN
crystal. Our angular dependence of the Raman spectra together with the results from the
Raman tensor calculations clearly indicate that the strong F2gmode located at 45 cm−1 can be
eliminated by choosing a crossed Nicols configuration with the polarization direction of the
incident laser along <110>c direction (see right panel in Fig. 6(c)).

Such special configuration allows us to observe the other low-wave number modes easily. Fig.
6 (d) shows the spectra obtained by this configuration. At the lowest temperature, a well-de‐
fined mode can be seen from the spectrum, which softens as increasing the temperature, indi‐
cating the occurrence of FE soft mode in PMN relaxor. Due to the multiple inhomogeneities of
the system, the shape of soft-mode of PMN relaxor is not as sharp as that observed in normal
displacive-type ferroelectrics. However, we still can estimate its frequency reliably from the
careful spectrum analysis. Its temperature dependence is shown in Fig. 6(e) (indicated by ●)
in comparison with the results obtained by neutron inelastic scattering (○) [31].
 Pb(Mg1/3Nb2/3)O3 (PMN) Relaxor: Dipole Glass or Nano-Domain Ferroelectric? 59
http://dx.doi.org/10.5772/52139

Figure 6. a) Room-temperature Raman spectra in PMN observed by the parallel (upper panel) and crossed (bottom
panel) Nicols configurations, with the polarization direction of the incident laser parallel to <100>c(P // <100>c). (b)
Scattering configurations used in measurements on the angular dependence of the Raman spectra. (c) Angular de‐
pendence of the low-wave number Raman spectra obtained at room temperature. (d) Temperature dependence of
Raman spectra observed by the crossed Nicols configuration with the polarization direction of the incident laser along
<110>c direction (P // <110>c). (e) Soft mode wave numbers obtained by Raman scattering (●) and by neutron inelas‐
tic scattering by Wakimoto et al. (○) [31].
60 Advances in Ferroelectrics

Figure 7. a)-(c) Temperature variation of TEM images observed for PMN relaxor. (a’)-(c’) & (a”)-(c”) show images of
PNR and COR derived from (a)-(c). (d)Micrometric domain structure observed in the ferroelectric phase at 130K. (e)
Schematic domain patterns shown in (d). Arrows and lines indicate the polarization directions and domain bounda‐
ries, respectively.

We find that the soft-mode exhibits softening towards Tc on heating and follows the conven‐
tional Curie–Weiss law (solid line) over a large temperature region. However, upon further
heating, the soft mode becomes over damped in a temperature region extending over ∼200
K, which does not allow us to estimate the frequency of the mode. At temperatures above
480 K, the soft mode recovers the under damped oscillation and hardens as the temperature
increases. These phenomena are very similar to those revealed by neutron inelastic scatter‐
ing [31]. A major difference is that the wave number of the soft mode in the present study is
significantly lower than that observed by the neutron inelastic scattering. This can be rea‐
sonably understood by the splitting of the soft mode due to the lowering of symmetry as
 Pb(Mg1/3Nb2/3)O3 (PMN) Relaxor: Dipole Glass or Nano-Domain Ferroelectric? 61
http://dx.doi.org/10.5772/52139

demonstrated in the NMR study [21]. According to previous results, the local symmetry in
the PNR changes from cubic to rhombohedral. Therefore, the soft mode can be assumed to
split from the F1u mode to the A1 and E modes. Generally, the A1 mode is higher in wave
number than the E mode due to the depolarization field effect.

In a short summary, we may say that the polarization in PMN is induced by the soft mode.
This interpretation is essentially consistent with the results described in the polarization
measurements, and the results obtained in previous neutron studies [36, 37], in which the
crystallographic structure of PNR is attributed to the displacement pattern of the soft mode.
The results of the Raman study also support that a ferroelectric state exists in PMN even at
the zero-bias field.

5. Ferroelectric domain structures observed by TEM

In order to understand the microstructures of COR and PNR together with the domain
structures and its evolution with temperature in the ferroelectric phase of PMN relaxor, we
have carried out a detailed TEM observation. The typical results are summarized in Fig. 7.
As shown in Fig. 7 (a”)-(c”), COR was found to be spherical shape and has size less than 5
nm. It is very stable and remains unchanged within the temperature range of 130 K-675K. In
the TEM observation, large amount of CORs were found to distribute in the PMN crystal. In
a previous HRTEM study, its volume fraction has been estimated to be ~1/3 of the crystal
[18]. CORs are thus considered to be the intense sources of the strong random fields.

30
Elliptical Sperical TEM
Yohsida et al.
20
Indensity

Indensity
Size (nm)

10
(a) Size
0
0 100 200 300 400 500 600
10 100
Neutrons
Correlation length x (nm)

(b) Xu. et al. PRB69

I0/x3~N |Qd|2

064112

N |Qd|2
5 x Tc ~Number of PNR
50

0 0
0 100 200 300 400 500 600
T (K)

Figure 8. Temperature variation of PNR observed by (a) TEM [38]and (b) Neutron scattering [4]. In (b), ξ is the correla‐
tion length, and I0 is the integrated diffuse scattering intensity and can be written to Nξ3|Qδ|2, where N is the total
number of PNR, δ is the average displacement of atoms within the PNR, and Q is the wave vector.
62 Advances in Ferroelectrics

In contrast to CORs, PNRs exhibit remarkable change with temperature. As shown in Fig.
7(a’)-(c’) and Fig. 8, PNRs with size of several nm were found to occur in the crystal for
T<TBurns. These spherical PNRs show continuous growth as lowering the temperature. How‐
ever, PNRs change from spherical shape to elliptical shape around Tc. Associating with the
change in shape, its intensity was also found to drop rapidly. These results are consistent
with those derived from neutron scattering (Fig. 8(b)) [4]. Neutron scattering study by Xu et
al. [4] shows that the ‘‘correlation length’’ ξ, which is a direct measure of the length scale of
the PNR, increases on cooling and changes remarkably around Tc. At the same time, the
number of PNR increases on cooling from high temperatures and then drops dramatically at
around Tc, remaining roughly constant below Tc.
Associating with the change in the number and the shape of PNR, micrometric ferroelectric
domains were found to occur for T<Tc. It is because of growing into macroscopic domain that
the number of PNR drop sharply in the ferroelectric phase. Figs. 7(d) and (e) show the struc‐
ture of a FE micrometric domain in the FE phase of 130 Kand its schematic patterns, respec‐
tively. The micrometric domains are formed in the crystal with the spontaneous Ps along the
<111>c direction. In comparison with the domain structure of normal ferroelectric such as Ba‐
TiO3, domain size is relatively small and the domain boundaries blur in PMN relaxor.

40

Uesu et al.JKPS 29( S703)

Jeong et al PRL94(147602)
Volume fraction (%)

PC(a/b=1:3)
20

TC
0
0 100 200 300 400 500 600 700
T (K)

Figure 9. Volume fraction of PNR estimated from neutron scattering measurements [37,39]. Solid line denotes the
threshold of percolation for elliptical shape [40].

The occurrence of micrometric domains, the soft-mode observed by Raman scattering, and
the macroscopic polarization all direct to the same conclusion: PMN is essentially ferroelec‐
tric but not dipole-glass at T<Tc although it exhibits some unique characteristic properties
including broadening soft-mode, smearing domain wall, and very large activation field re‐
quired for domain switching. Our TEM measurements clearly indicate that interactions
among PNRs for T<Tc are not random, but cooperative, which is different from the picture
expected in the SRBRF model [10]. It is due to such non-random interaction, PNRs team up
 Pb(Mg1/3Nb2/3)O3 (PMN) Relaxor: Dipole Glass or Nano-Domain Ferroelectric? 63
http://dx.doi.org/10.5772/52139

together to form micrometric domain in the FE phase. Thus, our TEM observations support
the random field model suggested by Fisch [13]. It should be emphasized that PNRs cannot
merge together completely due to the blocking of the intense CORs in the crystal (Fig. 10).

Here, we made a discussion on the volume fraction of PNRs in PMN crystal. Neutron scatter‐
ing technique has been used to estimate the volume fraction of PNRs. Fig. 9 replots two re‐
sults reported by Jeong et al. [37] and Uesu et al. [39], respectively. Both studies indicate that
PNRs occupy a volume fraction > 25% at the lowest measurement temperature. This volume
fraction is larger than the threshold of 22% to form a percolated ferroelectric state with an el‐
lipsoidal-shape [40], supporting again the picture of a ferroelectric state in PMN relaxor.

Figure 10. A physics picture of structure evolution in PMN relaxor.

6. A physics picture of relaxor

In summary, we propose a physics picture for relaxors. Figure 10 schematically shows a

model of structure evolution in PMN relaxor. Since COR has been observed at T>TBurns, it can
be considered that there is a coexistence of paraelectric phase of COR with Fm3̄m symmetry
and paraelectric Pm3̄mphasein this high temperature. Upon cooling, spherical PNRs occur
from paraelectric Pm3̄m phase for T<TBurns. Both number and size of PNR increase as lower‐
ing the temperature. Around room temperature, PNRs grow to a size of about 10 nm. For
T<Tc (~225K), neighboring PNRs merge together to form elliptical shape with anisotropy, as‐
sociating with the reduction of its number. Due to the blocking by the intense CORs, indi‐
vidual PNR merely grows to a size of about 20 nm at T<Tc. However, PNRs with elliptical
64 Advances in Ferroelectrics

shape tend to team up together to form a larger domain at T<Tc at which a ferroelectric state
occurs. The existence of a multi-scale inhomogeneity of ferroelectric domain structure pro‐
vides a key point to understand the huge electromechanical coupling effects in relaxors and
piezoelectrics with morphotropic phase boundary (MPB). This also gives idea to design new
material with domain structure to have large elastic deformation with the application of an
electric or magnetic field [41].

Acknowledgements

We thank Mr. M. Yoshida, Prof. N. Yamamoto and Prof. Shin-ya Koshihara of Tokyo Insti‐
tute of Technology for their contributions in this work. We acknowledge the support of a
Grant-in-Aid for Scientific Research, MEXT, Japan.

Author details

Desheng Fu1*, Hiroki Taniguchi2, Mitsuru Itoh2 and Shigeo Mori3

*Address all correspondence to: ddsfu@ipc. shizuoka. ac. jp

1 Division of Global Research Leaders, Shizuoka University, Johoku, Naka-ku, Hamamatsu,

Japan

2 Materials and Structures Laboratory, Tokyo Institute of Technology, Nagatsuta, Yokoha‐

ma, Japan

3 Department of Materials Science, Osaka Prefecture University, Sakai, Osaka, Japan

References

[1] Smolenskii, G. A., Agranovskaia, A. I. Sov. Phys. Tech. Phys. (1958), 3, 1380.
[2] Cross, L. E. Relaxor ferroelectrics: An overview. Ferroelectrics (1994), 151, 305-320.
[3] Burns, G., Dacol, F. H. Glassy polarization behavior in ferroelectric compounds
Pb(Mg1/3Nb2/3)O3 and Pb(Zn1/3Nb2/3)O3 . Solid State Commun. (1983), 48, 853-856.
[4] Xu, G., Shirane, G., Copley, J. R. D. , Gehring, P. M. Neutron elastic diffuse scattering
study of Pb(Mg1/3Nb2/3)O3. Phys. Rev. B (2004), 69, 064112.
[5] Swainson, I. P., Stock, C., Gehring, P. M., Xu, G., Hirota, K., Qiu, Y., Luo, H., Zhao,
X., Li, J.-F., Viehland, D., Soft phonon columns on the edge of the Brillouin zone in
the relaxor PbMg1/3Nb2/3O3. Phys. Rev. B (2009), 79, 224301.
 Pb(Mg1/3Nb2/3)O3 (PMN) Relaxor: Dipole Glass or Nano-Domain Ferroelectric? 65
http://dx.doi.org/10.5772/52139

[6] Vugmeister, B. E. Polarization dynamics and formation of polar nanoregions in relax‐

or ferroelectrics. Phys. Rev. B (2006), 73, 174117.
[7] Grinberg, I., Juhas, P., Davies, P. K., Rappe, A. M. Relationship between local struc‐
ture and relaxor behavior in perovskite oxides. Phys. Rev. Lett. (2007), 99, 267603.
[8] Colla, E.V., Koroleva, E. Yu., Okuneva, N. M., Vakhrushev, S. B. Long-time relaxa‐
tion of the dielectric response in lead magnoniobate. Phys. Rev. Lett. (1995), 74,
1681-1684.
[9] Levstik, A., Kutnjak, Z., Filipič, C., Pirc, R. Glassy freezing in relaxor ferroelectric
lead magnesium niobate. Phys. Rev. B (1998), 57, 11204-11211.
[10] Pirc, R., Blinc, R. Spherical random-bond–random-field model of relaxor ferroelec‐
trics. Phys. Rev. B (1999), 60, 13470-13478.
[11] Bobnar, V., Kutnjak, Z., Pirc, R., Blinc, R., Levstik, A. Crossover from glassy to inho‐
mogeneous-ferroelectric nonlinear dielectric response in relaxor ferroelectrics. Phys.
Rev. Lett. (2000), 84, 5892-5895.
[12] Westphal, V., Kleemann, W., Glinchuk, M. D. Diffuse phase transitions and random-
field-induced domain states of the ‘‘relaxor’’ ferroelectric PbMg1/3Nb2/3O3. Phys. Rev.
Lett. (1992), 68, 847.
[13] Fisch, R. Random-field models for relaxor ferroelectric behavior. Phys. Rev. B 2003;
67, 094110.
[14] Moriya, Y., Kawaji, H., Tojo, T., Atake, T. Specific-heat anomaly caused by ferroelec‐
tric nanoregions in Pb(Mg1/3Nb2/3)O3 and Pb(Mg1/3Ta2/3)O3 relaxors. Phys. Rev. Lett.
(2003), 90, 205901.
[15] Fu, D., Taniguchi, H., Itoh, M., Koshihara, S., Yamamoto, N., and Mori S. Relaxor
Pb(Mg1/3Nb2/3) O3: A ferroelectric with multiple inhomogeneities. Phys. Rev. Lett.
(2009), 103, 207601.
[16] Mathan, N. de, Husson, E., Calvarn, G., Gavarri, J. R., Hewat, A. W., Morell, A. A
structural model for the relaxor PbMg1/3Nb2/3O3 at 5 K. J. Phys. Condens. Matter (1991),
3, 8159.
[17] Hilton, A. D., Barber, D. J., Randall, C.A., Shrout, T. R. On short range ordering in the
perovskite lead magnesium niobate. J. Mater. Sci. (1990), 25, 3461-3466.
[18] Boulesteix, C., Varnier, F., Llebaria, A., Husson, E. Numerical determination of the
local ordering of PbMg1/3Nb2/3O3 (PMN) from high resolution electron microscopy
images. J. Solid State Chem. (1994), 108, 141-147.
[19] Chen, J., Chan, H. M., Harmer, M. P. Ordering structure and dielectric properties of
undoped and La/Na-doped Pb(Mg1/3Nb2/3)O3. J. Am. Ceram. Soc. (1989), 72, 593-598.
[20] Jeong, I. K., Darling, T. W., Lee, J. K., Proffen, Th., Heffner, R. H., Park, J. S., Hong, K.
S., Dmowski, W., Egami, T. Direct observation of the formation of polar nanoregions
66 Advances in Ferroelectrics

in Pb(Mg1/3Nb2/3)O3 using neutron pair distribution function analysis. Phys. Rev. Lett.
(2005), 94, 147602.

[21] Blinc, R., Laguta, V. V., Zalar, B. Field cooled and zero field cooled 207Pb NMR and
the local structure of relaxor PbMg1/3Nb2/3O3. Phys. Rev. Lett. (2003), 91, 247601.

[22] Wieder, H. H. Electrical behavior of barium titanatge single crystals at low tempera‐
tures. Phys. Rev. (1955), 99, 1161-1165.

[23] Wieder, H. H. Activation field and coercivity of ferroelectric barium titanate. J. Appl.
Phys. (1957), 28, 367-369.

[24] Wieder, H. H. Ferroelectric polarization reversal in rochelle salt. Phys. Rev. (1958),
110, 29-36.

[25] Merz, W. J. Domain formation and domain wall motions in ferroelectric BaTiO3 sin‐
gle crystals. Phys. Rev. (1954), 95, 690-698.

[26] Fatuzzo, E., Merz, W. J. Switching mechanism in triglycine sulfate and other ferro‐
electrics. Phys. Rev. 1959; 116, 61-68.

[27] Fatuzzo, E. Theoretical Considerations on the Switching transient in ferroelectrics.

Phys. Rev. (1962), 127, 1999-2005.

[28] Shin, Y-H., Grinberg, I., Chen, I-W., Rappe, A. M. Nucleation and growth mechanism
of ferroelectric domain-wall motion. Nature (2007), 449, 881-884.

[29] Glazounov, A. E., Tagantsev, A. K. Phenomenological model of dynamic nonlinear

response of relaxor ferroelectrics. Phys. Rev. Lett. (2000), 85, 2192-2195.

[30] Dec, J., Miga, S., Kleemann, W., Dkhil, B. Nonlinear dielectric properties of PMN re‐
laxor crystals within Landau-Ginzburg-Devonshire approximation. Ferroelectrics
(2008), 363, 141-149.

[31] Wakimoto, S., Stock, C., Birgeneau, R. J., Ye, Z.-G., Chen, W., Buyers, W. J. L., Gehr‐
ing, P. M., Shirane, G. Ferroelectric ordering in the relaxor Pb(Mg1/3Nb2/3)O3 as evi‐
denced by low-temperature phonon anomalies. Phys. Rev. B (2002), 65, 172105.

[32] Taniguchi, H., Itoh, M., Fu, D. Raman scattering study of the soft mode in
Pb(Mg1/3Nb2/3)O3. J. Raman Spectrosc. (2010), 42, 706-714.

[33] Bussmann-Holder, A., Beige, H., Völkel, G. Precursor effects, broken local symmetry,
and coexistence of order-disorder and displacive dynamics in perovskite ferroelec‐
trics. Phys. Rev. B (2009), 79, 184111.

[34] Tai, Z. R., Namikawa, K., Sawada, A., Kishimoto, M., Tanaka, M., Lu, P., Nagashima,
K., Maruyama, H., Ando, M. Picosecond view of microscopic-scale polarization clus‐
ters in paraelectric BaTiO3. Phys. Rev. Lett. (2004), 93, 087601.

[35] Gehring, P. M., Hiraka, H., Stock, C., Lee, S.-H., Chen, W., Ye, Z.-G., Vakhrushev, S.
B., Chowdhuri, Z. Reassessment of the Burns temperature and its relationship to the
 Pb(Mg1/3Nb2/3)O3 (PMN) Relaxor: Dipole Glass or Nano-Domain Ferroelectric? 67
http://dx.doi.org/10.5772/52139

diffuse scattering, lattice dynamics, and thermal expansion in relaxor

Pb(Mg1/3Nb2/3)O3. Phys. Rev. B (2009), 79, 224109.

[36] Hirota, K., Ye, Z. G., Wakimoto, S., Gehring, P. M., Shirane, G. Neutron diffuse scat‐
tering from polar nanoregions in the relaxor Pb(Mg1/3Nb2/3)O3. Phys. Rev. B (2002), 65,
104105.

[37] Jeong, I. K., Darling, T. W., Lee, J. K., Proffen, T., Heffner, R. H., Park, J. S., Hong, K.
S., Dmowski, W., Egami, T. Direct observation of the formation of polar nanoregions
in Pb(Mg1/3Nb2/3)O3 using neutron pair distribution function analysis. Phys. Rev. Lett.
(2005), 94, 147602.

[38] Yoshida, M. Study of Pb(Mg1/3Nb2/3)O3 ferroelectric relaxor by Transmission Electron

Microscopy, Undergraduate thesis, Tokyo Institute of Technology, Tokyo, (1996).

[39] Uesu, Y., Tazawa, H., Fujishiro, K., Yamada, Y. Neutron scattering and nonlinear-op‐
tical studies on the phase transition of ferroelectric relaxor Pb(Mg1/3Nb2/3)O3. J. Korean
Phys. Soc. (1996), 29, S703-S705.

[40] Garboczi, E. I., Snyder, K. A., Douglas, J. F. Geometrical percolation threshold of

overlapping ellipsoids. Phys. Rev. E (1995), 52, 819-828.

[41] “Ferroelectrics: Nanoregions team together”, NPG Asia Materials, Feb. 1, 2010, doi:
10.1038/asiamat.2010.17.
 Chapter 4

Self Assembled Nanoscale Relaxor Ferroelectrics

Ashok Kumar, Margarita Correa, Nora Ortega,

Salini Kumari and R. S. Katiyar

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/54298

1. Introduction

Worldwide research on relaxor ferroelectric (RFE) has been carried out since 1950s. There
are several schools in the world who have defined the evolution and origin of relaxor prop‐
erties in the ferroelectric materials in their own way. One common consensus among the sci‐
entists is the presence of polar nano regions (PNRs) i.e. self assembled domains of short
range ordering typically of less than 20-50 nm in the ferroelectric relaxor materials which
causes the dielectric dispersion near the phase transition temperature. Another common ap‐
proach has been also believed among the relaxor ferroelectric scientists i.e. the existence of
random field at nanoscale. Random field model is considered on the experimental and theo‐
retical facts driven from the different dielectric dispersion response under zero field cooled
(ZFC) and field cooled (FC) among the relaxors.

Overall relaxor ferroelectrics have been divided into two main categories such as (i) classical
relaxors (only short range ordering), the most common example is PbMg1/3Nb2/3O3 (PMN),
(ii) Semi-classical relaxor ferroelectrics (a combination of short and long range ordering). In
the latter case, the relaxor properties can be arises due to compositional inhomogeneities, ar‐
tificially induced strain, growth conditions (temperature, pressure, medium, etc.), and due
to different ionic radii mismatched based chemical pressure in the matrix. The local domains
(PNRs) reorientation induces polar-strain coupling which makes RFE the potentially high
piezoelectric coefficient materials widely used in Micro/Nanoelectromechanical system
(MEMS/NEMS). The basic features of the RFE over a wide range of temperatures and fre‐
quencies are as follows (i) dispersive and diffuse phase transition, (ii) partially disordered
structure, (iii) existence of polar nano-ordered regions, etc. over a wide range of tempera‐
tures and frequencies. Physical and functional properties of relaxors are very different from

© 2012 Kumar et al.; licensee InTech. This is an open access article distributed under the terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
70 Advances in Ferroelectrics

normal ferroelectrics due to the presence of self assembled ordered regions in the configura‐
tional disorder matrix.

This article deals with the historical development of the relaxor ferroelectrics, microstructur‐
al origin of RFE, strain mediated conversion of normal ferroelectric to relaxor ferroelectrics,
superlattice relaxors, lead free classical relaxor ferroelectrics, distinction of classical relaxors
and semiclassical ferroelectric relaxors based on the polarization study, and their potential
applications in microelectronic industry.

2. History

Relaxor ferroelectric materials were discovered in complex perovskites by Smolenskii [1] in

early fifties of twentieth centuries. Since then a vast scientific communities have been work‐
ing on relaxor materials and related phenomena but the plethora of mesoscopic and micro‐
scopic heterogeneities over a range of lengths and timescales made difficult to systematic
observations [2]. The microscopic image and the dielectric response of relaxor are qualita‐
tively different for that of normal ferroelectrics. The universal signature of RFE is as follows
[3 - 18]: (i) the occurrence of broad frequency-dependent peak in the real and imaginary part
of the temperature dependent dielectric susceptibility (χ') or permittivity (ε') which shifts to
higher temperatures with increasing frequency, G. A. Smolenskii and A. I. Agranokskaya,
Soviet Physics Solid State 1, 1429 (1959), (ii) Curie Weiss law is observed at temperatures far
above dielectric maxima temperature (Tm), (iii) slim hysteresis loops because polar domains
are nanosized and randomly oriented, (iv) existence of polar nano domains far above Tm, (v)
no structural phase transition (overall structure remains pseudo-cubic on decreasing tem‐
perature but rhombohedral-type distortion occurs in crystal at local level) across Tm in relax‐
ors in contrast with the normal ferroelectric in which phase transition implies a macroscopic
symmetry change,(vii) history dependent functional properties and skin effects (surface be‐
havior is quite different than the interior of the system) (vi) in most cases, relaxor crystal
showed no optical birefringence (either far below the freezing temperature and/or under ex‐
ternal electric field).

As we know ferroelectric and related phenomenon are synonyms of ferromagnetism, anti‐

ferromagnetism, spin glass, and random field model which have been originally studied for
magnetic materials. Relaxors ferroelectrics possess a random field state, as initially proposed
by Westphal, Kleemann and Glinchuk [16-18]. Near Burns temperature, small polar nano re‐
gions start originating in different directions inside the crystal at mesoscopic scale; however,
these polar nano regions are not static in nature at Burns temperature. At low temperature
these polar nanoregions (PNRs) become static and developed a more defined regions called
random field, the nature of these fields are short range order. The evidence of the existence
of nanosized polar domains at temperatures well above the dynamic transition temperature
comes for experimental observations. The presence of these polar nanoregions (PNRs) was
established by measuring properties that depend on square of the polarization (P2) and by
direct imaging with TEM studies. The first evidences came from a report by Burns and Da‐
 Self Assembled Nanoscale Relaxor Ferroelectrics 71
http://dx.doi.org/10.5772/54298

col [5] who studied the electro-optical effect in a PMN crystal. In case of normal FE, the tem‐
perature dependence of the refraction index (n) show a linear decrease of n from the
paraelectric phase down to phase transition temperature (Tc), below Tc n deviates from line‐
arity. The deviation is proportional to the P2 and it increases as the polarization changes
with temperature. Burns and Dacol observed deviation from linear n(T) in relaxor PMN
crystal well above Tm, the onset of the deviation was observed at 620 K, almost 350 K above
Tm. The temperature in which onset of deviation from linearity of n(T) occurs (in any relax‐
or) had been identified in the literature as the Burns temperature (TB or Td).
Electrostriction is a property which depends on P2. Thermal strain in a cubic perovskite has
two components, one due to the linear coefficient of thermal expansion, α, and another due
to electrostriction accounted by the electrostrictive coefficients Qijkl. Measures on the temper‐
ature dependence of thermal expansion in RFE crystals have shown that the contribution
due to electrostriction vanishes only above TB where P=0.
The existence of PNRs well above Tm and the growth of these domains with decreasing tem‐
perature have been demonstrated by TEM [8 - 12]. Transmission electron studies also ac‐
count for the B-cation order in complex perovskites [11 - 12]. Ordering of the B-site cations
occurs if there is sufficiently large interaction energy between neighboring cations.

3. Theory of relaxor ferroelectricity

The general formula of perovskite having A and B-site cations with different charge states can
be written as A′xA′′1−xB′yB′′1−yO3. The randomness occupancy of A′,A′′ and B′,B′′ in A, B site
respectively, depends on the ionic sizes, distribution of cations ordering at sub lattices and
charge of cations. If the charges of cations at B-sites are same it is unlikely to have the polar ran‐
domness at nanoscale. Long range order (LRO) is defined as a continuous and ordered distri‐
bution of the B cations on the nearest neighbor sites. The short coherence length of LRO occurs
when the size of the ordered domains are in a range of 20 to 800 Å in diameter. The long coher‐
ence range of LRO occur when the size of the ordered domains are much greater than 1000 Å.
Randall et al. made a classification of complex lead perovskite and their solid solutions based
on B-cation order studied by TEM and respective dielectric, X-rays and optical properties [11]-
[12]. This classification divides the complex lead perovskites into three subgroups; random oc‐
cupation or disordered, nanoscale or short coherent long-range order and long coherent long-
range order of B-site cations.
Diffuse phase transition behavior is characteristic of the disordered structures. In these
structures, random lattice disorder introduces dipolar impurities and defects that influence
the static and dynamic properties of these materials. The presence of the dipolar entities on a
lattice site of the highly polarizable FE structure, induced dipoles in a region determined by
the correlation length (rc). The correlation length is a measure of the extent of dipoles that
respond in a correlated manner. In normal FE, rc is larger than the lattice parameter (a) and it
is strongly temperature dependent. On decreasing the temperature, a faster increase of rc
promotes growing of polar domains yielding a static cooperative long-range ordered FE
72 Advances in Ferroelectrics

state at T < Tc. This is not the case for RFE where a small correlation length of dipoles leads
to formation of polar nanodomains frustrating the establishment of long-range FE state.
Therefore, the dipolar nanoregions form a dipolar-glass like or relaxor state at low tempera‐
ture with some correlation among nanodomains.

Figure 1. Temperature evolution of dielectric constant showing the characteristic temperatures in RFE. Representative
hysteresis loops for each temperature interval are showed below.

These PNRs are dynamic and they experience a slowing down of their fluctuations at T ≤ Tm.
The dielectric relaxation does not fit the classical Debye relaxation model; instead there is a
distribution of relaxation times related to the sizes of the nanodomains. The temperature de‐
pendence of dielectric constant as shown in Fig. 1 indentifies the main temperatures associ‐
ated with relaxor ferroelectric behavior. These temperatures are TB, Tm and Tf, we already
defined TB and Tm but the definition of Tf follow from the fit of the frequency dispersion of
Tm with the Vogel-Fulcher law [15]. The dynamics of polar nanoregions does not follow Ar‐
rhenius type temperature dependence; instead nice fit of the frequency dispersion for each
relaxor system is obtained with the Vogel-Fulcher law:

f = f 0exp ( - Ea
k B (T m - T f ) ) (1)

where f0 is the attempt frequency which is related to the cut-off frequency of the distribution
of relaxation times, Ea is the activation barrier to dipole reorientation, Tm is the dielectric
maxima temperature, and Tf is the freezing temperature where polarization fluctuations
“frozen-in”.
 Self Assembled Nanoscale Relaxor Ferroelectrics 73
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The temperature dependence of the dielectric constant below TB and in the vicinity of Tm is
normally fitted by the empirical power law [19]:

1
ε (ω, T ) = ( 1
εmax (ω, T ) )(1 + ( T - T max )γ
2δ 2
) (2)

where γ and δ are parameters describing the degree of relaxation and diffuseness of the
transition respectively. The parameter γ varies between 1 and 2, where values closer to 1 in‐
dicate normal ferroelectric behavior whereas values close to 2 indicate good relaxor behav‐
ior. Above TB the inverse of dielectric permittivity is fitted by the Curie-Weiss law:

C
χ= T -Θ
(3)

where C and Θ are the Curie constant and Curie temperature respectively.

Last sixty years of extensive research in the field of relaxor ferroelectrics, several models
have been proposed to explain the unusual dielectric behavior of these materials. Some of
these models are: statistical composition fluctuations [20, 21], superparaelectric model [22],
dipolar glass model [23], random field model [24], spherical random field model [25] etc.
These models can explain much of the experimental observed facts but a clear understand‐
ing of the relaxor nature or even a comprehensive theory is not available yet. Despite the
absence of a comprehensive theory of relaxor ferroelectricity, the literature agree to define
relaxor materials in terms of the existence of polar nano regions as motioned above, these
ordered regions exist in a disordered environment.

4. Strain induced relaxor phenomenon

The influence of epitaxial clamping on ferroelectric properties of thin films to rigid sub‐
strates has been largely studied and successfully explained in a Landau-Ginzburg-Devon‐
shire (LGD) framework [26-30]. However, when the same treatment was applied to RFE,
discrepancies among the predicted values and those observed in experiments were found
[30]. For instance, a downward shift in Tm of PMN films in the presence of compressive in-
plane strain was found, contrary to the expected upward shift. Catalan [30] et al. developed
a model to analyze the influence of epitaxial strain on RFE. This model is based on LGD
theory but assuming a quadratic dependence on (T-Tm), rather than linear, for the first coeffi‐
cient of the free energy. Catalan’s model shows that the shift in Tm for relaxors thin films do
not depend on the sign of the epitaxial mismatch strain, but rather on the thermal expansion
mismatch between substrate and film. Reference [30] also provided a list of compounds
which exhibited shift in Tm when they were grown in film forms. We have already observed
in-plane strain in our Pb(Sc0.5Nb0.25Ta0.25)O3(PSNT)/La0.5Sr0.5CoO3 (LSCO)/MgO heterostruc‐
ture, which may have caused the measured shift of Tm with respect to bulk values [31-33].
74 Advances in Ferroelectrics

We have calculated shift in the peak position of the dielectric maxima of PSNT films com‐
pared to bulk values following the model developed by Catalan et.al. The model is as fol‐
low: In LGD formalism, the thermodynamical potential of a perovskite dielectric thin films
is described as [27-28].

∆G = ( 12 α - Qi3 X i )P32 + 14 βP32 - 12 sij ( X i X j ) (4)

where α and β correspond to linear and nonlinear terms of the inverse permittivity, and sij,
Xi, and Qi3 are the elastic compliances, the stress tensor, and the electrostriction tensor in
Voigt notation; P3 is out of the plane polarization. Strain gradients across the films are ne‐
glected. The inverse permittivity is the second derivative of the free energy with respect to
the polarization:

∂2 ΔG Y
χ3' = ∂P 2
= α - 4Q13 1 - ν xm + 3βP32 (5)

where xm, Y, and ν are the mismatch strain, Young’s modulus, and Poisson’s ratio of the
film respectively. For conventional ferroelectrics, α is usually expanded in a power series
of (T-Tc):

1
α= C ε0 (T - T c ) + f (T - T c )2 (6)

which directly leads to Curie-Weiss behavior, where C is the Curie constant. Substituting α
into the above equation showing that the strain shifts the critical temperature for a ferroelec‐
tric by:

Y
ΔT c = 4Cε0Q13 1 - ν xm (7)

Since Q13 is always negative, it has been observed that the shift in the critical temperature
depends on the sign of in-plain strain: Tc decreases for the tensile strain and it increases for
compressive strain. Equation 7 is not adequate to explain the shifts in the dielectric maxi‐
mum temperature for the relaxor ferroelectric materials

In case of PSNT films, we observed a quadratic temperature dependence of the permittivity:

1 1 1
ε (ω, T ) - εm(ω, T ) = 2εmε0 (T - T m ) 2 (8)

Since the inverse of the dielectric constant is the second derivative of free energy with re‐
spect to polarization (Equation 5), the measured dielectric constant can be related to the ap‐
propriate coefficients in the LGD thermodynamical potential. For P=0 and xm=0 (in the
absence of strain), χ correlates with the first coefficient of the Landau equation, i.e.
 Self Assembled Nanoscale Relaxor Ferroelectrics 75
http://dx.doi.org/10.5772/54298

1
χ (T , f ) = α (T , f ) = 2εmε0 (T - T m)2 (9)

We substituted the values of α in Equation 5 and calculated the dielectric maxima tempera‐
ture under strain (T m'). To calculate T m', we differentiated the inverse of permittivity with re‐
spect to temperature at T m'.

(T m' - T m) - 4Q13 1Y- ν

∂χ ' 1 ∂ xm
∂ T m'
=0= ε0εmδ 2 ∂T (10)

where it is assumed that Q13, Y, and ν do not change substantially [34] with temperature in
the dielectric maxima regions; only the mismatch strain changes due to differential thermal
expansion:

∂ xm ∂ (a film 1 - λsubstrate (T - T 0) - abulk )

= (11)
∂T ∂T abulk

where λsubstrate is the coefficient of thermal expansion of the substrate, afilm and abulk are the lat‐
tice constant of the film and the bulk respectively. Using Equations, 9, 10, and 11 the expect‐
ed shift in Tm is:

Y a film
ΔT m = 4δ 2εmε0Q13 1 - ν abulk λsubstrate (12)

We have used the above equation to calculate the shift in the position of dielectric maxima
of PSNT films. Due to lack of experimental mechanical data in literature for PSNT films or
ceramics, we have used the standard Q13 for PST thin films [34] and Y value for the PMN
single crystal [35] other values we got from our experimental observation i.e. (δ, εm, afilm,
abulk,). For MgO substrate, λsubstrate = 1.2x10-5 K-1. Putting all these data in Equation 12 we got a
shift in the dielectric maximum temperature (Tm) of the same magnitude order than those of
experimental observation.

5. Experimental observation of strain induced relaxor phenomenon

Fig. 2 shows the dielectric behavior and the microstructures of the PSNT thin films and their
bulk matrix [31-33]. It has been shown that the two-dimensional (2D) clamping of films by
the substrate may change profoundly the physical properties of ferroelectric heterostructure
with respect to the bulk material. We observed a transfer and relaxing of epitaxial strain be‐
tween the layers due to in-plane oriented heterostructure. However the mismatch strain due
to different thermal expansion properties of each layer provokes a shift of 62 K in the tem‐
perature of the dielectric maxima.
76 Advances in Ferroelectrics

(a (b

(c

Figure 2. Microstructure of the PSNT bulk nanoceramics (a) and the thin films (b) grown on the LSCO coated MgO
substrate, Fig.2
and a Microstructure of the PSNT
drastic shift in dielectric bulktemperature
maxima nanoceramics(c) (a) and thin
in PSNT the thin
film films (b) grown
with respect sameoncompositions
the of
their bulk counterpart. The microstructures of film and ceramic support the existence of strain induced relaxor phe‐
nomenon,LSCOas theircoated MgO substrate,
microstructures- and correlation
property a drastic shift in dielectric
indicate maxima
the presence of temperature
some ordered(c)polar
in PSNT
nano-regions in
the thin films whereas absence of such effect in bulk. Figure 2(a) was adapted from Ref. [31] and reproduced with
permissionthin film with
(© 2008 Johnrespect same
Wiley and compositions of their bulk counterpart. The microstructures of film
Sons).

and ceramic support the existence of strain induced relaxor phenomenon, as their
Transmission electron microscopy (TEM) images of PSNT in bulk (Fig. 2(a)) and thin film
(Fig. 2(b)) form are shown in Fig. 2. The interlayer of about 20 nm between MgO and
LSCO and the fibril structures along a single direction in the film confirm the in-plane
strain state of the film. TEM image of bulk shows well ordered nanoregions in the grain
13 
matrix that
  meet a basic ingredient to produces relaxor behavior: the existence of nano-or‐
dered regions surrounding by a disordered structure, however, it is unable to produce it.
It has been observed from the neutron diffraction data that if the ordered nanoregions are
in the range of ~ 5-10 nm, then it is capable of yielding frequency dispersion in the dielec‐
tric spectra [30]. But the relaxor state also depends on the coherency with what the di‐
poles respond to the probing field (and frequency). They can establish long range or short
range coherent response. PSNT ceramic was incapable to produce the frequency disper‐
sion behavior, but in thin films form the in plane strain and the breaking of long range or‐
 Self Assembled Nanoscale Relaxor Ferroelectrics 77
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dering response, induced dielectric dispersion and shifting in dielectric maxima

temperature towards lower temperature side. We have observed from the temperature
evolution of the Raman spectra of bulk PSNT ceramic [31-33], the competitions between
ordered domains of short and long-range order due to Nb- and Ta-rich regions respective‐
ly. The average disorder arrangement of Sc3+/Nb5+/Ta5+ ions in the B-site octahedra leads to
the observed diffuse phase transition. In film only short range ordering in B'/B'' ions was
developed within the disordered matrix. Although bulk matrix exhibited nano-ordered re‐
gions its average size must be higher than film. Stress effects change the ionic positions
somehow favoring short-range ordering. These microstructural differences trigger the dif‐
ferent observed dielectric responses. The microstructure-property relation of PSNT thin
films and ceramics, one can build conclusions that perovskite with similar compositions
have well defined relaxor behavior than their bulk matrix.

6. Birelaxors

We have discussed the origin and functional properties of relaxor, in nutshell the basic charac‐
teristic of relaxors are the existence of ordered PNRs in a disordered matrix [37-42]. Similarly,
relaxor ferromagnets (synonyms: “Mictomagnets”) are also known in the literature since the
1970s. A mictomagnet is described as having magnetic clusters (superparamagnetism) which
form a spin glass and have a tendency to form short-range ordering [40, 41]. The materials hold
both ferroelectric and magnetic orders at nanoscale are called “birelaxors”. Birelaxors are sup‐
pose to possess only short range order over the entire temperature range with broken symme‐
try such as “global spatial inversion” and “time reversal symmetry” at nanoscale. Nanoscale
broken symmetries and length scale coherency make birelaxors difficult to investigate micro‐
scopically; it is advisable to use optical tools for proper probing. Birelaxors do not usually show
linear ME coupling (aij Pi Mj) but may have large nonlinear terms such as bP2M2. Since linear
coupling is not allowed, local strain-mediated PNR-PNR, PNR-MNR (magnetic nanoregions),
and MNR-MNR interactions may provide very strong ME effects [43-44].

A single-phase perovskite PbZr0.53Ti0.47O3 (PZT) and PbFe2/3W1/3O3 (PFW), (40% PZT-60 %

PFW) solid solutions thin film grown by pulsed laser deposition system have shown inter‐
esting birelaxor properties. Raman spectroscopy, dielectric spectroscopy and temperature-
dependent zero- field magnetic susceptibility indicate the presence of both ferroic orders
at nanoscale [45].

Dipolar glass and spin glass properties are confirmed from the dielectric and magnetic re‐
sponse of the PZT-PFW system, the micro Raman spectra of this system also revealed the
presence of polar nanoregions. Dielectric constant and tangent loss show the dielectric dis‐
persion near the dielectric maxima temperature that confirms near-room-temperature re‐
laxor behavior. Magnetic irreversibility is defined as (Mirr= MFC-MZFC) and it represents the
degree of spin glass behavior. PZT-PFW demonstrates special features in Mirr data at 100
Oe indicate that irreversibility persists above 220 K up to 4th or 5th order of the magni‐
tude, Tirr (inset Fig. 3 (b)). The evidence of ZFC and FC splitting at low field ~100 Oe and
78 Advances in Ferroelectrics

even for high 1 kOe field suggests and supports glass-like behavior with competition be‐
tween long-range ordering and short-range order. The behavior of the ZFC cusp is the
same for the entire range of field (>100 Oe), with a shift in blocking transition tempera‐
ture (TB) (maximum value of magnetization in ZFC cusp) to lower temperature, i.e. from
48 K to 29.8 K with increasing magnetic field. The ZFC cusps disappeared in the FC proc‐
ess, suggesting that competing forces were stabilized by the field- cooled process. Magnet‐
ic irreversibilities were found over a wide range of temperature with a sharp cusp in the
ZFC data, suggesting the presence of MNRs with spin-glass-like behavior. The detailed
fabrication process, the complete characterization process and the functional properties
are reported in reference [43]. This is not only the unique system to have birelaxor proper‐
ties, however, Levstik et al also observed the birelaxor properties in 0.8Pb(Fe1/2Nb1/2)O3–
0.2Pb(Mg1/2W1/2)O3 thin films [38].

1500
Dielectric constant(e)

(a)
1200
900
3.2 Experimental
VF fitting
(103/Tm)

600
3.0
300 4 6 8 10 12
Ln(f)
150 300 450 600
Temperature (K)
Mirr(emu/cm3)

(b) @ 100 Oe
Magnetization (emu/cm3)

7.0 1.20
0.90
0.60
6.5 0.30
0.00
6.1 0 100 200 300
T (K)
5.6 FC
@ 100 Oe
ZFC
0 100 200 300
Temperature (K)

Figure 3. (a) Dielectric response and Vogel-Fulcher fitting (inset), (b) Zero field cooled and field cool magnetic re‐
sponse of PZT-PFW thin films indicate the presence of PNRs and MNRs at nanoscale. Adapted from Ref. [45] and repro‐
duced with permission (© 2011 AIP).
 Self Assembled Nanoscale Relaxor Ferroelectrics 79
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7. Superlattice relaxors and high energy density capacitors

Material scientists are looking for a system or some novel materials that possess high
power density and high energy density or both. Relaxors demonstrate high dielectric
constant, low loss, non linear polarization under external electric field, high bipolar den‐
sity, nano dipoles (polar nano regions (PNRs) and moderate dielectric saturation, these
properties support their potential candidature for the high power as well as high ener‐
gy devices. At present high-k dielectric (dielectric constant less than 100, with linear di‐
electric) dominates in the high energy, high power density capacitor market. The high-k
dielectrics show very high electric breakdown strength (> 3 MV/cm to 12 MV/cm) but
their dielectric constant is relatively very low which in turns offer 1-2 J/cm3 volume en‐
ergy density. Recently, polymer ferroelectric, antiferroelectric, and relaxor ferroelectric
have shown better potential and high energy density compare to the existing linear die‐
lectrics [46-51].

BaTiO3/Ba0.30Sr0.70TiO3 (BT/BST) superlattices (SLs) with a constant modulation period of Λ=

80 Å were grown on (001) MgO substrate by pulsed laser deposition. The modulation perio‐
dicity Λ/2 was precisely maintained by controlling the number of laser shots; the total thick‐
ness of each SL film was ~6,000 Å = 0.6 μm. An excimer laser (KrF, 248 nm) with a laser
energy density of 1.5 J/cm2, pulse repetition rate of 10 Hz, substrate temperature 830 °C, and
oxygen pressure at 200 mTorr was used for SL growth. The detailed growth and characteri‐
zation techniques are presented elsewhere [52].

Dielectric responses of BT/BST SLs display the similar response as for normal relaxor fer‐
roelectric which can be seen in Figure 4. It follows the non linear Vogel- Fulcher relation‐
ship (inset Figure. 4 (a)), frequency dispersion near and below the dielectric maxima
temperature (Tm), merger of frequency far above the Tm, shift in Tm towards higher tem‐
perature side (about 50-60 K) with increase in frequencies, low dielectric loss, and about
60-70% dielectric saturation.

BT/BST SLs demonstrate a “in-built” field in as grown samples at low probe frequency (<1
kHz), whereas it becomes more symmetric and centered with increase in probe frequency
system (>1 kHz) that ruled out the effect of any space charge and interfacial polarization.
Energy density were calculated for the polarization-electric field (P-E) loops provide ~
12.24 J/cm3 energy density within the experimental limit, but extrapolation of this data in
the energy density as function of applied field graph for different frequencies (see inset in
Figure 4) suggests huge potential in the system such as it can hold and release more than
40 J/cm3 energy density.

Experimental limitations restrict to proof the extrapolated data, however the current density
versus applied electric field indicates exceptionally high breakdown field (5.8 to 6.0 MV/cm)
and low current density (~ 10-25 mA/cm2) near the breakdown voltage. Both direct and indi‐
rect measurements of the energy density indicate that it has ability to store very high energy
density storage capacity (~ 46 J/cm3).
80 Advances in Ferroelectrics

Dielectric Constant 1000 (a) 1 kHz

750
50 kHz
500 3.08
1000/Tm (K-1)
Exp. data
3.04 VF Fit

3.00

250 2.96
2.92

6 7 8 9 10 11
Ln (f)
0
200 300 400 500
Temperature (K)
103
Energy Density (J/cm3)

(b)
102
101
100
10-1
10-2
1 kHz
10-3
12 kHz
10-4
10-3 10-2 10-1 100 101
Electric Field (MV/cm)

Figure 4. (a) Dielectric responses of BT/BST superlattice relaxors as function of temperature over wide range of fre‐
quencies, nonlinear Vogel-Fulcher relationship (inset), (b) Energy density capacity as function of applied electric filed,
red dots show the extrapolated data. Adapted from Ref. [46] and reproduced with permission (© 2012 IOP).

The above experimental facts suggest the relaxor nature of BT/BST ferroelectric superlatti‐
ces. It also indicates their potential to store and fast release of energy density which is com‐
parable to that of high-k (<100) dielectrics, hopefully in the coming years it might be suitable
for high power energy applications. These functional properties of relaxor superlattices
make it plausible high energy density dielectrics capable of both high power and energy
density applications.
 Self Assembled Nanoscale Relaxor Ferroelectrics 81
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8. Conclusions

Extensive studies on the relaxor ferroelectrics suggest the presence of localized nano size
ordered regions in the disordered matrix or static random field are responsible for the die‐
lectric dispersion near Tm. The nano regions and their coherence length are also critical for
the relaxor behavior. A normal ferroelectric with diffuse phase transition system can be
turn to relaxor ferroeletrics in their thin film forms under the suitable applications of
strain, utilizing highly lattice mismatch substrate, growth conditions (thermal, oxygen par‐
tial pressure, atmosphere), etc.. It also indicates that the defects, oxygen vacancies, order‐
ing of cations at A and B site of perovskite, tensile or comprehensive strain across the
interface, etc. originate the ordered nano regions in films mainly responsible for dielectric
dispersion. Materials with same compositions can have normal ferroelectric in bulk form
whereas become relaxor in the thin film. Birelaxors hold both ferroics orders at nano scale
with only short range ordering (SRO). These nanocale SRO make it potential candidates
for non linear biquadratic magneto-electric coupling suitable for magnetic field sensors
and non volatile memory applications. BT/BST superlattice has shown very high dielectric
constant, high breakdown field, relaxor, and high energy density functional properties. A
Relaxor superlattice with high functional properties is capable for both high power and
energy density applications.

Acknowledgement

This work was partially supported by NSF-EFRI-RPI-1038272 and DOE-DE-

FG02-08ER46526 grants.

Author details

Ashok Kumar1,2, Margarita Correa2, Nora Ortega2, Salini Kumari2 and R. S. Katiyar2

*Address all correspondence to: [email protected]

1 National Physical Laboratory, Council of Scientific and Industrial Research (CSIR), New
Delhi, India

2 Department of Physics and Institute for Functional Nanomaterials, University of Puerto

Rico, San Juan, Puerto Rico
82 Advances in Ferroelectrics

References

[1] G. A. Smolenskii and A. I. Agranokskaya, Soviet Physics Solid State 1, 1429 (1959)
[2] R. E. Cohen, Nature, 441, 941 (2006)
[3] Eric Cross, Ferroelectrics, 151, 305, (1994)
[4] G. A. Samara, J. Phys.: Condens. Matter 15, R367, (2003)
[5] G. Burns and F. H. Dacol, Solid State Communications, 48, 853, (1983)
[6] G. A. Samara, Solid State Physics, vol. 56, Edited by H. Ehrenreich, and R. Spaepen,
New York: Academic, New York (2001)
[7] B. Krause, J. M. Cowley, and J. Wheatly, Acta Cryst. A35, 1015 (1979)
[8] C.A. Randall, D. J. Barber, and R. W. Whatmore, J. Micro. 145, 235 (1987)
[9] J. Chen, H. Chen, and M. A. Harmer, J. Am. Ceram. Soc. 72, 593 (1989)
[10] I. M. Brunskill, H. schmid, and P. Tissot, Ferroelectrics 37, 547 (1984)
[11] C. A. Randall, A. S. Bhalla, T. R. Shrout, and L. E. Cross, J. Mater. Res., 5, 829 (1990)
[12] C. A. Randall and A. S. Bhalla, Japanese Journal of Applied Physics, 29, 327 (1990)
[13] Ferroelectrics and Related Materials, G. A. Smolenskii (Ed.), V. A. Bokov, V. A. Isu‐
pov, N. N. Krainik, R. E. Pasynkov and A. I. Sokolov, Gordon & Breach Science Pub‐
lisher, New York (1984)
[14] Z.-G Ye, Key Engineering Materials, 155-156, 81 (1998)
[15] H. Vogel. Z. Phys. 22, 645 (1921). G. Fulcher. J. Am. Ceram. Soc. 8, 339 (1925)
[16] V.Westphal,W. Kleeman, and M.D. Glinchuk, Phys. Rev. Lett. 68, 847 (1992).
[17] R. Pirc and R. Blinc, Phys. Rev. B. 60, 13470 (1999).
[18] R. Blinc, J. Dolinsek, A. Gregorovic, B. Zalar, C. Filipic, Z. Kutnjak, A. Levstik, and R.
Pirc, Phys. Rev. Lett. 83, 424 (1999).
[19] H.T. Martirena and J.C. Burfoot. Ferroelectrics, 7, 151 (1974)
[20] G. A. Smolenskii, V. A. Isupov, A. I. Agranovskaya and S. N. Popov, Soviet Phys.-
Solid State. 2, 2584 (1961).
[21] G. A. Smolenskii, J. Phys. Soc. Jpn. 28, Suppl. 26 (1970).
[22] L.E. Cross, Ferroelectrics 76, 241 (1987).
[23] D. Viehland, J. F. Li, S. J. Jang, and L. E. Cross and M. Wuttig. Phys. Rev. B. 43, 8316
(1991).
[24] R. Fisch. Phys. Rev. B. 67, 094110 (2003).
 Self Assembled Nanoscale Relaxor Ferroelectrics 83
http://dx.doi.org/10.5772/54298

[25] R. Pirc and R. Blinc, Phys. Rev. B. 60, 13470 (1999)

[26] F. Devonshire, Philos. Mag. 40, 1040, (1949); 42, 1065, (1951)
[27] G.A. Rossetti Jr., L.E. Cross, and K. Kushida, Appl. Phys. Lett., 59, 2504 (1991)
[28] N.A. Perstev, A.G. Zembilgotov, and A. K. Tagantsev, Phys. Rev. Lett., 80, 1988
(1998)
[29] M. Dawber, K.M. Rabe, and J.F. Scott, Reviews of Modern Physics, 77, 1083, (2005)
[30] G. Catalan, M. H. Corbett, R. M. Bowman, and J. M. Gregg, J. App. Phys., 91, [4] 2295
(2002).
[31] Margarita Correa, A. Kumar and R.S. Katiyar, J. Am. Cer. Soc. 91 (6) 1788 (2008).
[32] Margarita Correa, Ashok Kumar, and R. S. Katiyar, Applied Physic Letters, 91,
082905 (2007).
[33] Margarita Correa, Ashok Kumar, and R. S. Katiyar, Integrated Ferroelectrics, 100, 297
(2008)
[34] K. Brinkman, A. Tagantsev, P. Muralt, and N. Setter, Jpn. J. App. Phys., 45, [9B] 7288
(2006)
[35] Q.M. Zhang and J. Zhao, Appl. Phys. Lett., 71, 1649 (1997)
[36] D. L. Orauttapong, J. Toulouse, J. L. Robertson, and Z. G. Ye, Physical Rev. B , 64,
212101 (2001).
[37] A. Kumar, N. M. Murari, and R. S. Katiyar, Appl. Phys. Lett. 90, 162903 (2007).
[38] A. Levstik, V. Bobnar, C. Filipič, J. Holc, M. Kosec, R. Blinc, Z. Trontelj, and Z. Jagli‐
čič, Appl. Phys. Lett. 91, 012905, (2007).
[39] V. V. Shvartsman, S. Bedanta, P. Borisov, W. Kleemann, A. Tkach, and P. M. Vilarin‐
ho, Phys. Rev. Lett. 101, 165704 (2008).
[40] G. A. Samara, in Solid State Physics, edited by H. Ehrenreich and R. Spaepen Aca‐
demic, New York, 2001, Vol. 56, p. 239.
[41] J. Dho, W. S. Kim, and N. H. Hur, Phys. Rev. Lett. 89, 027202 (2002).
[42] R. Pirc and R. Blinc, Phys. Rev. B 76, 020101R (2007).
[43] A. Kumar, G. L. Sharma, R. S. Katiyar, R. Pirc, R. Blinc, and J. F. Scott, J. Phys.: Con‐
dens. Matter 21, 382204 (2009).
[44] R. Pirc, R. Blinc, and J. F. Scott, Phys. Rev. B 79, 214114 (2009).
[45] A. Kumar, G. L. Sharma, R. S. Katiyar, Appl. Phys. Lett. 99, 042907 (2011).
[46] J. H. Tortai, N. Bonifaci, A. Denat, J. Appl. Phys. 97, 053304 (2005).
[47] M. Rabuffi, G. Picci, IEEE Trans. Plasma Sci. 30, 1939 (2002).
84 Advances in Ferroelectrics

[48] X. Hao, J. Zhai, and, X. Yao, J. Am. Ceram. Soc., 92, 1133 (2009).

[49] J. Parui, S. B. Krupannidhi, Appl. Phys. Lett., 92, 192901 (2008).

[50] R. M. Wallace, G. Wilk, MRS Bulletin. 27, 186 (2002).

[51] G. D. Wilk, R. M. Wallace, J. M. Anthony, J. Appl. Phys. 89, 5243 (2001).

[52] N. Ortega, A Kumar, J. F. Scott, Douglas B. Chrisey, M. Tomazawa, Shalini Kumari,

D. G. B. Diestra and R. S. Katiyar. J. Phys.: Condens. Matter. 24 445901 (2012).
 Chapter 5

Relaxor Behaviour in Ferroelectric Ceramics

A. Peláiz-Barranco, F. Calderón-Piñar,
O. García-Zaldívar and Y. González-Abreu

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52149

1. Introduction

Ferroelectric materials are commonly characterized by high dielectric permittivity values [1].
Usually, for the well-known ‘normal’ ferroelectrics the temperature of the maximum real di‐
electric permittivity (Tm) corresponds to the ferroelectric-paraelectric (FE-PE) phase transi‐
tion temperature (TC) [2]. On the other hand, there are some kinds of ferroelectrics, so-called
relaxor ferroelectrics, which have received special attention in the last years because of the
observed intriguing and extraordinary dielectric properties [3-25], which remain not clearly
understood nowadays. For instance, some remarkable characteristics of the dielectric re‐
sponse of relaxor materials can be summarized as follows: i- they are characterized by wide
peaks in the temperature dependence of the dielectric permittivity, ii- the temperature of the
corresponding maximum for the real (ε') and imaginary (ε'') component of the dielectric per‐
mittivity (Tm and Tε''max, respectively) appears at different values, showing a frequency de‐
pendent behaviour, and iii- the Curie-Weiss law is not fulfilled for temperatures around Tm.
So that, the temperature of the maximum real dielectric permittivity, which depends on the
measurement frequency, cannot be associated with a FE-PE phase transition.

Lead zirconatetitanate (PZT) system is a typical ferroelectric perovskite showing ‘normal’

FE-PE phase transition [1]. Nevertheless, the partial substitution by different elements, such
as lanthanum, contributes to enhance such relaxor characteristics [11-15]. In fact, for some
lanthanum concentrations, the distortion of the crystalline lattice in the PZT system due to
ions displacement could promote the formation of the so-called polar nanoregions (PNRs).
Another interesting relaxor ferroelectric perovskite is known as PZN-PT-BT [16-19]. The
Pb(Zn1/3Nb2/3)O3 ferroelectric material (PZN) belongs to the relaxor ferroelectrics family, re‐
ceiving special attention for its technical importance [20]. However, its preparation usually
needs the addition of BaTiO3 (BT) and PbTiO3 (PT) to obtain pure phases [16,21].

© 2012 Peláiz-Barranco et al.; licensee InTech. This is an open access article distributed under the terms of the
Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
86 Advances in Ferroelectrics

On the other hand, a considerable number of compositions from the Aurivillius family exhibit
a relaxor ferroelectric behaviour [22-26]. The Aurivillius compounds are layered bismuth
[Bi2O2]2+[An−1BnO3n+1]2−, where the sites A and B can be occupied for different elements. These
are formed by the regular stacking of Bi2O2 slabs and perovskite-like blocks An−1BnO3n+1. These
materials have received great attention due to their large remanent polarization, lead-free na‐
ture, relatively low processing temperatures, high Curie temperatures and excellent piezo‐
electric properties, which made them good candidates for high-temperature piezoelectric
applications and memory storage [27]. The origin of the relaxor behaviour for these materials
have been associated to a positional disorder of cations on A or B sites of the perovskite blocks
that delay the evolution of long-rage polar ordering [28].

Several models have been proposed to explain the dielectric behaviour of relaxor ferroelec‐
trics. The basic ideas have been related to the dynamics and formation of the polar nanore‐
gions (PNRs). In this way, Smolenskii proposed the existence of compositional fluctuations
on the nanometer scale taking into account a statistical distribution for the phase transition
temperature [29]. On the other hand, Cross extended the Smolenskii’s theory to a superpara‐
electric model associating the relaxor behaviour to a thermally activated ensemble of super‐
paraelectric clusters [30]. Viehland et al. have showed that cooperative interactions among
these superparaelectric clusters could produce a glass-like freezing behaviour, commonly
exhibited in spin-glass systems [31]. Later, Qian and Bursill [32] analyzed the possible influ‐
ence of random electric fields on the formation and dynamics of the polar clusters, which
can be originated from nano-scaled chemical defects. They have also proposed that the re‐
laxor behaviour can be associated to a dipolar moment in an anisotropic double-well poten‐
tial, taking into account only two characteristic relaxation times. According to this model,
the dispersive behaviour is produced by changes in the clusters size and the correlation
length (defined as the distance, above which such PNRs become non-interactive regions) as
a function of the temperature, which provides a distribution function for the activation ener‐
gy. However, despite their very attractive physical properties, the identification of the na‐
ture of the dielectric response in relaxors systems still remains open and requires additional
theoretical and experimental information, which can be very interesting to contribute to the
explanation of the origin of the observed anomalies.

The present chapter shows the studies carried out on several relaxor ferroelectric ceramic
materials, which have been developed by the present authors. Lanthanum modified lead
zirconatetitanate ceramics will be evaluated considering different La3+ concentrations and
Zr/Ti ratios. It will be discussed the dynamical behaviour of the PNRs taking into account a
relaxation model, which considers a distribution function for the relaxation times. The influ‐
ence of A or B vacancies on the relaxor behaviour will be also analyzed considering the de‐
coupling effects of these defects in the Pb-O-Ti/Zr bounding. For the PZN-PT-BT system, the
relaxor behaviour will be explained considering the presence of local compositional fluctua‐
tion on a macroscopic scale. Finally, the relaxor behaviour of Sr0.50Ba0.50Bi2Nb2O9 ferroelectric
ceramics, which belong to the Aurivillius family, will be discussed considering a positional
disorder of cations on Aor B sites of the perovskite blocks.
 Relaxor Behaviour in Ferroelectric Ceramics 87
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2. Lanthanum modified Lead Zirconate Titanate (PLZT)

2.1. Relaxor behaviour and coexistence of AFE and FE phases

Several researches concerning PZT properties have shown that very good properties can be
obtained by suitable selection of the Zr/Ti ratio and the substitution of a small amount of
isovalent or heterovalent elements for the Pb or (Zr,Ti) sublattices [1]. Especial attention re‐
ceives the Zr-rich PZT-type ceramics, which exhibit interesting dielectric and pyroelectric
characteristics, suitable for pyroelectric detectors, energy converters, imaging systems, etc
[1,33-34]. They show orthorhombic antiferroelectric (AFE-O), low temperature rhombohe‐
dral ferroelectric (FR-LT), high temperature rhombohedral ferroelectric (FR-HT) and cubic
paraelectric (PC) phase sequence [1].
One of the most common additives to the PZT ceramics is the lanthanum cation, which sub‐
stitute the Pb-ions in the A-site of the perovskite structure [1]. The lanthanum-modified lead
zirconatetitanate Pb1-xLax(Zr1-yTiy)1-x/4O3 (PLZT) ferroelectric ceramics show excellent proper‐
ties to be considered for practical applications, especially PLZT x/65/35, x/70/30 and x/80/20
compositions due to the relaxor ferroelectric behaviour [35-36]. For Zr-rich PZT ceramics,
which are close to the antiferroelectric-ferroelectric (AFE-FE) phase boundary, the FE phase
is only marginally stable over the AFE [33]. In this way, as the FE state is disrupted by lan‐
thanum modification, the AFE state is stabilized [33].

Figure 1. Temperature dependence of the real (ε') and imaginary (ε'') parts of the dielectric permittivity at several fre‐
quencies for PLZT 6/80/20 ferroelectric ceramic system.

Figure 1 shows the temperature dependence of the real (ε') and imaginary (ε'') parts of the
dielectric permittivity, at several frequencies, for PLZT 6/80/20 ferroelectric ceramic system.
Typical characteristics of relaxor ferroelectric behaviour are observed. The frequency de‐
pendence of ε' is very weak but the frequency dependence of ε'' clearly reflects the relaxor
nature of the system. The asymmetrical shape of the curves could suggest the existence of
more than one contribution. X-ray diffraction analysis for the PLZT 6/80/20 ceramic samples
88 Advances in Ferroelectrics

have previously shown a mixture of FE and AFE phases at room temperature [13]. Polarized
light microscopy studies were performed on the ceramic system in a wide temperature
range. Aggregates of individual regions were observed, which were associated to FE and
AFE phases. As the temperature increased, a gradual change was observed, suggesting a
transition to a single phase [13].

Figure 2 shows the hysteresis loops obtained for the PLZT 6/80/20 ceramics for two tempera‐
tures, as example of the obtained behaviour in a wide temperature range. Around 70oC a
double-loop-like behaviour was observed suggesting an induced FE-AFE transforma‐
tion.The FE state is disrupted by the lanthanum modification and the AFE state is stabilized,
which may be a consequence of the short-range nature of the interaction between the AFE
sublattices. The double-loop remains for higher temperature and around 120oC the loop dis‐
appears suggesting a transition to a PE phase. Then, it is possible to consider the coexistence
of two phase transitions: a FE-AFE phase transition observed around 70oC and an AFE-PE
phase transition around 120oC. Note, that the maximum of ε' is observed around 120oC.
Negative values for TC were found, which has confirmed that around 120oC an AFE-PE tran‐
sition take places [13]. Thus, the relaxor ferroelectric behaviour for this system could be as‐
sociated to the coexistence of FE and AFE phases in the studied material.

Figure 2. Hysteresis loops for PLZT 6/80/20 ferroelectric ceramic system.

2.2. A relaxation model

The nature of the relaxor behaviour is determined by the existence of PNRs, which possess
different relaxation times [32,37]. The relaxation time (τ) represents the time response of
such PNRs or polarization mechanisms to change with the applied electric field. However,
this process does not occur instantaneously. Indeed, there exists certain inertia, which is the
cause of the pronounced dielectric relaxation in relaxor ferroelectrics. The polar nanoregions
appear below a certain temperature, the so-called the Burns’ temperature (TB) [38], which is
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typically hundreds degrees above the temperature of the maximum real dielectric permittiv‐
ity (Tm). On cooling, the number, size (some of them) and the interaction of the PNRs in‐
crease [39]. The increase of such interactions promotes the freezing of some regions around
certain temperatures below Tm, known as the freezing temperature (TF). Two fundamental
polarization mechanisms have been reported, which have been associated with the dynam‐
ics of the PNRs; (i) dipole reorientation [37,40] and (ii) domain wall vibrations [32]. Both
mechanisms have a characteristic time response, which depends on the temperature and
size of the PNRs. If the contributions of an ensemble of these regions are considered, the
macroscopic polarization function, at fixed temperature, can be expressed by [41]:

t t t t
- - - -
+ ..... = å P0 i e
t1 t2 t3 ti (1)
P(t ) = P01e + P02 e + P03 e
i

where τiis the relaxation time of the ith PNR and P0i takes the form of equation (2), in analogy
with the Debye single relaxation time model, which takes into account a distribution func‐
tion of relaxation times [41]:

es - e¥
P0 i = g(t i ) (2)
ti

2s 1
g(t i ) =
p ti 2 (3)
4(ln ) + s 2
t0

In these relations g(τi) is a distribution function for the logarithms of the relaxation times,
which has been assumed to be a Lorentz rather than a Gaussian distribution function; τ0 and
σ are the mean relaxation time and the Standard Deviation, respectively. According to the
Debye model, the frequency dependence of the complex dielectric permittivity can be ex‐
pressed as:

e * (w ) = e ¢ - ie ¢¢ = e ¥ + ò P(t )e - iwt dt (4)

where εs and ε∞ are the low (static) and high (optical) dielectric permittivity, respectively, ω
the measurement frequency, and P(t) the decay polarization function. Substituting equations
(1), (2) and (3) into equation (4), the real and imaginary component of the dielectric permit‐
tivity for the multi-relaxation times approximation can be obtained and expressed as in
equations (5) and (6). It is important to point out that equations (5) and (6) have been de‐
90 Advances in Ferroelectrics

rived from the discrete expression (1), taking into account the values of the relaxation times
(τi) close to each other [41].

+¥
2s 1
e ¢(w ,T ) = e ¥ + (e s - e ¥ )
p ò (4 z 2 + s 2 )(1 + w 2t 2 exp(2 z)) dz (5)
-¥ 0

+¥
2s wt exp( z)
e ¢¢(w ,T ) = (e s - e ¥ )
p ò (4 z 2 + s 2 )(10 + w 2t 2 exp(2 z) dz (6)
-¥ 0

It has been considered in equations (5) and (6) that z = lnτ/τ0. By using the experimental re‐
sults of ε'(ω,T) and ε''(ω,T) for two frequencies, the temperature dependence of dielectric pa‐
rameters, such as, τ0, εs and σ can be obtained as a solution of the equations system. After
that, by using the theoretical results of τ0(T), εs(T) and σ(T), the theoretical dependences of
ε'(ω,T) and ε''(ω,T) can be obtained for the studied frequency and temperature ranges. The
parameter ε∞ has been considered negligible because of the high values of the dielectric per‐
mittivity in ferroelectric systems [1].

Figures 3 and 4 show the temperature dependence of the real (ε') and imaginary (ε'') compo‐
nents of the dielectric permittivity (symbols), at several frequencies, for the studied PLZT
10/80/20 composition. A relaxor characteristic behaviour can be observed. The maximum re‐
al dielectric permittivity decreases, while its corresponding temperature (Tm) increases, with
the increase of the measurement frequency. There is not any peak for ε'' due to the low tem‐
perature range where the maximum of the real part of the dielectric permittivity appears, i.e.
the maximum for ε'' should appear below the room temperature.

Figure 3. Temperature dependence of the real part (ε') of the dielectric permittivity at several frequencies for PLZT
10/80/20 ferroelectric ceramic system. The experimental values are represented by solid points and the theoretical re‐
sults by solid lines. It has been included the theoretical temperature dependence of the static dielectric permittivity (εS).
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Figure 4. Temperature dependence of the imaginary part (ε'') of the dielectric permittivity at several frequencies for
PLZT 10/80/20 ferroelectric ceramic system. The experimental values are represented by solid points and the theoreti‐
cal results by solid lines.

The number of PNRs able to follow the applied external electric field switching decreases
with the increase of the frequency, so that only such inertial-less regions contribute to the
dielectric permittivity (those regions whose activation energy is close to thermal energy kBT,
being kBthe Boltzmann constant). Therefore, due to the cooperative nature, the real compo‐
nent of the dielectric permittivity should decrease with the increase of the measurement fre‐
quency.
The maximum for ε' in relaxor systems is not related to a crystallographic transition. Indeed,
such a maximum corresponds to rapid changes of the fraction of the frozen Polar Regions [39].
Hence, the shift up to higher temperatures of the maximum for ε' with the increase of the fre‐
quency is a direct consequence of the delay in dielectric response of the frozen regions.
By using equations (5) and (6) and the experimental data of Figures 3 and 4, the temperature
dependences of εs, σ and τ0 were obtained. The results were obtained by numerical methods
because there was no analytical solution for the equation system. The theoretical curves for
ε' and ε'' were obtained for all the studied frequency range, and shown in the same Figures 3
and 4 as solid lines, for the studied system. The temperature dependence of the static dielec‐
tric permittivity (εs) is also shown in Figure 3. A good agreement between experimental and
theoretical results can be observed. It is important to point out that the deviation between
the experimental and theoretical results, observed at low frequencies for the temperature de‐
pendence of ε'', can be associated with the contribution of the electric conductivity to the di‐
electric response, which has not been considered in the proposed model.
Figure 5 shows the temperature dependence of lnτ0 and σ for the studied composition. As
can be seen, lnτ0 increases with the increase of the temperature, passes through a maximum
and then decreases for higher temperatures. Similar results have been previously reported
by Lin et al [41]. According to the model, the logarithmic mean relaxation time (lnτ0) should
have has approximately the same tendency as that of σ(T). Both parameters increases when
92 Advances in Ferroelectrics

the temperature decreases which can be understood as a consequence of the increased iner‐
tia of the dipolar clusters as they become more correlated with each other upon cooling. This
observation also could reflect a dynamic change in the well potential for the shifting ions.
However, the reduction in lnτ0(T) at lower temperatures possibly could reflect a freezing
phenomenon of some clusters that are saturated in correlation, which leads to the frustration
of cooperative interactions and, hence, leaves only relatively unstrained or smaller clusters
available to couple with the electric field. Also, one could speculate that such clusters are the
regions within the domain boundaries between the frozen regions.

Figure 5. Temperature dependence of the main relaxation time (logarithmic representation, lnτ0) and its standard de‐
viation (σ), for PLZT 10/80/20 ferroelectric ceramic system.

In this way, the size and the interaction between PNRs increase on cooling from the high
temperature region and its contribution to the dielectric permittivity becomes negligible be‐
low the freezing temperature (T F) [39]. In this temperature range (T < TF), the applied electric
field is not strong enough to break such interactions and only the smallest regions can
switch with the electric field, i.e. that is to say, there is a frustration of the cooperative effect.
For temperatures above TF, there are fluctuations between equivalent polarization states
[30], leading to a decrease of the macroscopic polarization upon heating [42]. The applied
electric field cannot reorient the ferroelectric dipoles because of the thermal fluctuation. The
potential barrier between equivalent polarization states decreases with the increase of the
temperature and the thermal energy promotes the spontaneous switching of the dipoles,
even when an electric field is applied. The contribution to the dielectric permittivity is due
to those PNRs, which can switch with the applied electric field. Thus, for temperatures
slightly above TF all the PNRs could contribute to the dielectric permittivity and a maximum
value of the mean relaxation time could be expected. Therefore, the temperature corre‐
sponding to the maximum of lnτ0 can be related to the freezing temperature. The standard
deviation (σ), which can be interpreted as the correlation between the PNRs [32,41], decreas‐
es upon heating and it is relatively small at high temperatures. When the temperature in‐
creases the thermal energy is high enough to break down the interaction between the PNRs.
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So that, a decrement of the correlation between the PNRs is promoted by an increase of the
temperature and the Standard deviation decreases up to a relatively constant value around
the Burns’ temperature (TB) [38,43], where the PNRs completely disappear.

Figure 6. Temperature dependence of the frequency (lnf versus 1/(Tm–TF) curve) for PLZT 10/80/20 ferroelectric ce‐
ramic system. Solid lines represent the fitting by using the Vogel–Fulcher relation.

The freezing temperature (TF) was determined by using the Vogel–Fulcher relation [44], as
expressed by equation (7):

U
-
kB (Tm -TF ) (7)
f = fD e

where fD is the Debye frequency and U is the activation energy. Figure 6 show the tempera‐
ture dependence of the frequency (lnf versus 1/(Tm–TF) curve) and the fitting by using equa‐
tion (7). In order to maintain the standard representation, the temperature in Figure 6 was
expressed in Kelvin. The fitting parameters U, fD and TF have been included in the figure.
The results are in agreement with previously reported results in the literature [42]. The disa‐
greement between the TF value, which has been determined by using the Vogel-Fulcherrela‐
tion, and the temperature corresponding to the maximum value of lnτ0 could be associated
to the diffusivity of the phase transition in the studied system.

2.3. Relaxor behaviour and vacancies.

Relaxor ferroelectrics are formed by temperature dependent Polar Nanometric Regions

(PNRs), which possess different volumes [45] and orientations for the polarization
[30,37,46-47]. The PNRs appear at elevated temperatures (in the paraelectric state), at the so-
called Burns’ temperature (TB) [38,48-49], due to short-range interactions, which establish a
local polarization thermally fluctuating between equivalents polar states.
94 Advances in Ferroelectrics

The disorder in the arrangement of different ions on the crystallographic equivalent sites is
the common feature of relaxors [50]. This is associated, in general, with a complex perov‐
skite of the type A(B'B'')O3, where the B sites of the structure are occupied by different cati‐
ons. Nevertheless, in lead zirconate titanate based ceramics (PZT) the disorder due to the
arrangement of the isovalent cations Zr4+ and Ti4+, in the B site of the structure, does not lead
to relaxor behaviour for any Zr/Ti ratio. The lanthanum modification on this system, above
certain La3+ concentrations, provides a relaxor ferroelectric state [11-12]. Electrical neutrality
can be achieved, stoichiometrically, considering the vacancies formation either in the A-site
(Pb2+) or in the B-site (Zr4+, Ti4+), or on both. The distortion of the crystalline lattice in the PZT
system could promote the formation of the PNRs. In this section, the results concerning the
influence of the A or B vacancies defects in the relaxor ferroelectric behaviour of lanthanum
modified PZT ceramic samples will be presented. The studied compositions will be
Pb0.85La0.10(Zr0.60Ti0.40)O3 and Pb0.90La0.10(Zr0.60Ti0.40)0.975O3, labelled as PLZT10-VA and PLZT10-
VB, respectively.

The temperature dependence of the real dielectric permittivity (ε') and the dielectric losses
(tan δ) are shown in the Figures 7 and 8, respectively, for several frequencies. Typical char‐
acteristics of relaxor ferroelectrics are exhibited for both samples, i.e. wide peaks for ε', the
maximum real dielectric permittivity shifts to higher temperatures with the increase of the
frequency, and the maximum dielectric losses temperature appears at temperatures below
Tm. On the other hand, it can be observed that the dielectric response is highly affected by
the type of compensation. The maximum values of the real dielectric permittivity in the
PLZT10-VA sample are lower than those obtained for the PLZT-10VB sample, and appear at
lower temperatures. The PLZT10-VA sample also exhibits a larger temperature shift of Tm
(ΔT=15oC), from 1 kHz to 1 MHz, than that of the PLZT10-VB sample (ΔT=9oC).

Figure 7. Temperature dependence of the real (ε') component of the dielectric permittivity at several frequencies, for
PLZT10-VA and PLZT10-VB ceramic samples.
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Figure 8. Temperature dependence of the dielectric losses (tan δ) at several frequencies for PLZT10-VA and PLZT10-VB
ceramic systems.

It has been previously commented that, in relaxors, the maximum real dielectric permittivity
is not a consequence of crystallographic changes but it is associated with a rapid change in
the volume fraction of frozen polar nanoregions [39]. During cooling, the PNRs grow in size
and number [39,43] as well as the interactions among them increases. Thus, a decrement of
its mobility is expected; the thermal energy (kBT) is not enough to switch the polar state of
the PNRs (freezing phenomenon). While the regions grow, with the decreasing of the tem‐
perature, the thermal energy kBT decreases. The freezing process begins at high tempera‐
tures and finish at low temperatures, below Tm, in the so called freezing temperature (TF),
where all the PNRs are frozen.

The dielectric and ferroelectric response in relaxor ferroelectrics strongly depend of the tem‐
perature dependence of the freezing process (dynamic of the PNRs) as well as on the inter‐
actions between external electric field and the dipole moment of the PNRs. When a weak
alternating electric field is applied, only the unfrozen regions and the frozen ones with acti‐
vation energies close to kBT could switch with the applied alternating electric field. There‐
fore, only these regions contribute to the dielectric permittivity. However, not all these
regions can switch at any excitation frequency; the number of PNRs able to follow the ap‐
plied external electric field switching decreases with the increase of the frequency [14]. The
response also depends on the relaxation time of each region [14, 41]. Thus, the dielectric re‐
sponse in relaxors depends of the number of regions that can contribute at each temperature
and the distribution of the corresponding relaxation times.

The Pb2+ ions (A-sites of the perovskite structure) establish the long-range order in PZT
based ceramics due to strong coupling of Pb-O-Ti/Zr bonding [51]. The coupling defines the
height of the energy barrier between polar states via Ti/Zr-hopping [51]. The Pb2+ substitu‐
tion by La3+ ions, above certain level of La3+ ions concentration, weakens this bonding result‐
ing in small and broadly distributed energy barriers [51], which disrupts the long-range
96 Advances in Ferroelectrics

order and promotes the PNRs formations. An additional contribution, which plays a funda‐
mental role in the relaxor behaviour, can be originated from the A- or B-sites vacancies for‐
mations. There are two important differences between the A- or B-site compensation, which
can explain the different dielectric behaviour observed in the studied samples: i) for the
same lanthanum concentration the number of lead vacancies is twice the Zr/Ti vacancies, if
it is considered A- or B-site compensation, respectively, i.e. 2La3+→1VPb and 4La3+→1VZr/Ti; ii)
the A-site vacancies generate large inhomogeneous electric fields, which reduce the barriers
between energy minima for different polarization directions [20], and promote the decou‐
pling of the Pb-O-Ti/Zr bonding, making the corresponding Ti/Zr-hopping easier due to the
lack of lead ions. For the case of the B-site vacancies, all the Ti/Zr ions are well coupled to
the lead or the lanthanum ions.

From this point of view, it could be pointed out that for the PLZT10-VA sample the defects con‐
centration, which could promote the PNRs formation, is higher than that for the PLZT10-VB
sample. On the other hand, the thermal energy, which could change the nanoregions polariza‐
tion state, is smaller for the PLZT10-VA sample as a consequence of the smaller hopping barri‐
er. Considering these analyses, it could be explained the lower Tm values of the real part of the
dielectric permittivity for the PLZT10-VA. The observed results are in agreement with previ‐
ous reports for lead based systems with and without Pb2+ vacancies [52].

The larger temperature shift of Tm, which was analyzed for the PLZT10-VA, could be related
to a higher temperature dependence of the freezing process around Tm, i.e. higher tempera‐
ture dependence in the change of the volume fraction of frozen polar nanoregions around
Tm. The number of PNRs, which can follow the electric field switching, decreases with the
increase of the frequency. Thus, the maximum value of ε' decreases when the frequency in‐
creases, and also shifts to higher temperatures.

From the Figure 8, it is observed that the maximum values of the dielectric losses, for both
samples, are observed in the same temperature range. No remarkable differences exist as
can be expected from the difference observed in the Tm values between both systems. This
could suggest similar dipolar dynamic in the temperature range for both ceramics.

Figure 9 shows the temperature dependence of the remanent polarization (PR) for both sam‐
ples. The PLZT10-VB sample exhibits higher values, which is in agreement with the previ‐
ous discussion concerning the hopping barrier. The decoupling introduced by A-site
vacancies affects the total dipolar moment of the system and, consequently, the macroscopic
polarization is affected. Thus, the magnitude of the polarization decreases with the increase
of the A-site vacancies concentration.

On the other hand, the remanent polarization for both samples shows an anomaly in the
same temperature region (70–85oC), which could be associated with the ‘offset’ of the freez‐
ing process [14, 53]. This result suggests that the freezing temperature (TF) could be the same
for both samples or, at less the dynamic of PNRs is the same in both systems for that tem‐
perature range. Furthermore, the anomaly is observed in the same region where the maxi‐
mum values of the dielectric losses have been observed, which could suggest a relation
between the freezing phenomenon and the temperature evolution of dielectric losses.
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Figure 9. Temperature dependence of remnant polarization for the PLZT10-VA and PLZT10-VB samples. The lines be‐
tween dots are only a guide to the eyes.

3. Other typical relaxor ferroelectric perovskites

Relaxor-based ferroelectric materials PbMg1/3Nb2/3O3–PbTiO3 (PMN–PT) and

PbZn1/3Nb2/3O3–PbTiO3 (PZN–PT) have been extensively studied due to their high electrome‐
chanical coupling factor and piezoelectric coefficient [3,8,16-21,43-44,54-57].
It is known that the large dielectric permittivity of perovskite relaxor ferroelectrics, such as
(PbMg1/3Nb2/3O3)1−x(PbTiO3)x, comes from ferroelectric like polar nanoregions [30]. Upon
lowering the temperature these nanoregions grow slightly [43] but do not form long-range
ferroelectric order. The temperature dependence of the dielectric permittivity shows a fre‐
quency-dependent peak as the polar nanoregion orientations undergo some sort of glassy
kinetic freezing. Analyses of the phase and microstructure evolution for these materials
have showed that the increase in the sintering temperature caused the weakening of the die‐
lectric relaxor behaviour [54]. It has been related to compositional fluctuation and the release
of the internal stresses, leading to the decrease in the short-range B-site order.
The PNRs freezing process in PbMg1/3Nb2/3O3 has been analyzed considering both polariza‐
tion and strain operating on subtly different timescales and length scales [57]. The strain
fields are considered as relatively weak but longer ranging, while the dipole interactions
tend to be short range and relatively strong. It has been discussed that the elastic shear
strain fields is partly suppressed by cation disordering and screened by the presence of anti‐
phase boundaries with their own distinctive strain and elastic properties, which provide a
mechanism for suppressing longer ranging correlations of strain fields.
On the other hand, the barium modified PZN-PT system has shown excellent piezoelectric
properties [58]. The preparation of PZN system usually needs the addition of BaTiO3 (BT) to
obtain pure phases. Therefore, the ternary system PZN-PT-BT has received wider attention,
98 Advances in Ferroelectrics

showing high values of the dielectric permittivity and the pyroelectric coefficient [21,59].
This material shows lower diffuseness of the phase transition and weaker frequency disper‐
sion of the dielectric response than that of the PZN-BT system [16]. It has been shown that it
could be interesting try to decrease the transition temperature and to grow the value of the
figure of merit in order to obtain better materials for practical applications [17-18,21,60-61].

The present authors have developed several researches concerning (Pb0.8Ba0.2)

[(Zn1/3Nb2/3)0.7Ti0.3]O3 (PZN-PT-BT) system [19,62-63]. A Positive Temperature Coefficient of
Resistivity (PTCR) effect has been studied. This effect has found extensive applications as ther‐
mal fuses, thermistors, safety circuits and other overload protection devices [64]. It has been
discussed that the PTCR behaviour primarily arise from the Schottky barrier formed at grain
boundary regions, which act as effective electron traps of the available electrons from the oxy‐
gen vacancies in the ceramic, increasing the Schottky barrier height of the material. Excellent
properties to be used in dielectric and pyroelectric applications have been also reported [63].

Figure 10 shows the temperature dependence of the real part (ε') of the dielectric permittivi‐
ty for the (Pb0.8Ba0.2)[(Zn1/3Nb2/3)0.7Ti0.3]O3 ferroelectric ceramic system at several frequencies.
Typical characteristics of relaxor ferroelectrics are observed. There is a strong dispersion of
the maximum of ε' and its corresponding temperature shift towards higher temperatures
when the frequency increases. On the other hand, the system did not follow a Curie–Weiss–
like behaviour above Tm. For relaxor ferroelectrics, some of the dipoles are frozen during the
time scale of measurement. The fraction of frozen dipoles in itself is a function of the tem‐
perature, so Curie-Weiss’s law is no longer valid.

Figure 10. Temperature dependence of the real (ε') part of the dielectric permittivity at several frequencies for
(Pb0.8Ba0.2)[(Zn1/3Nb2/3)0.7Ti0.3]O3 ferroelectric ceramic system.

For Pb(B´1/3B”2/3)O3 type pervoskites, it has been reported a particular microstructure where
the B-site 1:1 short-range-ordered nanodomains (rich in B’ ions) are embedded in a matrix
rich in B” ions, which promotes a compositional inhomogeneity [65]. The nonstoichiometric
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ordering induces strong charge effects; i.e., the ordered domains have a negative charge
with respect to the disordered matrix. Thus, the charge imbalance inhibits the growth of do‐
mains and nanodomains are obtained in a disordered matrix with polar micro-regions.

Figure 11. Hysteresis loops for (Pb0.8Ba0.2)[(Zn1/3Nb2/3)0.7Ti0.3]O3 ferroelectric ceramic system.

Figure 11 shows the hysteresis loops at several temperatures for the studied system. Slim P-
E loops and small remanent polarization values are observed. The slim-loop nature suggests
that most of the aligned dipole moments switch back to a randomly oriented state upon re‐
moval of the field. It could be interpreted in terms of correlated polar nanodomains embed‐
ded in a paraelectric matrix [44]. For relaxor ferroelectric materials, there is a micro- to
macro-domain transition [66]. In the absence of any external field, the domain structure of
relaxor ferroelectrics contains randomly oriented micropolar regions. When an electric field
is applied, the micro-domains are oriented along the field direction and the macro-domains
appear. The micro- to macro-domain transition has been confirmed by ‘in-situ’ switching by
means of an electron beam inducing local stresses to align the domains [66].

4. Lead free Aurivillius relaxor ferroelectrics

The temperature dependence of the real (ε') and imaginary (ε'') parts of the dielectric permit‐
tivity, at several frequencies, for the Sr0.5Ba0.5Bi2Nb2O9 sample are showed in the Figure 12. The
maximum of ε' decreases with the increase of the frequency; its corresponding temperature
(Tm) shifts with the frequency, showing a high frequency dispersion. For the imaginary part
(ε'') the maximum values are observed at lower temperatures than those the observed for ε'
and the corresponding temperature again shows a significant frequency dispersion. These
characteristics are typical of relaxor ferroelectric materials. On the other hand, an abrupt in‐
crease of ε'' is observed in the higher temperature zone, which is more clear in the low frequen‐
cy range. This behaviour could be associated to the conductivity losses.
100 Advances in Ferroelectrics

Figure 12. Temperature dependence of the real (ε') and imaginary (ε'') parts of the dielectric permittivity, at several
frequencies, for the Sr0.5Ba0.5Bi2Nb2O9.

The origin of the relaxor behaviour for this material can be explained from a positional dis‐
order of cations on A or B sites of the perovskite blocks that delay the evolution of long-
range polar ordering [28]. Previous studies in the SrBi2Nb2O9 system have showed that the
incorporation of barium to this system conduces to a relaxor behaviour in the ferroelectric-
paraelectric phase transition [28,67] and the increases of barium content enhance the degree
of the frequency dispersion of the dielectric parameters [67]. This behaviour can be ex‐
plained considering that the barium ions can substitute the strontium ions in the A site of
the perovskite block but enter in the Bi2O22+ layers, conducting to an inhomogeneous distri‐
bution of barium and local charge imbalance in the layered structure. The incorporation of
barium ions to bismuth sites takes care to reduce the constrain existent between the perov‐
skite blocks and the layered structure [68].

The relaxor behaviour is usually characterized by using the variation of Tm with frequency
(ΔT), degree of the frequency dispersion, and the critical exponent (δ) obtained from the fol‐
lowing law [67]:

d
1
-
1
=
(T - Tm ) (8)
e ¢ e max
¢ C
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whereε'max is the maximum value for the real part of the dielectric permittivity, and δ and C
are constants. For an ideal relaxor ferroelectric δ =2, while for a normal ferroelectric δ =1 and
the system follows the Curie-Weiss law.

For the studied material, ΔT=50oC between 1 kHz and 1 MHz, which is higher than that of
the obtained values for the PMN and PLZT 8/65/35 systems [67]. Thus, the studied material
shows higher frequency dispersion. However, ΔT is lower than that of the BaBi2Nb2O9 sys‐
tem (BBN), which is in agreement with previous reports where ΔT decreases with the de‐
crease of the barium concentration [67].

The Figure 13 shows the dependency of the log (1/ε'-1/ε'max) vs. log (T-Tm) at 1 MHz for the
study ceramic sample. The solid points represent the experimental data and the line the fit‐
ting, which was carried out by using the equation 8. The value obtained for δ parameter is
1.71, which is in agreement with other reports for the studied system [67].

Figure 13. Dependence of the log (1/ε'-1/ε''max) vs. log (T-Tm) at 1 MHz for the Sr0.5Ba0.5Bi2Nb2O9.

Figure 14. Dependence of the log f with Tm for the Sr0.5Ba0.5Bi2Nb2O9 considering a frequency range from 1 kHz to 1
MHz. The fitting was carried out by using the Vogel-Fulcher law.
102 Advances in Ferroelectrics

Figure 14 shows the dependence of log f with Tm for the studied material. The experimental
data was fitted by using the Vogel-Fulcher law (equation 7). The fitting parameters have
been included in the figure. The difference between Tm at 1 kHz and TF is about 100 K, a
higher value considering the studies carried out in PMN type relaxors [69]. On the other
hand, the BBN system has showed a difference higher than 300 K, which is agreement with
its strong shift of Tm [28, 69].

5. Conclusions

The relaxor behaviour has been discussed in ferroelectric perovskites-related structures. The
influence of the coexistence of ferroelectric and antiferroelectric phases on the relaxor behav‐
iour of lanthanum modified lead zirconate titanate ceramics has been analyzed. A relaxation
model to evaluate the dynamical behaviour of the polar nanoregions in a relaxor ferroelec‐
tric PLZT system has been presented and the results have been discussed considering the
correlation between the polar nanoregions and the freezing temperature. On the other hand,
the influence of A or B vacancies on the relaxor behaviour for PLZT materials have been
studied considering the decoupling effects of these defects in the Pb-O-Ti/Zr bounding and
in terms of the dynamic of PNRs. Other typical relaxor ferroelectrics were analyzed too. For
the PZN-PT-BT system, the relaxor behaviour was discussed considering the presence of lo‐
cal compositional fluctuation on a macroscopic scale. The Sr0.50Ba0.50Bi2Nb2O9 ferroelectric ce‐
ramic, which is a typical relaxor from the Aurivillius family, was analyzed considering a
positional disorder of cations on A or B sites of the perovskite blocks, which delay the evolu‐
tion of long-rage polar ordering.

Acknowledgement

The authors wish to thank to TWAS for financial support (RG/PHYS/LA No. 99-050, 02-225 and
05-043) and to ICTP for financial support of Latin-American Network of Ferroelectric Materials
(NET-43). Thanks to FAPESP, CNPq and FAPEMIG Brazilian agencies. Thanks to CONACyT,
Mexico. Dr. A. Peláiz-Barranco wishes to thank the Royal Society. M.Sc. O. García-Zaldívar
wishes to thanks to Red de Macrouniversidades / 2007 and to CLAF/ICTP fellowships NS 32/08.

Author details

A. Peláiz-Barranco, F. Calderón-Piñar, O. García-Zaldívar and Y. González-Abreu

*Address all correspondence to: [email protected]

Physics Faculty−Institute of Science and Technology of Materials, Havana University, San

Lázaro y L, Vedado, La Habana, Cuba
 Relaxor Behaviour in Ferroelectric Ceramics 103
http://dx.doi.org/10.5772/52149

References

[1] Xu Y. Ferroelectric Materials and Their Applications. Netherland: Elsevier Science

Publishers; 1991.

[2] Strukov BA., Levanyuk AP. Ferroelectric Phenomena in Crystals. Berlin: Springer-
Verlag; 1998.

[3] Tai CW., Baba-Kishi KZ. Relationship between dielectric properties and structural
long-range order in (x)Pb(In1/2Nb1/2)O3:(1 − x)Pb(Mg1/3Nb2/3)O3 relaxor ceramics. Acta
Materialia 2006;54; 5631-5640.

[4] Huang S., Sun L., Feng Ch., Chen L. Relaxor behaviour of layer structured
SrBi1.65La0.35Nb2O9. J. Appl. Phys. 2006;99; 076104.

[5] Ko JH., Kim DH., Kojima S. Correlation between the dynamics of polar nanoregions
and temperature evolution of central peaks in Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3 ferroelectric
relaxors. Appl. Phys. Lett. 2007;90; 112904.

[6] Kumar P., Singh S., Juneja JK., Prakash Ch., Raina KK. Dielectric behaviour of La
substituted BPZT ceramics. Physica B 2009;404(16) 2126–2129.

[7] Craciun F. Strong variation of electrostrictive coupling near an intermediate tempera‐

ture of relaxor ferroelectrics. Physical Review B 2010;81; 184111.

[8] Ko JH., Kim DH., Kojima S. Low-frequency central peaks in relaxor ferroelectric
PZN-9%PT single crystals. Ferroelectrics 2007; 347(1) 25-29.

[9] Samara GA. The relaxational properties of compositionally disordered ABO3 perov‐
skites. J. Phys.: Condens. Matter 2003;15(9) R367.

[10] Shvartsman VV., Lupascu DC. Lead-free relaxor ferroelectrics. J. Am. Ceram. Soc.
2012;95(1) 1–26.

[11] Dai X., Xu Z., Li JF., Viehland D. Effects of lanthanum modification on rombohedral
Pb(Zr1-xTix)O3 ceramics: Part I. Transformation from normal to relaxor ferroelectric
behaviours. J. Mat. Res. 1996;11( 3) 618-625.

[12] Dai X., Xu Z., Li JF., Viehland D. Effects of lanthanum modification on rombohedral
Pb(Zr1-xTix)O3 ceramics: Part II. Relaxor behaviour versus enhanced antiferroelectric
stability. J. Mat. Res. 1996;11( 3) 626-638.

[13] Peláiz-Barranco A., Mendoza ME., Calderón-Piñar F., García-Zaldívar O., López-No‐
da R., de los Santos-Guerra J., Eiras JA., Features on phase transitions in lanthanum-
modified lead zirconate titanate ferroelectric ceramics. Sol. Sta. Comm.
2007;144(10-11) 425-428.

[14] García-Zaldívar O., Peláiz-Barranco A., Calderón-Piñar F., Fundora-Cruz A., Guerra
JDS., Hall DA., Mendoza ME.. Modelling the dielectric response of lanthanum modi‐
104 Advances in Ferroelectrics

fied lead zirconate titanate ferroelectric ceramics - an approach to the phase transi‐
tions in relaxor ferroelectrics. J. Phys.: Cond. Matt. 2008;20; 445230.

[15] Peláiz Barranco A., Calderón Piñar F., Pérez Martínez O. Normal-Diffuse Transition
in (Pb,La)Zr0.53Ti0.47O3 Ferroelectric Ceramics. Phys. Sta. Sol. (b) 2000;220(1) 591-595.

[16] Fan HQ., Kong LB., Zhang LY., Yao X. Structure-property relationships in lead zinc
niobate based ferroelectric ceramics. J. Appl. Phys. 1998;83; 1625-1630.

[17] Zhu WZ., Yan M., Effect of Mn-doping on the morphotropic phase boundary of
PZN-BT-PT system. J. Mater. Sci. Lett. 2001;20(16) 1527-1529.

[18] Zhu WZ., Yan M., Kholkin AL., Mantas PQ., Baptista JL., Effect of tungsten doping
on the dielectric response of PZN–PT–BT ceramics with the morphotropic phase
boundary composition. J. Eur. Ceram. Soc. 2002;22(3) 375-381.

[19] Peláiz-Barranco A., González-Carmenate I., Calderón-Piñar F., Relaxor behaviour in

PZN-PT-BT ferroelectric ceramics. Sol. Sta. Comm. 2005;134; 519-522.

[20] Haertling HG. Ferroelectric Ceramics: History and Technology. J. Am. Ceram. Soc.
1999;82(4) 797-818.

[21] Halliyal A., Kumar U., Newnham RE., Cross LE. Stabilization of the perovskite phase
and dielectric properties of ceramics in the Pb(Zn1/3Nb2/3)O3-BaTiO3 system. Am. Ce‐
ram. Soc. Bull. 1987;66(4) 671-676.

[22] Jennet DB., Marchet P., El Maaoui M., Mercurio JP., From ferroelectric to relaxor be‐
haviour in the Aurivillius-type Bi4-xBaxTi3-xNbxO12 (0<x<1.4) solid solutions. Mat. Lett.
2005;59; 376-382.

[23] Karthik C., Ravishankar N., Maglione M., Vondermuhll R., Etourneau J., Varma
KBR. Relaxor behaviour of K0.5La0.5Bi2Ta2O9 ceramics. Sol. Sta. Comm. 2006;139; 268–
272.

[24] González-Abreu Y., Peláiz-Barranco A., Araújo EB., Franco Júnior A. Dielectric relax‐
ation and relaxor behaviour in bi-layered perovskite. Appl. Phys. Lett. 2009;94(26)
262903.

[25] Zhang H., Yan H., Reece MJ. High temperature lead-free relaxor ferroelectric: inter‐
growth Aurivillius phase BaBi2Nb2O9–Bi4Ti3O12 ceramics. J. Appl. Phys. 2010;107;
104111.

[26] Chakrabarti A., Bera J. Effect of La-substitution on the structure and dielectric prop‐
erties of BaBi4Ti4O15 ceramics. J. Alloys Comp. 2010;505; 668–674.

[27] Rabe KM., Ahn CA. Triscone JM., editors. Physics of Ferroelectrics. Berlin Heidel‐
berg, New York: Springer; 2007.

[28] Miranda C., Costa MEV., Avdeev M., Kholkin AL., Baptista JL., Relaxor properties of
Ba-based layered perovskites. J. Eur. Ceram. Soc. 2001;21; 1303-1306.
 Relaxor Behaviour in Ferroelectric Ceramics 105
http://dx.doi.org/10.5772/52149

[29] Smolienskii GA. Physical phenomena in ferroelectric with diffused phase transition.
J. Phys. Soc. Japan 1970;28,Supplement; 26-30.
[30] Cross LE. Relaxor ferroelectrics. Ferroelectrics 1987;76; 241-267.
[31] Viehland D., Jang SJ., Cross LE., Wutting M. Freezing of the polarization fluctuations
in lead magnesium niobate relaxors. J. Appl. Phys. 1990;68; 2916-2921.
[32] Quian H., Bursill LA., Phenomenological theory of the dielectric response of lead
magnesium niobate and lead scandium tantalate. Int. J. Mod Phys. B 1996;10;
2007-2025.
[33] Ishchuk VM., Baumer VN., Sobolev VL., The influence of the coexistence of ferroelec‐
tric and antiferroelectric states on the lead lanthanum zirconate titanate crystal struc‐
ture. J. Phys. Condens. Matter 2005;17(19) L177-L182.
[34] Peláiz-Barranco A., Hall DA. Influence of composition and pressure on the electric
field-induced antiferroelectric to ferroelectric phase transformations in lanthanum
modified lead zirconate titanate ceramics. IEEE Trans. Ultras. Ferroel. Freq. Cont.
2009;56(9) 1785-1791.
[35] Jullian Ch., Li JF., Viehland D. Comparisons of polarization switching in “hard,”
“soft,” and relaxor ferroelectrics. J. Appl. Phys. 2005;95(8) 4316-4318.
[36] Peláiz-Barranco A., García-Zaldívar O., Calderón-Piñar F., López-Noda R., Fuentes-
Betancourt J. A multi-Debye relaxation model for relaxor ferroelectrics showing dif‐
fuse phase transition. Phys. Sta. Sol. (b) 2005;242(9) 1864-1867.
[37] Bovtun V., Petzelt J., Porokhonskyy V., Kamba S., Yakimenko Y. Structure of the die‐
lectric spectrum of relaxor ferroelectrics. J. Eur. Ceram. Soc. 2001;21(10-11) 1307-1311.
[38] Burns G., Dacol FH., Crystalline ferroelectrics with glassy polarization behaviour.
Phys. Rev. B 1983;28; 2527-2530.
[39] Cheng ZY., Katiyar RS., Yao X., Bhalla AS. Temperature dependence of the dielectric
constant of relaxor ferroelectrics. Phys. Rev. B 1998;57; 8166-8177.
[40] Bokov AA. Recent advances in diffuse ferroelectric phase transitions. Ferroelectrics
1992;131; 49-55.
[41] Lin HT., Van Aken DC., Huebner W. Modelling the dielectric response and relaxa‐
tion spectra of relaxor ferroelectrics. J. Am. Ceram. Soc. 1999;82(10) 2698-2704.
[42] Dal-Young K., Jong-Jin Ch., Hyoun-Ee K. Birefringence study of the freezing mecha‐
nism of lanthanum-modified lead zirconate titanate relaxor ferroelectrics. J. Appl.
Phys. 2003;93; 1176-1179.
[43] Xu G., Shirane G., Copley JRD., Gehring PM. Neutron elastic diffuse scattering study
of Pb(Mg1/3Nb2/3)O3. Phys. Rev. B 2004;69; 064112.
[44] Viehland D., Li JF., Jang SJ., Cross LE., Wuttig M. Dipolar-glass model for lead mag‐
nesium niobate. Phys. Rev. B 1991;43; 8316-8320.
106 Advances in Ferroelectrics

[45] Xu G., Gehring PM., Shirane G. Coexistence and competition of local- and long-range
polar orders in a ferroelectric relaxor. Phys. Rev B 2006;74; 104110.
[46] Kirillov VV., Isupov VA. Relaxation polarization of PbMg1/3Nb2/3O3 (PMN) a ferro‐
electric with a diffused phase transition. Ferroelectrics 1973;5; 3-9.
[47] Isupov VA. Nature of physical phenomena in ferroelectric relaxors. Phys. Sol. Sta.
2003;45(6) 1107-1111.
[48] Pirc R., Blinc R. Vogel-Fulcher freezing in relaxor ferroelectrics. Phys. Rev. B 2007;76;
020101R.
[49] Jiménez R., Jiménez B., Carreaud J., Kiat JM., Dkhil B., Holc J., Kosec M., Algueró M.
Transition between the ferroelectric and relaxor states in
0.8Pb(Mg1/3Nb2/3)O3-0.2PbTiO3 ceramics. Phys. Rev. B 2006;74; 184106.
[50] Bokov AA., Ye Z-G. Recent progress in relaxor ferroelectrics with perovskite struc‐
ture. J. Mat. Sci. 2006;4(1) 31-52.
[51] Chen IW., Li P., Wang Y. Structural origin of relaxor perovskites. J. Phys. Chem. Sol.
1996;57(10); 1525-1536.
[52] Bellaiche L., Íñiguez J., Cockayne E., Burton BP. Effects of vacancies on the properties
of disordered ferroelectrics: A first-principles study. Phys. Rev. B 2007;75; 014111.
[53] Shen M., Han J., Cao W. Electric-field-induced dielectric anomalies in C-oriented
0.955Pb Zn1/3Nb2/3O3-0.045PbTiO3 single crystals. Appl. Phys. Lett. 2003;83(4) 731-733.
[54] Wu N-N., Hou Y-D, Wang Ch., Zhu M-K, Song X-M, Hui Y. Effect of sintering tem‐
perature on dielectric relaxation and Raman scattering of
0.65Pb(Mg1/3Nb2/3)O3−0.35PbTiO3 system. J. Appl. Phys. 2009;105; 084107.
[55] Park SE., Shrout TR. Ultrahigh strain and piezoelectric behaviour in relaxor based
ferroelectric single crystals. J. Appl. Phys. 1997;82(4) 1804-1811.
[56] Park SE., Shrout TR. Characteristics of relaxor-based piezoelectric single crystals for
ultrasonic transducers. IEEE Trans. Ultrason. Ferroelectr. Freq. Control 1997;44(5)
1140-1147.
[57] Carpenter MA., Bryson JFJ., Catalan G., Zhang SJ., Donnelly NJ. Elastic and inelastic
relaxations in the relaxor ferroelectric Pb(Mg1/3Nb2/3)O3: II. Strain–order parameter
coupling and dynamic softening mechanisms. J. Phys.: Condens. Matter 2012;24;
045902.
[58] Uchino K. High electromechanical coupling piezoelectrics: relaxor and normal ferro‐
electric solid solutions. Sol. Sta. Ion. 1998;108(1-4) 43-52.
[59] Deb KK., Hill MD., Roth RS., Kelly JF. Dielectric and pyroelectric properties of doped
lead zinc niobate (PZN) ceramic materials. Am. Cer. Bull. 1992;71; 349-352.
[60] Krumin A. Specific solid state features of transparent ferroelectric ceramics. Ferro‐
electrics 1986;69(1) 1-16.
 Relaxor Behaviour in Ferroelectric Ceramics 107
http://dx.doi.org/10.5772/52149

[61] Xia F., Yao X. Piezoelectric and dielectric properties of PZN-BT-PZT solid solutions.
J. Mat. Sci. 1999;34; 3341-3343.

[62] Peláiz Barranco A., González Carmenate I., Calderón Piñar F., Torres García E. AC
behaviour and PTCR effect in PZN-PT-BT ferroelectric ceramics. Sol. Sta. Comm.
2004;132; 431-435.

[63] Peláiz Barranco A., Gonzalez Carmenate I., Calderón Piñar F. Dielectric and pyro‐
electric behaviour of (Pb0.8Ba0.2)[(Zn1/3Nb2/3)0.7Ti0.3]O3 ferroelectric ceramics. Rev. Cub.
Fis. 2009;26(2B) 238-241.

[64] Chang H-Yi., Liu K-S., Lin IN. Modification of PTCR behaviour of (Sr0 2Ba0 8)TiO3 ma‐
terials by post-heat treatment after microwave sintering. J. Eur. Ceram. Soc.
1996;16(1) 63-70.

[65] Chen J., Chan H., Harmer MP. Ordering structure and dielectric properties of undop‐
ed and La/Na-doped Pb(Mg1/3Nb2/3)O3. J. Am. Ceram. Soc. 1989;72(4) 593-598.

[66] Randall CA., Barber DJ., Whatmore RW., Groves P. Short-range order phenomena in
lead-based perovskites. Ferroelectrics 1987;76(1) 277-282.

[67] Huang S., Feng Ch., Chen L., Wang Q. Relaxor Behaviour of Sr1–xBaxBi2Nb2O9 Ceram‐
ics. J. Am. Ceram. Soc. 2006;89(1) 328-331.

[68] Haluska MS., Misture ST. Crystal structure refinements of the three-layer Aurivillius
ceramics Bi2Sr2-xAxNb2TiO12 (A=Ca,Ba, x=0,0.5,1) using combined X-ray and neutron
powder diffraction. J. Solid State Chem. 2004;177; 1965-1975.

[69] Kholkin AL., Avdeev M., Costa MEV., Baptista JL. Dielectric relaxation in Ba-based
layered perovskites. Appl. Phys. Letters 2001;79(5) 662-664.
 Provisional chapter
Chapter 6

Electronic Band Structures and Phase Transitions of

Electronic Band
Ferroelectric Structures
and and Phase
Multiferroic Transitions of
Oxides
Ferroelectric and Multiferroic Oxides

Zhigao Hu, Junhao Chu,

Yawei
ZhigaoLi,Hu,
Kai Jiang
JunhaoandChu,
Ziqiang Zhu Li, Kai Jiang and
Yawei
Ziqiang Zhu
Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52189

1. Introduction
Perovskite ferroelectric (FE) materials have attracted considerable attention for a wide range
of applications, such as dynamic random access memories (DRAM), microwave tunable
phase shifters and second harmonic generators (SHGs). [1–3] Moreover, materials that
have coupled electric, magnetic, and structural order parameters that result in simultaneous
ferroelectricity, ferromagnetism, and ferroelasticity are known as multiferroics. [4–6] These
multiferroics materials have attracted a lot of attention in recent years because they can
potentially offer a whole range of new applications, including nonvolatile ferroelectric
memories, novel multiple state memories, and devices based on magnetoeletric effects.
Although there are some reports on the electrical and magnetic properties of perovskite-type
ferroelectric and multiferroics materials, optical properties and electronic transitions have not
been well investigated up to now. On the other hand, phase transition is one of the important
characteristics for the ferroelectric/multiferroics system. As we know, the phase transition is
strongly related to the structural variation, which certainly can result in the electronic band
modifications. Therefore, one can study the phase transition of the above material systems
by the corresponding spectral response behavior at different temperatures.
Among these materials, barium strontium titanate (BST) has been considered to be one of
the most promising candidates for devices due to its excellent dielectric properties of high
dielectric functions, low leakage current and an adjustable Curie temperature Tc through
variation of the composition between barium titanate (BT) and strontium titanate (ST).
However, the limited figure of merit at high frequency microwave region restricts the BST
practical applications. In order to improve the physical properties of the BST materials,
introducing small compositions of dopants has been used for several decades. Many
experimental and theoretical studies have been performed on the dielectric properties of
BST in the ferroelectric state by adding dopants such as Magnesium [7, 8], Aluminum [9],
Manganese (Mn) [10–12], Samarium [13], and different rare earth [14], In particular, the Mn

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distribution, et al.; licensee InTech.
reproduction in anyThis is an open
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Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
110 Advances in Ferroelectrics
2 Advances in Ferroelectrics

doping BST shows some advantages in reducing the dielectric loss, enhancing the resistivity,
and increasing dielectric tunability. It can significantly improve the dielectric properties,
which makes it a potential candidate for microwave elements. For example, the Mn doping
can cause the variation of the oxygen vacancy, which is the crucial role in modifying the
dielectric loss mechanism. On the other hand, the doping of Mn can also reduce the dielectric
constant peak and broaden the dielectric phase transition temperature range, which results
in a smaller temperature coefficient of capacitance in BSMT materials. [10] Therefore, it is
important to further investigate the physical properties of BSMT materials in order to develop
the potential applications.
Meanwhile, many research groups have focused on the doping effect on the fabrications and
dielectric properties for strontium barium niobate SrBi2 Nb2 O9 (SBN) materials. [15–20] The
substitution of Ca ions in the Sr site for the SBN ceramic induced the TC increasing, which is
useful for the application in high-temperature resonators. [15, 18] However, the substitution
of some rare earth ions such as La3+ or Pr3+ for Bi3+ in the Bi2 O2 layers can result in a shift
for the TC to lower temperature. [16, 20, 21] It is found that the behavior of the Nd-doped
SBN ceramic tends to change from a normal ferroelectrics to a relaxor type ferroelectrics
owing to the introduction of Nd ions in the Bi2 O2 layers. [16, 17, 20, 22] Up to now, a
detailed understanding of the lattice dynamic properties and the phase transition behavior
of Nd-doped SBN ceramics are still lacking. Raman spectroscopy is a sensitive technique
for investigating the structure modifications and lattice vibration modes, which can give
the information on the changes of lattice vibrations and the occupying positions of doping
ions. Thus, it is a powerful tool for the detection of phase transition in the doping-related
ferroelectric materials. [22, 23]
The optical properties such as the dielectric functions provide an important insight on
dielectric and ferroelectric behaviors of the material and play an important role in design,
optimization, and evaluation of optoelectronic devices. [24–27] In addition, the doping of
Mn or Nd can induce more defects in the lattice structure, which can affect its electronic
band structures and optoelectronic properties. Hence, the doping composition dependence
of optical properties for BST and SBN ceramics is technically important for practical
optoelectronic device development. Compared to film structure, the optical properties of
bulk material (single crystals and dense ceramics) are not affected by interface layer, stress
from clamping by the substrate, non-stoichiometry and lattice mismatch between film and
substrate. Hence, it is desirable to carry out a delicate investigation regarding the optical
properties of the BSMT and SBNN ceramics. Note that spectroscopic ellipsometry (SE),
Raman scattering, and transmittance spectra are potentially valuable techniques for the
studies of ferroelectric materials due to their high sensitivity of local structure and symmetry.
Compared with the other techniques, they can provide dielectric functions of the materials.
SE and transmittance spectra can provide optical band gap and optical conductivity, whereas
Raman spectra can provide Raman-active modes of the materials. [28–31]
On the other hand, bismuth ferrite (BiFeO3 , BFO) is known to be the only perovskite material
that exhibits multiferroic at room temperature (RT). At RT, it is a rhombohedrally distorted
ferroelectric perovskite with the space group R3c and a Curie temperature (TC ) of about 1100
K. [32–36] Since the physical properties of BFO films are related to their domain structure and
phase states, which is sensitive to the applied stress, composition, and fabrication condition
for BFO materials. PLD technique has the ability to exceed the solubility of magnetic
impurity and to permit high quality film grown at low substrate temperature. Recent studies
of photoconductivity, [35] photovoltaic effect, [37] and low open circuit voltage in a working
solar device, [38] illustrate the potential of polar oxides as the active photovoltaic material.
 Electronic Band Structures and Phase Transitions of Ferroelectric and Multiferroic Oxides 111
Electronic Band Structures and Phase Transitions of Ferroelectric and Multiferroic Oxides 3
http://dx.doi.org/10.5772/52189

In spite of the promising properties, there are no systematical reports focused on the optical
properties of BFO films. In order to make BFO useful in actual electrical and optoelectronic
devices, the physical properties, especially for electronic band structure and optical response
behavior, need to be further clarified.
The objectives of the chapter will tentatively answer the interesting questions: (1) Is there
an effective method to directly analyze electronic structure of FE materials by optical
spectroscopy? (2) What kind of temperature dependence have FE oxides from band-to-band
transitions? (3) Can spectral response at high-temperature be used to judge phase transition?
Correspondingly, this chapter is arranged in the following way. In Sec. 2, detailed growths
of Ba0.4 Sr0.6− x Mnx TiO3 (BSMT), SrBi2− x Ndx Nb2 O9 (SBNN) ceramics and BFO films are
described; In Sec. 3, solid state spectroscopic techniques are introduced; In Sec. 4, electronic
band structures of BSMT ceramics are presented; In Sec. 5, phase transitions of SBNN
ceramics are derived; In Sec. 6, temperature effects on electronic transitions of BFO films
have been discussed; In Sec. 7, the main results and remarks are summarized.

2. Experimental
2.1. Fabrications of FE ceramics
The ceramics based on Ba0.4 Sr0.6− x Mnx TiO3 (with x = 1, 2, 5 and 10%) specimens were
prepared by the conventional solid-state reaction sintering. High purity BaCO3 (99.8%),
SrCO3 (99.0%), TiO2 (99.9%), and MnCO3 were used as the starting materials. Weighted
powers were mixed by ball milling with zirconia media in the ethanol as a solvent for 24 h
and then dried at 110 ◦ C for 12 h. After drying, the powders were calcined at 1200 ◦ C for 4
h, and then remilled for 24 h to reduce the particle size for sintering. The calcined powders
were added with 8 wt.% polyvinyl alcohol (PVA) as a binder. The granulated powders were
pressed into discs in diameter of 10 mm and thickness of 1.0 mm. The green pellets were
kept at 550 ◦ C for 6 h to remove the solvent and binder, followed by sintering at 1400 ◦ C for
4 h. More details of the preparation process can be found in Ref. [39]. On the other hand,
the SBNN (x=0, 0.05, 0.1, and 0.2) ceramics were prepared by a similar method, and SrCO3 ,
Bi2 O3 , Nb2 O5 , and Nd2 O3 were used as the starting materials. Details of the fabrication
process for the ceramics can be found elsewhere. [17, 40]

2.2. Depositions of BFO films

The BiFeO3 films were deposited on c-sapphire substrates by the PLD technique. The BiFeO3
targets with a diameter of 3 cm were prepared through a conventional solid state reaction
method using reagent-grade Bi2 O3 (99.9%) and Fe2 O3 (99.9%) powders. Weighed powders
were mixed for 24 h by ball milling with zirconia media in ethanol and then dried at 100 ◦ C
for 12 h. The dried powders were calcined at about 680 ◦ C in air for 6 h to form the desired
phase, and followed by sintering at about 830 ◦ C for 2 h. Before the deposition of the BFO
films, c-sapphire substrates need to be cleaned in pure ethanol with an ultrasonic bath to
remove physisorbed organic molecules from the surfaces, followed by rinsing several times
with de-ionized water. Then the substrates were dried in a pure nitrogen stream before the
film deposition. A pulsed Nd:YAG (yttrium aluminum garnet) laser (532 nm wavelength,
5 ns duration) operated with an energy of 60 mJ/pulse and repetition rate of 10 Hz was
used as the ablation source. The films were deposited immediately after the target was
112 Advances in Ferroelectrics
4 Advances in Ferroelectrics

(110)
Ba Sr Mn
0.4 0.6- x

(111)

(211)
(200)

(220)
Intensity (arb.unit)

(310)
(210)
(100)

(300)
10%

5%

2%

1%

20 30 40 50 60 70 80
2 (Deg.)

Figure 1. The XRD patterns of the BSMT ceramics with the Mn composition of 1, 2, 5 and 10%, respectively.

preablated in order to remove any surface contaminants. The distance between the target
and the substrate was kept at 3 cm. The deposition time was set to about 30 min. Finally,
the films were annealed at 600 ◦ C in air atmosphere by a rapid thermal annealing process. A
detailed preparation of the films can be found in Ref. [6].

3. Optical spectroscopy
The ellipsometric measurements were carried out in the photon energy range of 0.7-4.2 eV
(300-1700 nm) with a spectral resolution of 5 nm by near-infrared-ultraviolet (NIR-UV) SE
(SC630UVN by Shanghai Sanco Instrument, Co., Ltd.). The measurements were performed
under the incident angle of 67◦ for all the ceramics corresponding to the experimental
optimization near the Brewster angle of the BSMT. Raman scattering experiments were
carried out using a Jobin-Yvon LabRAM HR 800 UV micro-Raman spectrometer, excited
by a 632.8 nm He-Ne laser with a spectral resolution of 0.5 cm−1 . Temperature dependent
measurements from 80 to 873 K were performed using the Linkam THMSE 600 heating stage,
and the set-point stability is of better than 0.5 K. The normal-incident transmittance spectra
were recorded using a double beam ultraviolet-infrared spectrophotometer (PerkinElmer
Lambda 950) at the photon energy from 0.5 to 6.5 eV (190-2650 nm) with a spectral resolution
of 2 nm. The samples at 5.3-300 K were mounted into an optical cryostat (Janis SHI-4-1) for
variable temperature experiments. [41]

4. Electronic band structures of BSMT ceramics

The XRD patterns of the BSMT ceramics with different Mn composition are shown in Fig. 1
and no secondary phase appears within the detection limit of the XRD. Besides the strongest
(110) peak, some weaker peaks (100), (111), (200), (210), (211), (220) can be also observed,
which indicate that the ceramics are polycrystalline with single perovskite phase. The
diffraction patterns are fitted by the Gaussian lineshape analysis to extract the peak positions
and full width at half maximum (FWHM). The lattice constant a of the BSMT ceramics,
which can be estimated from the (110) diffraction peak, is calculated to be about 3.954 Å. [39]
The ionic radius of Mn2+ (1.27 Å) is smaller than that of Sr2+ (1.44 Å) and Ba2+ (1.61 Å),
and is larger than that of Ti4+ (0.61 Å), which can be attributed to the change of the lattice
constant. When the Mn composition is below 5%, the (110) diffraction peak positions shift
from smaller angles to larger angles and the lattice constant slightly decreases, which can be
 Electronic Band Structures and Phase Transitions of Ferroelectric and Multiferroic Oxides 113
Electronic Band Structures and Phase Transitions of Ferroelectric and Multiferroic Oxides 5
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18
1%

(Deg.)
12 2%

5%

6
10%

(a)

120
(Deg.)
80

40
1 2 3 4
Figure 2. Experimental ellipsometric data (a) Ψ and (b) ∆ for the BSMT ceramics from near-infrared to ultraviolet photon energy
region at the incident angle of 67◦ . (Figure reproduced with permission from [39]. Copyright 2012, Springer.)

6
1

4
(a)

6
1%

4 2%
2

2
(b)

1 2 3 4
Photon energy (eV)

Figure 3. The (a) real and (b) imaginary parts of the NIR-UV dielectric functions for the BSMT ceramics with different Mn
composition. (Figure reproduced with permission from [39]. Copyright 2012, Springer.)

ascribed to the fact that Mn occupies the A site together with Ba2+ and Sr2+ . In order to
reduce distortion of the crystal lattice, the Mn mainly substitutes Sr2+ because the differences
in ionic radius between Mn ion and Ba ion is larger than that between Mn and Sr. On the
other hand, when the Mn composition is larger than 5%, the excess Mn can also substitute
the Ti site, which results in the increase of the lattice constant and the smaller shift of the
peak position. It can be concluded that the Mn ions substitute Sr sites of the BST lattice at
first, then occupy Ti sites when the Mn composition is beyond 5%.
The experimental ellipsometric spectra of Ψ and ∆ recorded at an incident angle of 67◦ for
the BSMT ceramics are depicted in Figs. 2(a) and (b), respectively. The observed changes
in the Ψ and ∆ data for different Mn composition may be attributed to the lattice distortion
and variation in atomic coordinate. Because the sample is bulk material with a thickness of
several millimeters, the dielectric functions of the BSMT ceramics can be directly calculated
114 Advances in Ferroelectrics
6 Advances in Ferroelectrics

eV cm )
-2
3.60

2
3.45

12
(eV)
2

E) /(x10
0 5 10

Mn Composition (%)

2
1% 5%

2% 10%

( 0
2.0 2.5 3.0 3.5 4.0

Photon energy (eV)

Figure 4. Absorption coefficient vs. incident photon energy near the optical band gap of the BSMT ceramics. The insert is
the optical band gap Eg with the different Mn composition. (Figure reproduced with permission from [39]. Copyright 2012,
Springer.)

according to the ellipsometric spectra Ḟigs. 3(a) and (b) show the real (ε 1 ) and imaginary (ε 2 )
parts of the dielectric functions in the photon energy range of 0.7-4.2 eV, respectively. The
evolution of ε with the photon energy is a typical optical response behavior of ferroelectric
and/or semiconductors. The optical band gap (Eg ) of the BSMT ceramics is one of the
important optical behaviors, which is calculated by considering a direct transition from the
VB to the CB when the photon energy falls on the materials. In the BSMT system, the
VB is mainly composed of the O 2p orbital and the CB is mainly composed of the Ti 3d
orbital. It should be noted that because of the splitting of the Ti 3d conduction bands into
t2g and e g subbands, the lowest CB arises from the threefold degenerate Ti 3d t2g orbital,
which has lower energy than the twofold degenerate Ti 3d e g orbital. [42] The absorption
coefficient related Eg of the BSMT ceramics can be determined according to the Tauc’s law:
(αE)2 = A( E − Eg ), where A is a constant, α and E are the absorption coefficient and incident
photon energy, respectively. For the allowed direct transition, the straight line between (αE)2
and E will provide the value of the band gap, which is extrapolated by the linear portion
of the plot to (αE)2 =0, as seen in Fig. 4. The Eg is estimated to 3.65, 3.57, 3.40 and 3.60 eV
corresponding to x=1, 2, 5 and 10% for the BSMT ceramics, respectively, as shown in the
inset of Fig. 4. The results suggest that the band gap of the BSMT ceramics decreases and
then increases with increasing Mn composition.
As we know, the optical band gap can be affected by some factors such as grain size, oxygen
vacancy, stress and amorphous nature of the materials. [2] The decreasing trend of the
band gap with the Mn composition below 5% can be attributed to the increase of the grain
size and the smaller lattice constant, which are caused by the Mn introduction in the A
sites. When the Mn composition is 10%, there is a sharp increase in the optical band gap
because the excess Mn will substitute the Ti site at the Mn composition of 10%, causing the
increase of the oxygen vacancies. In addition, the creation of an oxygen vacancy which is
associated with the generation of free charge carriers can be described as the following:
′′ ·· + O ; O → V·· + 2e− + 1/2O , where V·· represents the
MnO(−TiO2 ) → MnTi + VO O O O 2 O
doubly charged oxygen vacancy, OO is an oxygen ion at its normal site, e− is the free
electronic charge generated through the vacancy formation. [9, 43] The heavy doping blocks
the lowest states in the CB and the effective band-gap increases, which is known as the
Burstein-Moss (BM) effect. [44] When a large number of vacancy-related charge carriers are
 Electronic Band Structures and Phase Transitions of Ferroelectric and Multiferroic Oxides 115
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61 840
207 (b)

210
A1g[O]
179

Intensity (arb. units)

A1g[Nb] 834

200
97
0.0 0.1 0.2
281
Nd composition 835
310
579
456
435
x=0
x=0.05
x=0.1

(a)
x=0.2

200 400 600 800

-1
Raman shift (cm )

Figure 5. Raman scattering spectra of the SBNN ceramics with different Nd composition (x) recorded at RT. The dashed lines
clearly indicate some Raman-active phonon modes. The inset shows the peak frequency variation of the A1g [Nb] phonon mode
at about 207 cm−1 and the A1g [O] phonon mode at about 836 cm−1 as a function of Nd composition. (Figure reproduced with
permission from [46]. Copyright 2012, Wiley.)

generated in the system, the lowest lying states in the CB are filled and the vertical distance
needed for the optical transition increases. [44] Hence, it can be concluded that, when the Mn
composition is 10%, the sharply increase in the band gap may be attributed to the BM shift
caused by electrons generated by oxygen vacancies. Besides, the grain size for the ceramic
decreases induced by the heavy doping with the Mn composition of 10%, which may also
result in a sharply increase of the optical band gap. It can be concluded that the difference
of the optical band gap could be due to the dopant composition, the oxygen vacancies, and
the crystallinity of the BSMT ceramics.

5. Phase transitions of SBNN ceramics

The general formula of bismuth layer structure ferroelectrics (BLSFs) is given as (Bi2 O2 )2+
( Am−1 Bm O3m+1 )2− , where A and B are the two types of cations that enter the perovskite
unit, and m is the the number of perovskite unit cell between bismuth oxide layers. [20]
SBN, which is known to be m=2 member of BLSFs family, has been regarded as a promising
ferroelectric material due to low dielectric constants and excellent fatigue resistance. [40] Fig.
5(a) shows the Raman spectra of the SBNN ceramics with different Nd compositions at RT
in the spectral range of 50 − 950 cm−1 . The Raman selection rules allow 18 phonon modes
(4A1g + 2B1g + 6B2g + 6B3g ) for SBN ceramics at RT. [45] However, less than 10 phonon
modes are observed because of the possible overlap of the same symmetry vibration or the
weak feature of some vibration bands. [46, 47] According to the assignment of SrBi2 Nb2 O9
single crystal, [45] the Raman phonon modes at about 61, 207 and 835 cm−1 can be assigned
to the A1g phonon mode, the vibrations at about 179 and 579 cm−1 can be assigned to the Eg
phonon mode. However, the assignment of other phonon modes are still not clear now. The
internal vibrations of NbO6 octahedra occur in the high-frequency mode region above 200
cm−1 because the intragroup binding energy within the NbO6 octahedra is much larger than
the intergroup or crystal binding energy. [15] The composition dependence of the frequencies
for two typical phonon modes is illustrated in Fig. 5(b). Note that the A1g [Nb] phonon mode
at 207 cm−1 , which arises from the distortion of NbO6 octahedra, generally decreases with
the Nd composition, whereas the A1g [O] phonon mode at 835 cm−1 mode corresponding to
the symmetric Nb−O stretching vibration, increases with the introduction of Nd ions.
116 Advances in Ferroelectrics
8 Advances in Ferroelectrics

#
873 K A1g[O] (b) A1g[O] (d)

A1g[Bi]
#
#
#

Intensity (arb.units)
80 K

600 900 600 900

A1g[Nb]
Eg[Nb] x=0 x=0.2
80-873 K

(a) (c)

* *
* *

100 200 300 100 200 300

-1
Raman shift (cm )

Figure 6. Temperature dependence of the SBNN ceramics with the composition of (a)(b) x=0 and (c)(d) x=0.2. The solid arrows
indicate the temperature increasing from 80 K to 873 K, and the dash arrows show the shift of the frequency for the phonon
modes with the temperature. The symbol asterisk (∗) and pound sign (#) indicate the two weak Eg phonon modes in the range
of 281-310 cm−1 and 435-456 cm−1 , respectively. (Figure reproduced with permission from [46]. Copyright 2012, Wiley.)

In order to further understand the effect of Nd3+ ion substitution on the phonon modes, Fig.
6 presents the temperature dependence of the Raman spectra for the SBNN ceramics with
two Nd compositions of x=0 and 0.2 in the temperature range from 80 to 873 K. It suggests
that the intensities for all the phonon modes increase with the temperature except for the
phonon mode at about 579 cm−1 , whose peak has been overwhelmed at high temperature.
The broadening band can be assigned to a rigid sublattice mode, in which all the positive and
negative ion displacements are equal and opposite. [48] It is found that a strong broadening
peak can be observed at 80 K due to the combined effects of two modes splitting from the Eg
character mode. However, with increasing the temperature, the frequency and intensity of
the mode present a decreasing trend. Because the mode is assigned to the asymmetric Nb−O
vibration, it can be concluded that the NbO6 octahedra is sensitive to the temperature. On the
other band, the phonon modes at about 281 and 310 cm−1 (labeled by ∗), which are associated
with the O−Nb−O bending, become more difficult to be distinguished as the temperature
increases and disappear at high temperature. Similar phenomena can be observed for the
phonon modes in the range of 435-456 cm−1 (labeled by #). The band at about 456 cm−1 ,
which is described to a Ti−O torsional mode, has been assigned as the Eg character and splits
into two phonon modes centered at 435 and 456 cm−1 at lower temperature. As pointed out
by Graves et al., [45] it can be ascribed to the fact that the several Eg phonon modes split into
the B2g and B3g phonon modes during the tetragonal to orthorhombic transition. Moreover,
the splitting of the phonon modes reveals the structural changes in the SBNN ceramics with
the temperature.
Considering that the phase transition temperature is related to the distortion extent of the
NbO6 octahedra for the SBNN ceramics, the temperature dependence of the Raman shift
for the A1g [Nb] phonon mode is plotted in Fig. 7(a)-(d). For all the SBNN ceramics, the
decrease of the A1g [Nb] phonon mode can be observed as the temperature is increased. Note
that an obviously anomalous vibration occurs around the phase transition temperatures: the
Raman shift sharply increases with increasing the temperature. In addition, the temperature
 Electronic Band Structures and Phase Transitions of Ferroelectric and Multiferroic Oxides 117
Electronic Band Structures and Phase Transitions of Ferroelectric and Multiferroic Oxides 9
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208 710 K

200
(a)

x=0

Intensity (arb.units)
Frequency (cm )
207

-1
665 K

(b)
198 x=0.05

203 625 K

(c)
196 x=0.1

203
550 K

(d)
196 x=0.2
(e)

200 400 600 800 200 400 600 800

Temperature (K)

Figure 7. (a)-(d) Raman shift and (e) intensities of the A1g [Nb] phonon mode as a function of the temperature for the SBNN
ceramics. The arrows indicate that the anomalous vibration occurs around the ferroelectric to paraelectric phase transition
temperatures. (Figure reproduced with permission from [46]. Copyright 2012, Wiley.)
STO(111)

STO(222)
Intensity (arb. unit)

BFO(111)

BFO(222)

39 42 84 87
2 (Deg.)

Figure 8. The XRD patterns of the BFO films deposited on STO (111) substrate. (Figure reproduced with permission from [5].
Copyright 2010, American Institute of Physics.)

of the anomalous points is different for the four ceramics: 710 K for x=0, 665 K for x=0.05,
625 K for x=0.1 and 550 K for x=0.2. The different anomalous points can be ascribed to
the Nd3+ incorporation in the Bi2 O2 layers. In addition, the phase transition from the
orthorhombic to the tetragonal phase may occur at the temperature when the frequency
of the A1g [Nb] phonon mode shows the anomalous behavior. Therefore, the sharp change
in the temperature dependence of both wavenumber and intensity of the A1g [Nb] phonon
mode was successfully applied to probe the phase transition of the SBNN ceramics.

6. Temperature effects on electronic transitions of BFO films

BFO film with the nominal thickness of about 330 nm was prepared on STO (111) substrate
by pulsed laser deposition. [5] Fig. 8 shows the XRD pattern of the BFO film and
there is no impurity phase. As can be seen, the film is well crystallized with the
rhombohedral phase and presents a (111) single crystalline orientation. According to the
known Scherrer’s equation, the grain size from the (111) diffraction peak was evaluated
to about 32 nm. A three-phase layered structure (air/film/substrate) was constructed to
118 Advances in Ferroelectrics
10 Advances in Ferroelectrics

0.6
BiFeO
3

5.3 K

Transmittance
0.8
150 K

0.3

300 K

0.4 0.0
2.4 2.8

Photon energy (eV)

+0.2

0.0

1 2 3 4 5 6

Photon energy (eV)

Figure 9. Experimental (dotted curves) and fitting (solid curves) transmittance spectra at temperatures of 300 and 5.3 K,
respectively. The inset shows the enlarged band gap region of the BFO film at temperatures of 300, 200, and 5.3 K, respectively.
(Figure reproduced with permission from [5]. Copyright 2010, American Institute of Physics.)

simulate the transmittance spectra of the BFO film. It should be emphasized that the
normal-incident transmittance spectra cannot be sensitive to the thinner surface rough layer,
which could be several nanometers and much less than the film thickness. Therefore,
the surface rough layer can be reasonably neglected owing to a slight contribution in the
evaluation of the optical properties. The optical constants of the BFO film can be expressed
using four Tauc-Lorentz (TL) oscillators. [50] As an example, the experimental and fitting
transmittance spectra of the BFO film at 300 and 5.3 K are shown in Fig. 9 with the dotted
and solid curves, respectively. Note that the symmetrical interference period indicates that
the film is of good uniformity and crystallization. From Fig. 9, it can be observed that the
absorption edge remarkably shift toward the lower energy with increasing the temperature,
suggesting that the OBG of the film has a negative temperature coefficient. Note that
the shift at high temperature region (100-300 K) is larger than that at low temperature
region (5.3-100 K). This is because the quantities of the conduction band downward and
the valence band upward are different under the distinct temperature regions. Especially,
two broadening shoulder structures appear and the intensities become much stronger with
decreasing the temperature. The similar phenomena have been observed at 2.5 eV when the
temperature decreases to about 4 K, which represents the onset of the optical absorption.
[51] Furthermore, the shoulders are simply low-lying features of the electronic structure or
evidence for excitonic character.
Based on the theoretical calculations and experimental observations, the four energy bands
can be uniquely assigned to the following electronic transitions: (1) on-site Fe3+ d to d
crystal field transition; (2) majority channel Fe 3d to O 2p charge transfer excitation; (3)
minority channel dipole-allowed O p to Fe d charge transfer excitation; and (4) strong
hybridized majority channel O p and Fe d to Bi p state excitation, respectively. [51–55]
Within the experimental error bars, the energy positions shift toward the higher energy at the
temperature of 5.3 K except for the second excitation, which can be attributed to the energy
band variations. Nevertheless, the origin of the abnormal shift for the second excitation is
unclear in the present work. Under the influence of the tetrahedral crystal field, the Fe 3d
orbital states split into t2g and e g state and the t2g state strongly hybrided with the O p orbital.
[52] With decreasing the temperature, the t2g and e g states can be located at different level in
 Electronic Band Structures and Phase Transitions of Ferroelectric and Multiferroic Oxides 119
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20 5.3 K

200 K

300 K
10

1
0

-10

2.70
30 (eV)
Eg
2.68

20

2.66
BiFeO /SrTiO
3 3

10
0 100 200 300
Temperature (K)

0
1 2 3 4 5 6

Figure 10. The dielectric functions of the BFO films in the photon energy range of 0.5-6.5 eV at 300, 200, and 5.3 K,
respectively. The inset shows the temperature dependence of the Eg (dotted curve) and Bose-Einstein model fitting result (solid
curve). (Figure reproduced with permission from [5]. Copyright 2010, American Institute of Physics.)

the energy space, which can affect the electronic excited ability of the Bi, Fe, and O states. On
the other hand, the evaluated optical constants of the BFO film is presented in Fig. 10. The
real and imaginary parts of dielectric functions increase with the temperature at the lower
photon energy while decrease with further increasing the photon energy. With decreasing the
temperature, both the ε 1 and ε 2 shift toward the higher energy. The phenomena are related
to the modification of the electronic structure such as the fundamental band gap absorption
under the lower temperature. From the inset of Fig. 10, it can be found that the Eg value
increases from 2.65 ± 0.01 to 2.69 ± 0.01 eV, corresponding to decreasing the temperature
from 300 to 5.3 K, which indicates that the total shift value of the Eg is about 40 meV. The
observed decrease in the Eg with the temperature can be described using the Bose-Einstein
model. It is widely recognized that the electron-phonon interaction and the lattice thermal
expansion are responsible for the shrinkage in the optical band gap with the temperature.

7. Conclusion and remarks

In summary, electronic band structures and phase transitions of perovskite (ABO3 )-type
Manganese (Mn) doped Ba0.4 Sr0.6 TiO3 ceramics, SrBi2− x Ndx Nb2 O9 , and BiFeO3
materials have been investigated from infrared to ultraviolet transmittance, SE and
temperature-dependent Raman scattering techniques. The interband electronic transitions
and dielectric functions of these materials could be readily obtained in the wider
photon energy region. Meanwhile, the phase transition temperature can be easily
determined by phonon scattering measurements, indicating that the present solid state
spectroscopy is useful to further clarify the physical phenomena for perovskite-type
ferroelectric/multiferroics oxides.
It should be emphasized that optical properties and their related phenomena, such as phase
transition and domain status have not been well investigated. The following factors must
be addressed: (1) Growth of high-quality perovskite FE materials (crystal, ceramic and
120 Advances in Ferroelectrics
12 Advances in Ferroelectrics

film); (2) Theoretical model and explanations; (3) Improved experimental methods. As for
solid state spectroscopic technique, however, it can uniquely discover the electronic band
structure of FE system. One can think that the electronic transition will be changed during
the phase transition process owing to the crystal structure variation. Thus, we can check
the status by recording the spectral response. Evidently, some optical setup at elevated
temperatures are necessary because most of FE materials have the high TC . In our research
group, Transmittane/Reflectance, SE, and Raman systems from LHe temperature to about
800 K have been developed. Our next goal is to characterize the physical information of some
typical FE materials in a wider spectral and temperature ranges, which play an important
role in clarifying the structure transitions and the intrinsic origin.

Acknowledgments
The authors would like to thank Dr. Wenwu Li for valuable discussions. This work
was financially supported by the Major State Basic Research Development Program of
China (Grant Nos. 2011CB922200 and 2013CB922300), the Natural Science Foundation
of China (Grant Nos. 11074076, 60906046 and 61106122), the Program of New Century
Excellent Talents, MOE (Grant No. NCET-08-0192) and PCSIRT, the Projects of Science and
Technology Commission of Shanghai Municipality (Grant Nos. 11520701300, 10DJ1400201
and 10SG28), and the Program for Professor of Special Appointment (Eastern Scholar) at
Shanghai Institutions of Higher Learning.

Author details
Zhigao Hu1,⋆ , Junhao Chu1,2,⋆ ,
Yawei Li1 , Kai Jiang1 and Ziqiang Zhu1
1 Key Laboratory of Polar Materials and Devices, Ministry of Education, Department of
Electronic Engineering, East China Normal University, Shanghai, People’s Republic of China
2 National Laboratory for Infrared Physics, Shanghai Institute of Technical Physics, Chinese
Academy of Sciences, Shanghai, People’s Republic of China

References
[1] Nagaraj, B.; Sawhney, T.; Perusse, S.; Aggarwal, S.; Ramesh, R.; Kaushik, V. S.; Zafar, S.;
Jones, R. E.; Lee, J. -H.; Balu, V. & Lee, J. (1999). (Ba,Sr)TiO3 thin films with conducting
perovskite electrodes for dynamic random access memory applications. Appl. Phys.
Lett., 74, 21, 3194-3196

[2] Roy, S. C.; Sharma, G. L. & Bhatnagar, M. C. (2007). Large blue shift in the optical
band-gap of sol-gel derived Ba0.5 Sr0.5 TiO3 thin films. Solid State Commun., 141, 5,
243-247

[3] Kozyrev, A. B.; Kanareykin, A. D.; Nenasheva, E. A.; Osadchy, V. N. & Kosmin, D. M.
(2009). Observation of an anomalous correlation between permittivity and tunability of
a doped (Ba,Sr)TiO3 ferroelectric ceramic developed for microwave applications. Appl.
Phys. Lett., 95, 01, 012908(1-3)
 Electronic Band Structures and Phase Transitions of Ferroelectric and Multiferroic Oxides 121
Electronic Band Structures and Phase Transitions of Ferroelectric and Multiferroic Oxides 13
http://dx.doi.org/10.5772/52189

[4] Catalan, G. & Scott, J. F. (2009). Physics and applications of bismuth ferrite. Adv. Mater.,
21, 24, 2463-2485

[5] Li, W. W.; Zhu, J. J.; Wu, J. D.; Gan, J.; Hu, Z. G.; Zhu, M. & Chu, J. H. (2010).
Temperature dependence of electronic transitions and optical properties in multiferroic
BiFeO3 nanocrystalline film determined from transmittance spectra. Appl. Phys. Lett.,
97, 12, 121102(1-3)

[6] Jiang, K.; Zhu, J. J.; Wu, J. D.; Sun, J.; Hu, Z. G. & Chu, J. H. (2011). Influences of oxygen
pressure on optical properties and interband electronic transitions in multiferroic
bismuth ferrite nanocrystalline films grown by pulsed laser deposition. ACS Appl.
Mater. Interfaces, 03, 12, 4844-4852

[7] Su, B. & Button, T. W. (2004). Microstructure and dielectric properties of Mg-doped
barium strontium titanate ceramics. J. Appl. Phys., 95, 03, 1382-1385

[8] Xu, S.; Qu, Y. & Zhang, C. (2009). Effect of Mg2+ content on the dielectric properties of
Ba0.65− x Sr0.35 Mgx TiO3 ceramics. J. Appl. Phys., 106, 01, 014107(1-5)

[9] Kim, S. S. & Park, C. (1999). Leakage current behaviors of acceptor- and donor-doped
(Ba0.5 Sr0.5 )TiO3 thin films. Appl. Phys. Lett., 75, 17, 2554-2556

[10] Yuan, Z.; Lin, Y.; Weaver, J.; Chen, X.; Chen, C. L.; Subramanyam, G.; Jiang, J. C. &
Meletis, E. I. (2005). Large dielectric tunability and microwave properties of Mn-doped
(Ba,Sr)TiO3 thin films. Appl. Phys. Lett., 87, 15, 152901(1-3)

[11] Zhang, J. J.; Zhai, J. W. & Yao, X. (2009). Dielectric tunable properties of low-loss
Ba0.4 Sr0.6 Ti1−y Mny O3 ceramics. Scripta Mater., 61, 07, 764-767

[12] Liu, M.; Ma, C.; Collins, G.; Liu, J.; Chen, C.; Shui, L.; Wang, H.; Dai, C.; Lin, Y.;
He, J.; Jiang, J.; Meletis, E. I. & Zhang, Q. (2010). Microwave dielectric properties with
optimized Mn-doped Ba0.6 Sr0.4 TiO3 highly epitaxial thin films. Cryst. Growth Des., 10,
10, 4221-4223

[13] Li, Y. L. & Qu, Y. F. (2009). Dielectric properties and substitution mechanism of
samarium-doped Ba0.68 Sr0.32 TiO3 ceramics. Mater. Res. Bull., 44, 01, 82-85

[14] Zhang, J. J.; Zhai, J. W.; Chou, X. J. & Yao, X. (2008). Influence of rare-earth addition on
microstructure and dielectric behavior of Ba0.6 Sr0.4 TiO3 ceramics. Mater. Chem. Phys.,
111, 02, 409-413

[15] Huang, S. M.; Li, Y. C.; Feng, C. D.; Gu, M. & Liu, X. L. (2008). Dielectric and structural
properties of layer-structured Sr1− x Cax Bi2 Nb2 O9 . J. Am. Ceram. Soc., 91, 09, 2933-2937

[16] Huang, S. M.; Feng, C. D.; Chen, L. D. & Wen, X. W. (2005). Dielectric properties of
SrBi2− x Prx Nb2 O9 ceramics (x=0, 0.04 and 0.2). Solid State Commun., 133, 6, 375-379

[17] Sun, L.; Feng, C. D.; Chen, L. D. & Huang, S. M. (2007). Effect of substitution of
Nd3 for Bi3 on the dielectric properties and structures of SrBi2− x Ndx Nb2 O9 bismuth
layer-structured ceramics. J. Appl. Phys., 101, 08, 084102(1-5)
122 Advances in Ferroelectrics
14 Advances in Ferroelectrics

[18] Wu, Y.; Forbess, M. J.; Seraji, S.; Limmer, S. J.; Chou, T. P.; Nguyen, C. & Cao, G.
(2001). Doping effect in layer structured SrBi2 Nb2 O9 ferroelectrics. J. Appl. Phys., 90,
10, 5296-5302

[19] Liu, G. Z.; Wang, C.; Gu, H. S. & Lu, H. B. (2007). Raman scattering study of La-doped
SrBi2 Nb2 O9 ceramics. J. Phys. D: Appl. Phys., 40, 24, 7817-7820

[20] Fang, P.; Fan, H.; Li, J. & Liang, F. (2010). Lanthanum induced larger polarization
and dielectric relaxation in Aurivillius phase SrBi2− x Lax Nb2 O9 ferroelectric ceramics.
J. Appl. Phys., 107, 06, 064104(1-4)

[21] Verma, M.; Sreenivas, K. & Gupta, V. (2009). Influence of La doping on structural and
dielectric properties of SrBi2 Nb2 O9 ceramics. J. Appl. Phys., 105, 02, 024511(1-6)

[22] Speghini, A.; Bettinelli, M.; Caldiño, U.; Ramírez, M. O.; Jaque, D.; Bausá, L. E. & Solé,
J. G. (2006). Phase transition in Srx Ba1− x Nb2 O6 ferroelectric crystals probed by Raman
spectroscopy. J. Phys. D: Appl. Phys., 39, 23, 4930-4934

[23] Tenne, D. A.; Bruchhausen, A.; Kimura, N. D. L.; Fainstein, A.; Katiyar, R. S.; A.
Cantarero,; Soukiassian, A.; Vaithyanathan, V.; Haeni, J. H.; Tian, W.; Schlom, D. G.;
Choi, K. J.; Kim, D. M.; Eom, C. B.; Sun, H. P.; Pan, X. Q.; Li, Y. L.; Chen, L. Q.; Jia, Q. X.;
Nakhmanson, S. M.; Rabe, K. M. & Xi, X. X. (2006). Probing nanoscale ferroelectricity
by ultraviolet Raman spectroscopy. Science, 313, 5793, 1614-1616

[24] Zhu, J. J.; Li, W. W.; Xu, G. S.; Jiang, K.; Hu, Z. G. & Chu, J. H.
(2011). A phenomenalogical model of electronic band structure in ferroelectric
Pb(In1/2 Nb1/2 )O3 -Pb(Mg1/3 Nb2/3 )O3 -PbTiO3 single crystals around morphotropic
phase boundary determined by temperature-dependent transmittance spectra. Acta
Materialia, 59, 17, 6684-6690

[25] Zhang, W. J.; Li, W. W.; Chen, X. G.; Hu, Z. G.; Liu, W.; Wang, G. S.;
Dong, X.L. & Chu, J.H. (2011). Phonon mode and phase transition behaviors
of (1 − x )PbSc1/2 Ta1/2 O3 -xPbHfO3 relaxor ferroelectric ceramics determined by
temperature-dependent Raman spectra. Appl. Phys. Lett., 99, 04, 041902(1-3)

[26] Zhu, J. J.; Li, W. W.; Xu, G.S.; Jiang, K.; Hu, Z. G.; Zhu, M. & Chu, J. H. (2011).
Abnormal temperature dependence of interband electronic transitions in relaxor-based
ferroelectric (1 − x )Pb(Mg1/3 Nb2/3 )O3 -xPbTiO3 (x=0.24 and 0.31) single crystals. Appl.
Phys. Lett., 98, 09, 091913(1-3)

[27] Chen, X.; Jiang, K.; Hu, Z. G.; Chen, X. F.; Wang, G. S.; Dong, X. L. & Chu, J. H.
(2012). Abnormal electronic transition variations of lanthanum-modified lead zironate
stannate titanate ceramics near morphotropic phase boundary: A spectroscopic
evidence. Appl. Phys. Lett., 101, 01, 011914(1-5)

[28] Liao, Y. Y.; Li, Y. W.; Hu, Z. G. & Chu, J. H. (2012). Temperature dependent phonon
Raman scattering of highly a-axis oriented CoFe2 O4 inverse spinel ferromagnetic films
grown by pulsed laser deposition. Appl. Phys. Lett., 100, 07, 071905(1-4)
 Electronic Band Structures and Phase Transitions of Ferroelectric and Multiferroic Oxides 123
Electronic Band Structures and Phase Transitions of Ferroelectric and Multiferroic Oxides 15
http://dx.doi.org/10.5772/52189

[29] Li, W. W.; Yu, Q.; Liang, J. R.; Jiang, K.; Hu, Z. G.; Liu, J.; Chen, H. D.; & Chu, J. H.
(2011). Intrinsic evolutions of optical functions, band gap, and higher-energy electronic
transitions in VO2 film near the metal-insulator transition region. Appl. Phys. Lett., 99,
24, 241903(1-3)

[30] Han, M. J.; Jiang, K.; Zhang, J. Z.; Li, Y. W.; Hu, Z. G. & Chu, J. H. (2011). Temperature
dependent phonon evolutions and optical properties of highly c-axis oriented CuGaO2
semiconductor films grown by the sol-gel method. Appl. Phys. Lett., 99, 13, 131104(1-3)

[31] Yu, W. L.; Jiang, K.; Wu, J. D.; Gan, J.; Zhu, M.; Hu, Z. G. & Chu, J. H. (2011). Electronic
structures and excitonic transitions in nanocrystalline iron-doped tin dioxide diluted
magnetic semiconductor films: an optical spectroscopic study. Phys. Chem. Chem. Phys.,
13, 13, 6211-6222

[32] Wang, J.; Neaton, J. B.; Zheng, H.; Nagarajan, V.; Ogale, S. B.; Liu, B.; Viehland, D.;
Vaithyanathan, V.; Schlom, D. G.; Waghmare, U. V.; Spaldin, N. A.; Rabe, K. M.; Wuttig,
M. & Ramesh, R. (2003). Epitaxial BiFeO3 multiferroic thin film heterostructures.
Science, 299, 1719-1722

[33] Singh, M. K. & Katiyar, R. S. (2011). Phonon anomalies near the magnetic phase
transitions in BiFeO3 thin films with rhombohedral R3C symmetry. J. Appl. Phys., 109,
07, 07D916(1-3)

[34] Choi, S. G.; Yi, H. T.; Cheong, S. W.; Hilfiker, J. N.; France, R. & Norman, A. G. (2011).
Optical anisotropy and charge-transfer transition energies in BiFeO3 from 1.0 to 5.5 eV.
Phys. Rev. B, 83, 10, 100101(R)(1-4)

[35] Basu, S. R.; Martin, L. W.; Chu, Y. H.; Gajek, M.; Ramesh, R.; Rai, R. C.; Xu, X. &
Musfeldt, J. L. (2008). Influence of sample processing parameters on thermal boundary
conductance value in an Al/AlN system. Appl. Phys. Lett. 92, 09, 091905(1-3)

[36] Balke, N.; Choudhury, S.; Jesse, S.; Huijben, M.; Chu, Y. H.; Baddorf, A. P.; Chen, L.
Q.; Ramesh, R. & Kalinin, S. V. (2009). Deterministic control of ferroelastic switching in
multiferroic materials. Nature Nanotechnology, 4, 12, 868-875

[37] Yang, S. Y.; Martin, L. W.; Byrnes, S. J.; Conry, T. E.; Basu, S. R.; Paran, D.; Reichertz, L.;
Ihlefeld, J.; Adamo, C.; Melville, A.; Chu, Y. H.; Yang, C. H.; Musfeldt, J. L.; Schlom, D.
G.; Ager, I. J. W. & Ramesh, R. (2009). Photovoltaic effects in BiFeO3 . Appl. Phys. Lett.,
95, 06, 062909(1-3)

[38] Choi, T.; Lee, S.; Choi, Y. J.; Kiryukhin, V. & Cheong, S.-W. (2009). Switchable
ferroelectric diode and photovoltaic effect in BiFeO3 . Science, 324, 5923, 63-66.

[39] Jiang, K.; Zhang, J. Z.; Yu, W. L.; Hu, Z. G. & Chu, J. H. (2012). Manganese doping
effects on interband electronic transitions, lattice vibrations, and dielectric functions of
perovskite-type Ba0.4 Sr0.6 TiO3 ferroelectric ceramics. Appl. Phys. A-Mater. Sci. Process.,
106, 04, 877-884

[40] Zhu, M.; Sun, L.; Li, W. W.; Yu, W. L.; Li, Y. W.; Hu, Z. G. & Chu, J. H. (2010).
Lattice vibrations and dielectric functions of ferroelectric SrBi2− x ,Ndx Nb2 O9 bismuth
124 Advances in Ferroelectrics
16 Advances in Ferroelectrics

layer-structured ceramics determined by infrared reflectance spectra. Mater. Res. Bull.,

45, 11, 1654-1658

[41] Yu, W. L.; Li, W. W.; Wu, J. D.; Sun, J.; Zhu, J. J.; Zhu, M.; Hu,
Z. G. & Chu, J. H. (2010). Far-infrared-ultraviolet dielectric function, lattice
vibration, and photoluminescence properties of diluted magnetic semiconductor
Sn1− x Mnx O2 /c-sapphire nanocrystalline films. J. Phys. Chem. C, 114 , 18, 8593-8600

[42] Kohiki, S.; Arai, M.; Yoshikawa, H.; Fukushima, S.; Oku, M. & Waseda, Y. (2000).
Energy-loss structure in core-level photoemission satellites of SrTiO3 , SrTiO3 :La, and
SrTiO3 :Nb. Phys. Rev. B, 62, 12, 7964-7969

[43] Warren, W. L.; Vanheusden, K.; Dimos, D.; Pike, G. E. & Tuttle, B. A. (1996). Oxygen
vacancy motion in perovskite oxides. J. Am. Ceram. Soc., 79, 02, 536-538

[44] Burstein, E. (1954). Anomalous optical absorption limit in InSb. Phys. Rev., 93, 03,
632-633

[45] Graves, P. R.; Hua, G.; Myhra, S. & Thompson, J. G. (1995). The Raman modes of the
Aurivillius phases: Temperature and polarization dependence. J. Solid State Chem., 114,
01, 112-122

[46] Jiang, K.; Chen, X. G.; Li, W. W.; Zhan, Z. N.; Sun, L.; Hu, Z. G. & Chu, J. H. (2012).
Doping effect on the phase transition temperature in ferroelectric SrBi2− x Ndx Nb2 O9
layer-structured ceramics: A micro-Raman scattering study. J. Raman Spectrosc., 43, 04,
583-587

[47] Liang, K.; Qi, Y. J. & Lu, C. J. (2009). Temperature-dependent Raman scattering in
ferroelectric Bi4− x Ndx Ti3 O12 (x=0, 0.5, 0.85) single crystals. J. Raman Spectrosc., 40, 12,
2088-2091

[48] Dobal, P. S. & Katiyar, R. S. (2002). Studies on ferroelectric perovskites and Bi-layered
compounds using micro-Raman spectroscopy. J. Raman Spectrosc., 33, 06, 405-423

[49] Kitaev, Y. E.; Aroyo, M. I. & Mato, J. M. P. (2007). Site symmetry approach to
phase transitions in perovskite-related ferroelectric compounds. Phys. Rev. B, 75, 06,
064110(1-11)

[50] Jellison, G. E. Jr. & Modine, F. A. (1996). Parameterization of the optical functions of
amorphous materials in the interband region. Appl. Phys. Lett., 69, 03, 371-373. Erratum:
”Parameterization of the optical functions of amorphous materials in the interband
region”. 69, 03, 2137

[51] Basu, S. R.; Martin, L. W.; Chu, Y. H.; Gajek, M.; Ramesh, R.; Rai, R. C.; Xu, X. &
Musfeldt, J. L. (2008). Photoconductivity in BiFeO3 thin films. Appl. Phys. Lett., 92, 09,
091905(1-3)

[52] Chen, P.; Podraza, N. J.; Xu, X. S.; Melville, A.; Vlahos, E.; Gopalan, V.; Ramesh, R.;
Schlom, D. G. & Musfeldt, J. L. (2010). Optical properties of quasi-tetragonal BiFeO3
thin films. Appl. Phys. Lett., 96, 13, 131907(1-3)
 Electronic Band Structures and Phase Transitions of Ferroelectric and Multiferroic Oxides 125
Electronic Band Structures and Phase Transitions of Ferroelectric and Multiferroic Oxides 17
http://dx.doi.org/10.5772/52189

[53] Xu, X. S.; Brinzari, T. V.; Lee, S.; Chu, Y. H.; Martin, L. W.; Kumar, A.; McGill, S.; Rai, R.
C.; Ramesh, R.; Gopalan, V.; Cheong, S. W. & Musfeldt, J. L. (2009). Optical properties
and magnetochromism in multiferroic BiFeO3 . Phys. Rev. B, 79, 13, 134425(1-4)

[54] Ramirez, M. O.; Kumar, A.; Denev, S. A.; Podraza, N. J.; Xu, X. S.; Rai, R. C.; Chu, Y. H.;
Seidel, J.; Martin, L. W.; Yang, S. -Y.; Saiz, E.; Ihlefeld, J. F.; Lee, S.; Klug, J.; Cheong, S.
W.; Bedzyk, M. J.; Auciello, O.; Schlom, D. G.; Ramesh, R.; Orenstein, J.; Musfeldt, J. L.
& Gopalan, V. (2009). Magnon sidebands and spin-charge coupling in bismuth ferrite
probed by nonlinear optical spectroscopy. Phys. Rev. B, 79, 22, 224106(1-9)

[55] Ramirez, M. O.; Kumar, A.; Denev, S. A.; Chu, Y. H.; Seidel, J.; Martin, L. W.; Yang,
S. -Y.; Rai, R. C.; Xue, X. S.; Ihlefeld, J. F.; Podraza, N. J.; Saiz, E.; Lee, S.; Klug, J.;
Cheong, S. W.; Bedzyk, M. J.; Auciello, O.; Schlom, D. G.; Orenstein, J.; Ramesh, R.;
Musfeldt, J. L.; Litvinchuk, A. P. & Gopalan, V. (2009). Spin-charge-lattice coupling
through resonant multimagnon excitations in multiferroic BiFeO3 . Appl. Phys. Lett., 94,
16, 161905(1-3)
 Chapter 7

Phase Diagram of The Ternary BaO-Bi2O3-B2O3 System:

New Compounds and Glass Ceramics Characterisation

Martun Hovhannisyan

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52405

1. Introduction
Restriction and an interdiction on use of toxic materials in electronics products since 2006 have
promoted an intensification of development new ecologically friendly materials (glasses, glass
ceramics, ceramics) with attractive properties. It has stimulated new lead (cadmium) free
systems with good glass forming abilities investigations and new stoiciometric and eutectic
points revealing and characterization. Alkaline-earth bismuth borate ternary systems were a
good candidate for this purpose, because the binary Bi2O3-B2O3 system have propensity for
glass formation and set of binary compounds and eutectics [1 - 3]. Furthermore, bismuth borate
single crystals and glass ceramics have nonlinear optical (NLO) properties and other attrac‐
tive properties [4 - 7]. Both these factors are reasons for further study of binary and ternary
bismuth borate systems, and the glasses which they form.
The phase diagram of the Bi2O3–B2O3 system was first determined by Levin &Daniel in 1962
[2] and five crystalline compounds, Bi24B12O39, Bi4B2O9, Bi3B5O12, BiB3O6 and Bi2B8O15, were
identified. Later Pottier revealed a sixth compound, BiBO3 (bismuth orthoborate) [8], which
was missing in the original phase diagram [2]. There are no doubts about the existence of
BiBO3 now: Becker with co-workers have confirmed existence of bismuth orthoborate [5, 9,
10] and its transparent colourless single crystals of BiBO3 have recently been grown from the
melt and characterized by Becker & Froehlich [10]. Monophase samples of both crystalline
BiBO3 modifications were obtained by crystallisation below 550°C of bismuth borate glasses
with 50-57 mol% B2O3 [10]. However, these authors did not correct the phase diagram, and
did not determine the melting point of BiBO3 or the eutectic composition between BiBO3 and
Bi3B5O12. The compound BiBO3 and this eutectic point are clearly given on the Zargarova &
Kasumova’s version of the B2O3–Bi2O3 phase diagram, without indication of their melting
points and the eutectic composition [11].

© 2012 Hovhannisyan; licensee InTech. This is an open access article distributed under the terms of the
Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
128 Advances in Ferroelectrics

Kargin with co-authors [12] by DTA and X-ray analysis have studied conditions of metasta‐
ble phases formation at system Bi2O3-B2O3 melts crystallization. They have confirmed exis‐
tence of metastable BiBO3 compound and for the first time have specified on congruent
character of its melting. Authors also establish formation of a metastable phase of
5Bi2O3•3B2O3 composition. Both compounds together with initial Bi2O3 and B2O3 are present
on the metastable state diagram of the Bi2O3-B2O3 system constructed by them.
Presence of five compounds on the known Bi2O3-B2O3 phase diagram has naturally led to
formation of five eutectics compositions containing (mol % B2O3): 19.14 (622°C), 44.4 (646 °C),
73.5 (698°C), 76.6 (695°C) and 81.04 (709°C). There is an area of phase separation traditional
for borate systems, observed for compositions containing 81-100 mol % B2O3 [2]. Though
according to [12], the area of stable phase separation is stretched to 58-95 mol % B2O3.
Interest to ternary alkali free bismuth borate systems MxOy-Bi2O3-B2O3 (M=Zn,Sr,Ca,Ba)
studies has amplified recently. Various research groups (Russian, Canadian, Armenian)
worked in this area during 1990-2009 and revealed a number of ternary compounds, deter‐
mined their structure, optical and nonlinear optical properties. Thus, three ternary zinc bis‐
muth borate compounds have been revealed in the ZnO-Bi2O3-B2O3 system. At first
Zargarova& Kasumova have revealed ZnBi4B2O10 and ZnBiBO4 compounds [11]. Later Barb‐
ier with co-authors by solid-state reaction have synthesized third melilite type ZnBi2B2O7
compound with large SHG (four time higher as KDP) [13].
Barbier & Cranswick at first two novel noncentrosymmetric MBi2B2O7 or MBi2O(BO3)2
(M=Ca, Sr) compounds have synthesized by solid-state reactions in air at temperatures in
the 600–700°C range [14]. Their crystal structures have been determined and refined using
powder neutron diffraction data. CaBi2B2O7 compound has SHG response two time higher
as KDP [14]. However, authors didn’t pay attention for both compounds melting behavior.
Egorisheva with co-authors have studied phase relation in the CaO-Bi2O3-B2O3 system and
constructs the 600 °C (subsolidus) section of its phase diagram [15]. A new ternary com‐
pound of composition CaBi2B4O10 was identified and the existence of CaBi 2B2O7 ternary com‐
pound was comfirmed. Both compounds had incongruent melting at 700 and 783 °C
respectively and liquidus temperature about 900-930 °C.
Kargin with co-workers have studied phase relation in the SrO-Bi2O3-B2O3 system in subsoli‐
dus at 600 °C [16]. Two new ternary compound of Sr7Bi8B18O46 and SrBiBO4 compositions were
identified. Both compounds had incongruent melting at 760 and 820 °C without indication
liquidus temperature. However, later Barbier et el. have discribe new novel centrosymmet‐
ric borate SrBi2OB4O9 (SrBi2B4O10) forming in the SrO–Bi2O3–B2O3 system [17], thereby hav‐
ing substituted under doubt existence of previously reported Sr7Bi8B18O46 compound [16].
The uniqueness of the BaO-Bi2O3-B2O3 system is shown by the available sets of compounds
and eutectics both in the binary Bi2O3–B2O3 and BaO–B2O3 systems. Seven compounds are
known in the BaO-B 2O3 system. Four congruent melting binary compounds Ba3B2O6, BaB2O4,
BaB4O7, BaB8O13 with melting points(m.p.) 1383, 1105, 910, 889°C accordingly were found by
Levin & McMurdie [18, 19]. Further, Green and Wahler have found out new congruent melt‐
ed at 890°C Ba2B5O17 compound at the ternary BaO-B2O3-Al2O3 system investigation [20].
 Phase Diagram of The Ternary BaO-Bi2O3-B2O3 System: New Compounds and Glass Ceramics Characterisation 129
http://dx.doi.org/10.5772/52405

Hubner confirmed an existence of the congruent melted Ba2B5O17 compound with m.p. 890
°C, and revealed two new compounds Ba4B2O7, Ba2B2O5 [21]. However, all scientists and re‐
searches have used the melting diagram of the BaO-B2O3 system created by Levin & McMur‐
die up to now, without the indication in it the specific areas of existence of new compounds
and eutectic points among them [18].

Both these factors were the reason of the BaO-B2O3 system phase diagram correction made
by Hovhannisyan R.M. [22]. Author has revealed fields of Ba2B5O17 and BaB4O7 compounds
crystallisation and new eutectic points which are absent on the diagram constructed by Lev‐
in & McMurdie [18]. Six binary eutectic compositions containing 31.5, 37.5, 63.5, 68.5, 76.0,
83.4 mol % B2O3 with melting points 1025, 915, 905, 895, 869 and 878°C accordingly were on
the diagram after correction.

Area of two immiscible liquids established by Levin & McMurdie [35] in the BaO-B2O3 in an
interval of 1.5 to 30wt. % BaO content, it has been confirmed in the subsequent by other au‐
thors. However, the temperature of the liquation couple, which are 1150, 1180, 1256 °C ac‐
cording to [23] and 1539°C according to [24] is discussed till now.

There are no full version of the phase diagram of the BaO-Bi2O3 system till now [1]. It is very
complex system, which is very critical to atmosphere and pressure at experiment carrying
out [25 - 28]. Two low melted eutectic areas (740-790°C) clear observed on phase diagram
studied in air or oxigen in high bismuth content region around 5-7 mol%BaO and 25-30 mol
%BaO [26 - 28].

All research groups payd special attention to BaO-Bi2O3-B2O3 system studies and new ter‐
nary compounds revealing and characterisation. Barbier et al. have studied seven compo‐
sitions in the ternary BaO-B2O3-Bi2O3 system by solid state synthesis at temperatures below
650°C and BaBiBO4, or BaBi(BO3)O, a novel borate compound, has been made and chrac‐
terisised [29]. Above 650°C it decays with bismuth borate glass formation. A powder sam‐
ple of BaBiBO4 had a second harmonic signal with a NLO efficiency equal to five times
that of KDP.

Practically in parallel, Egorysheva with co-workers have been investigated phase equilibri‐
um in the Bi2O3-BaB2O4-B2O3 system by X-ray analysis and DTA [30, 31]. Studies were spent
by the samples solid state synthesis in closed Pt crucibles in muffle furnaces at the tempera‐
ture range 500-750 0C, that corresponds to sub-solidus area. The synthesis duration (with in‐
termediate cakes regrinding) were 6-16 days. They confirmed presence of BaBiBO4 and have
revealed three new compounds: BaBiB11O19, BaBi2B4O10, Ba3BiB3O9. BaBiB11O19, BaBi2B4O10
have congruent melting at 830 and 730 °C respectively and BaBiBO4 melt incongruently at
7800C. Ba3BiB3O9 undergoes a phase transition at 850°C and exist up to 885°C, were decom‐
pose in the solid state [31].

Recently single crystals of BaBi2B4O10 composition were grown by cooling of a melt with the
stoichiometric composition with cooling rate 0.5 K/h [32]. They have once again confirmed
existence of BaBi2B4O10 stoichometric compound earlier obtained by solid state synthesis.
130 Advances in Ferroelectrics

In 1972 Elwell with co-workers investigated the BaO–B2O3–Bi2O3 system by hot stage micro‐
scopy and a new ternary eutectic composition, 23.4BaO•62.4Bi2O3•14.2B2O3 (wt%), with a
low liquidus temperature of 600°C, was revealed for ferrite spinel growth [33].
Using different melts cooling rates Hovhannisyan, M. with co-authors at first have deter‐
mined large glass-forming field in the BaO-Bi2O3-B2O3 system, which includes all eutectics in
the binary Bi2O3-B2O3, BaO-B2O3 and BaO-Bi2O3 systems and covers majority of the concen‐
tration triangles, reaching up to 90 mol% Bi2O3. [34, 35].
The methodology based on glass samples investigation was more effective at BaO-Bi2O3-
B2O3 system phase diagram construction, than a traditional technique based on solid state
sintered samples studies. Because DTA curves of glasses, to the contrary DTA curves of sol‐
id state sintered samples, indicates their all characteristics temperatures, includes exother‐
mal effects of glass crystallizations and endothermic effects of formed crystalline phases
melting. It has allowed us to reveal two new BaBi2B2O7 and BaBi10B6O25 congruent melted at
725 and 690°C respectively compounds in the BaO-Bi2O3-B2O3 system [34 - 36].
However, our further studies of glasses and glass ceramics in this system have shown neces‐
sity of glass forming diagram correction and phase diagram construction in the ternary BaO-
Bi2O3-B2O3 system and present these data to scientific communitty. Another aim of this work
is both known and novel stoichiometric ternary barium bismuth borates compounds charac‐
terisation in glassy, glass ceramic and ceramic states for further practical application.

2. Experimental
About three hundred samples of various binary and ternary compositions have been synthe‐
sized and tested in BaO- Bi2O3-B2O3 system. Compositions were prepared from “chemically
pure” grade BaCO3, H3BO3 and Bi2O3 at 2.5-5.0 mol % intervals. The most part of samples
has been obtained as glasses by various cooling rates depending on melts glass forming abil‐
ities: as bulk glass plates with thickness 6,5 ÷7mm by casting on metallic plate (up to 10 K/s),
as monolithic glass plates with thickness up to 3mm by casting between two steel plates(~102
K
/s), and glass tapes samples with thickness 30–400 μm through super cooling method
( 103÷104 K/s). Glass formation was determined visually or by x-ray analysis. The glass melt‐
ing was performed at 800–1200°C for 15–20 min with a 20–50 g batch in a 20–50 ml uncov‐
ered quartz glass or corundum crucible, using an air atmosphere and a “Superterm 17/08”
electric furnace. Compositions in the BaO-B2O3 system were melted in a 25 or 50 ml uncov‐
ered Pt crucibles at 1400–1500°C for 30 min with a 20–50 g batch. The chemical composition
of some glasses was determined by traditional chemical analysis, and the results indicate a
good compatibility between the calculated and analytical amounts of B2O3, BaO and Bi2O3.
SiO2 contamination from quartz glass crucibles did not exceed 2 wt%, and alumina contami‐
nation did not exceed 0 5–1 wt%, according to the chemical analysis data.
Samples of compositions laying outside of a glass formation field or having high melting
temperature, have been obtained by solid-phase synthesis. Mixes (15-20 g) were carefully
 Phase Diagram of The Ternary BaO-Bi2O3-B2O3 System: New Compounds and Glass Ceramics Characterisation 131
http://dx.doi.org/10.5772/52405

frayed in an agate mortar, pressed as tablets, located on platinum plates and passed the
thermal treatment in “Naber”firm electric muffles. After regrinding powders were tested by
DTA and X-ray methods. The synthesized samples of binary barium borate system composi‐
tions containing 60 mol% and more of BaO and also compositions containing over 90mol %
B2O3 had very low chemical resistance and were hydrolyzed on air at room temperature. In
this connection the synthesized samples were kept in a dryer at 200°C.

DTA and X-ray diffraction data of glass and crystallized glass samples have been used for
phase diagram construction in the ternary BaO- Bi2O3 -B2O3 system. The DTA analysis (pure
Al2O3 crucible, powder samples weight ~600 mg, heating rates 10 K/min) on Q-1500 type de‐
rivatograph were carried out. Glass transition -Tg, crystallization peaks -Tcr, melting -Tm and
liquidus -TL temperatures have been determined from DTA curves. Reproducibility of tem‐
peratures effects on DTA curves from melting to melting was ±10K. The accuracy of temper‐
ature measurement is ±5 K.

Thermal expansion coefficient (TEC) and glass transition temperature (Tg) measurements
were made on a DKV-4A type vertical quartz dilatometer with a heating rate of 3K/min.
Glass samples in the size of 4×4×50 millimeters have been prepared for TEC measurement.
The dilatometer was graduated by the quartz glass and sapphire standards. The TEC meas‐
urement accuracy is ±(3÷4)∙10-7K-1, Tg ±5 °C.

X-ray patterns were obtained on a DRON-3 type diffractometer (powder method, CuKα–ra‐
diation, Ni-filter). Samples for glass crystallization were prepared with glass powder press‐
ed in the form of tablets. Crystallization process was done in the electrical muffles of
“Naber” firm by a single-stage heat treatment. This was done within 6-12 hours around a
temperature at which the maximum exothermal effects on glasses by DTA were observed.

Crystalline phases of binary and ternary compounds formed both at glasses crystalliza‐
tion and at solid-phase synthesis have been identified by using JCPDS-ICDD PDF-2 re‐
lease 2008 database [43].

Computerized methodic of ferroelectric hysteresis test and measurement of ferroelectric

properties such as coercive field and remanent polarization at wide temperature (up to
250°C and frequency (10-5000Hz) ranges was used. Methodic based on the well known Saw‐
yer – Tower’s [44] modified scheme, which is allowing to compensate phase shifts con‐
cerned with dielectric losses and conductivity. The desired frequency signal from waveform
generator is amplifying by high voltage amplifier and applying to sample. The signals, from
the measuring circuit output, proportional to applied field and spontaneous polarization are
passing throw high impedance conditioning amplifiers, converting by ADC and operating
and analyzing in PC. The technique allows to perform tests of synthesized glass ceramics
obtained by means of controlling crystallization of thin (above 30 micrometer thick) mono‐
lithic tape (film) specimens by applying up to 300kV/cm field to our thin samples (~50 mi‐
crometer thick) and obtain hysteresis loops for wide diversity of hard FE materials.
132 Advances in Ferroelectrics

3. Results

3.1. Glass forming and phase diagrams of the of the BaO-Bi2O3-B2O3 system

The traditional method of phase diagram construction based on solid-phase sintered sam‐
ples investigation takes long time and is not effective. The glass samples investigation tech‐
nique is progressive, because the DTA curves have registered all processes taking place in
glass samples, including the processes of glass crystallizations, quantity of crystal phases
and temperature intervals of their formation and melting. However, inadequate amount of
glass samples restrict their use during phase diagram construction. The super-cooling meth‐
od promotes the mentioned problem solving and open new possibilities for phase dia‐
grams constructions.

Hovhannisyan R.M. with co-workes sucseffuly developed this direction last time and have
constructed phase diagrams in binary and ternary alkiline-eath bismuth borate, barium bor‐
on titanate, barium aluminum boron titanate, barium gallium borate, yttrium aluminum bo‐
rate, yttrium gallium borate, lantanum gallium borate, zinc tellurium molibdate and other
systems [34 - 42].

3.1.1. Glass forming diagram of the BaO-Bi2O3-B2O3 system

Figure 1 shows the experimental data on glass formation in the BaO-Bi2O3-B2O3 system ob‐
tained by different authors from 1958 to 2007 [45 - 49]. For defining the glass forming ability
of the pointed system, the authors of the mentioned works used different amounts of melt,
glass melting crucibles, temperature–time melting regimes, and technological methods of
melt cooling. Imaoka & Yamazaki studied glass formation by melts cooling on air Glasses
were melted at temperatures below 1200 °C in gold-palladium or platinum-rhodium cruci‐
bles (Fig.1.1) [45]. Janakirama-Rao glass formation studied by melts cooling on air. Glasses
melted in platinum crucibles at 600- 1400 °C with 0.5-1.0 h melts exposition and its cooling
in air (Fig. 1.2) [46]. Izumitani [47] experiments spent in 10g crucibles at 1100-1350 °C with
melts cooling on air (Fig. 1.3). Milyukov with co-authors glass formation studied by melts
casting in steel mold. Glasses melted in platinum crucibles at 600-1400 °C with melts stirring
by Pt stirrer for 1h (Fig. 1.4) [48]. Kawanaka & Matusita glass formation studied by silica rod
stirred melts pouring into preheated to 250-300°C carbon mold (Fig. 1.5) [49].

Authors used different weights of glass forming melts, melting crucibles, temperature-time
of melting regimes and technological methods of melts cooling. Obtained data are difficultly
comparable and remote from two basic criteria promoting glass formation: liquidus temper‐
ature and speeds of melts cooling.
 Phase Diagram of The Ternary BaO-Bi2O3-B2O3 System: New Compounds and Glass Ceramics Characterisation 133
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Figure 1. Glass forming regions in the BaO-Bi2O3-B2O3 system according to the data of the authors: 1- [45], 2-[ 46],
3-[ 47], 4-[ 48], 5-[ 49].

Figure 2 shows corrected glass formation diagram in the BaO-Bi2O3-B2O3 system based on
phase diagrams of the BaO–B2O3, BaO–Bi2O3, and B2O3–Bi2O3 binary systems and controlla‐
ble melt cooling rates. Using the term “diagram,” but not the glass formation region, we
take into account the interrelation between the phase diagram and the glass forming ability
of the system.

Figure 2. Glass forming diagram in the BaO-Bi2O3-B2O3 system depending of melts cooling rates: 1-up to 10 K/s;
2~102K/s; 3-(103-104) K/s; 4- stable phase separation region.

Area of glass compositions with low crystallization ability and stable glass formation in the
studied ternary BaO-Bi2O3 -B2O3 system have been determined at melts cooling rate ~ 10 K/s
134 Advances in Ferroelectrics

(Fig.2-1). It included binary Bi4B2O9, BiBO3, Bi3B5O12, BiB3O6, Bi2B8O15, Ba2B10O17, BaB8O13 com‐
pounds in the BaO-Bi2O3 and BaO-B2O3 systems and five ternary BaBiB11O19(D), Ba‐
Bi2B4O10(C), BaBi 2B2O7 (E), BaBi 10B6O25 (F), and BaBiBO4 (B) compounds. However, we didn't
comfirm presence of Ba3BiB3O9 (A) compound in area of stable glasses at melts cooling rate ~
10 K/s, which was reported earlier [34, 35].

Increasing of melts cooling speed up to ~102 K/s has led to glass formation area expansion
(Fig.2-2). This cooling rate is enough for monolithic glass plates with thickness up to 3mm
fabrication by melts casting between two steel plates (Fig.2-2). The glass plates of composi‐
tions correspondings to Ba3BiB3O9 (A) and supposed BaBi8B2O16 (G) compounds have been
obtained by this way.

Super cooling technique constructed by our group allowed to expand the borders of glass
formation in studied system under high melts cooling rates equal to (103-104 ) K/s (Fig.2-3).
Determined glassforming area include compositions content: 80 – 95 mol% Bi2O3 in the bina‐
ry B2O3–Bi2O3 system; 43-70 mol% BaO in the binary BaO–B2O3 system, including BaB2O4
composition. Area of glass formation from both these areas moves to 55-95 mol% content
compositions in the binary BaO–Bi2O3 system (Fig.2-3).

Traditional for borate systems a stable phase separation region was also observed for high
B2O3 content compositions contents more than 84 -87 mol%B2O3 (Fig.2-4).

3.1.2. Phase diagram of the BaO-Bi2O3-B2O3 system

Our investigation of the ternary BaO-B2O3-Bi2O3 system have purposefully been directed on
construction of the phase diagram through first of all glass forming diagram construction
and revealing both new compounds and eutectic compositions. Constructed by us glass
forming diagram (Fig.2) practically occupies the most part of the BaO-B2O3-Bi2O3 concentra‐
tion triangles. It has allowed to use synthesized glasses as initial compositions at phase dia‐
gram construction. It was basic difference of our methodology from technologies used by
other authors. Phase equilibriums reached at isothermal sections construction do not allow
to have a full picture of processes in cases of the solid state synthesized samples investiga‐
tions. Whereas at glass samples studies we determine not only characteristic points of
glasses(Tg and Ts) by DTA, but also quantity of crystal phases, temperatures of their crystal‐
lization and then temperatures of their melting. It has allowed us to reveal new stoichiomet‐
ric compositions which have been lost by other research groups at isothermal sections
construction by traditional methods. In some cases we also in parallel used samples ob‐
tained by solid state synthesis for comparison with their glassy analogues or in those cases,
when their obtaining in the glassy form was impossible.
 Phase Diagram of The Ternary BaO-Bi2O3-B2O3 System: New Compounds and Glass Ceramics Characterisation 135
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Figure 3. The BaO-B2O3-Bi2O3 system triangulation

Experimental data concerning phase diagrams of binary systems Bi2O3-B2O3, BaO-B2O3, BaO-
Bi2O3 and pseudo-binary sections in the BaO-B2O3-Bi2O3 system have allowed us to estimate
fields of primary crystallization of co-existing phases and divided all concentration triangle
into elementary triangles, i.e. to make triangulation.

The triangulation scheme in the BaO-B2O3-Bi2O3 system is presented on Fig. 3. By means

of a triangulation all concentration triangle is divided into following elementary trian‐
gles: BiBO3-F-C, BiBO3-F-Bi4B2O9, BiBO3-C-Bi3B5O12, F-E-C, C-BaB2O4-E, C-Bi3B5O12-D,
Bi4B2O9-F-Bi2O3, E-Bi2O3-F, C-BaB2O4-Ba2B10O17, Ba2B10O17-D-C, Ba2B10O17-D-B2O3, Bi3B5O12-D-
Bi2B8O15, D-Bi2B8O15-B2O3.

3.1.2.1. Phase diagram of the binary Bi2O3–B2O3 system

First of all we have attempt to finished phase diagram construction in area of compositions
around of BiBO3 compound. Compositions containing 45–65 mol% B2O3 in the Bi2O3–B2O3
system were tested to determine the melting point of BiBO3 and to determine the eutectic
composition between BiBO3 and Bi3B5O12. The compositions used to correct the B2O3–Bi2O3
phase diagram were prepared by solid state synthesis at 520°C, with steps of 0.5–1.0 mol%
В2О3 over the interval 45–55 mol% В2О3. As a result, the eutectic composition,
48.5Bi2O3•51.5B2O3 (mol%), between BiBO3 and Bi3B5O12, was determined, and its melting
point was measured by DTA as 665±5°С (Fig. 4). It was also found that BiBO3 melts con‐
gruently at 685±5°С.
136 Advances in Ferroelectrics

Figure 4. Corrected phase diagram of the Bi2O3-B2O3 system in the interval 30–65 mol% B2O3.

3.1.2.2. Phase diagram of the pseudo-binary BiBO3–BaB2O4 system

BaBi2B4O10 is a congruently melting compound, with a melting point of 730°C, and it occu‐
pies the central area of the BiBO3–BaB2O4 pseudo-binary system (Fig. 5). This system forms
two simple pseudo-binary eutectics, E1 at 15 mol% BaB2O4, with a melting point of 620°C, and
E2 at 60 mol% BaB2O4, with a melting point of 718°C.

Figure 5. Phase diagram of the pseudo-binary system BiBO3-BaB2O4

3.1.2.3. Phase diagram of the pseudo-binary Bi4B2O9–BaBi2B2O7 system

The introduction of 12 mol% BaBi2B2O7 in the pseudo-binary system Bi4B2O9-BaBi2B2O7 re‐

duced the melting point of initial Bi4B2O9, and resulted in the formation of a simple pseudo-
binary eutectic, E3, with melting point 605°C (Fig. 6). A maximum of the liquidus with melting
point of 690°C is seen at 33.33 mol% BaBi2B2O7, which indicates the formation of the new
congruently melting ternary compound BaBi10B6O25 (11.11BaO•55.55Bi2O3•33.33B2O3). Fur‐
ther increase of the BaBi2B2O7 content (49 mol%) leads to a second pseudo-binary eutectic, E4,
with melting point 660°C. Increasing of the liquidus temperature is observed in the post eutectic
region of composition, with a maximum at 725°C. It corresponds to the formation of the new
congruently melting ternary compound BaBi2B2O7 (Fig. 6).
 Phase Diagram of The Ternary BaO-Bi2O3-B2O3 System: New Compounds and Glass Ceramics Characterisation 137
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Figure 6. Phase diagram of the pseudo-binary system Bi4B2O9-BaBi2B2O7.

Two new crystalline ternary compounds, BaBi2B2O7 and BaBi10B6O25, were revealed by crystal‐
lisation at the same glass composition. Both compounds, BaBi2B2O7 and BaBi10B6O25, melt
congruently at 725±5°С and 690±5°С, respectively. The X-ray characteristics of BaBi2B2O7 and
BaBi10B6O25 were determined and are given in Tables 1 and 2.

No. dexp I/I0 hkl No. dexp I/I0 hkl No. dexp I/I0 hkl
1 6.23 9 101 20 2.15 25 140 39 1.349 7 125
2 5.02 9 111 21 2.12 5 232 40 1.33 3 543
3 4.80 5 201 22 2.06 24 123 41 1.28 8 035
4 4.29 5 020 23 2.01 6 523 42 1.24 6 560
5 4.11 14 120 24 1.977 25 241 43 1.217 5 263
6 3.88 6 300 25 1.84 15 142 44 1.21 9 843
7 3.67 4 021 26 1.826 7 133 45 1.206 13 271
8 3.59 26 301 27 1.786 6 004 46 1.19 14 145
9 3.56 50 121 28 1.729 52 114 47 1.173 12 245
10 3.52 23 220 29 1.679 23 250 48 1.17 4 1010
11 3.19 100 112 30 1.636 34 251 49 1.14 6 126
12 3.12 8 221 31 1.63 5 532 50 1.11 6 662
13 3.05 9 202 32 1.57 4 052 51 1.10 6 326
14 2.91 43 030 33 1.556 10 243 52 1.09 4 180
15 2.696 90 122 34 1.522 8 034 53 1.042 6 146
16 2.51 12 222 35 1.488 23 632 54 1.021 9 065
17 2.376 21 003 36 1.458 6 060 55 1.018 9 943
18 2.31 5 421 37 1.428 10 811 56 1.01 5 274
19 2.254 22 113 38 1.373 11 821

Table 1. X-ray characteristics of the new ternary compound BaBi2B2O7, synthesized at the same glass composition
crystallization (640°C, 20 h).
138 Advances in Ferroelectrics

Single crystals of BaBi10B6O25 were obtained by cooling of a melt with the stoichiometric
composition. Glass powder of composition 11.11BaO•55.55Bi2O3•33.33B2O3 (mol%) was
heated in a quartz glass ampoule up to 750°C at a rate 10 K/min. After 2 h exposition at high
temperature, the melt was cooled at a rate 0.5 K/h. Single crystals with sizes up to
1.66×0.38×0.19 mm3 were grown.

No. dexp I/I0 hkl No. dexp I/I0 hkl No. dexp I/I0 hkl
1 9.21 3.0 012 23 2.91 31 0110 45 2.01 5.2 321
2 6.26 3.0 101 24 2.8 6 221 46 1.98 23.7 323
3 6.02 3.0 005 25 2.7 75.9 206 47 1.92 3.0 1214
4 5.01 7.3 006 26 2.64 3.4 045 48 1.88 3.0 0314
5 4.89 10.8 104 27 2.57 3.0 2.07 49 1.86 3.0 162
6 4.63 6.5 024 28 2.53 4.3 046 50 1.84 15.1 254
7 4.19 4.3 025 29 2.52 5.2 144 51 1.83 3.0 1412
8 4.18 4.3 122 30 2.49 6.9 230 52 1.82 3.0 164
9 4.11 10 115 31 2.47 9.5 1210 53 1.81 3.0 255
10 3.92 6.0 030 32 2.45 4.7 232 54 1.79 3.4 165
11 3.80 3.4 032 33 2.38 16 0310 55 1.77 3.0 328
12 3.65 10.8 033 34 2.35 4.3 050 56 1.75 3.4 1413
13 3.56 39.7 107 35 2.34 5.2 051 57 1.73 55.2 341
14 3.51 9.5 125 36 2.33 3.9 1012 58 1.71 4.3 343
15 3.41 3.4 117 37 2.31 3.4 1212 59 1.69 3.0 069
16 3.38 7.3 130 38 2.25 17.2 228 60 1.68 16.4 070
17 3.33 8.6 131 39 2.21 7.8 150 61 1.65 3.0 259
18 3.27 9.1 132 40 2.19 3.0 055 62 1.64 31.0 074
19 3.18 100 133 41 2.15 21.2 237 63 1.61 2.9 400
20 3.07 14.7 203 42 2.09 3.4 312 64 1.6 6.0 402
21 3.04 9.2 212 43 2.06 21.6 304 65 1.55 6.5 421
22 2.94 14.2 040 44 2.03 3.0 314 66 1.52 9.5 177

Table 2. X-ray characteristics of the new ternary BaBi10B6O25 single crystals.

The x-ray powder diffraction patterns of BaBi2B2O7 and BaBi10B6O25 could be indexed on an
orthorhombic cell with lattice parameters as follows:

• for BaBi2B2O7 a=11.818 Å, b=8.753 Å, c=7.146 Å, cell volume V=739.203 Å3, Z=4;
• for BaBi10B6O25 a=6.434 Å, b=11.763 Å, c=29.998 Å, cell volume V=2270.34 Å3, Z=8.

3.1.2.4. Phase diagram of the pseudo-binary BiBO3–BaBi10B6O25 system

BiBO3– BaBi10B6O25 is a very important system (Fig.7). Initial BiBO3 has a melting point of
685°C. The second maximum in the liquidus curve (Fig.7) of 690°C is connected with the for‐
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mation of the new ternary compound BaBi10B6O25. There is a simple pseudo-binary eutectic
E5 between these two compounds at 54 mol%BaBi10B6O25, with a melting point of 595°C.

Figure 7. Phase diagram of the pseudo-binary system BiBO3- BaBi10B6O25.

3.1.2.5. Phase diagram of the pseudo-binary BaBi10B6O25 - BaBi2B4O10 system

The BaBi10B6O25–BaBi2B4O10 system confirms the presence of the new congruently melting
ternary compound BaBi10B6O25, with a melting point of 690°C (Fig.8). BaBi2B4O10 melts con‐
gruently at 730°C. There is a simple pseudo-binary eutectic E6 between these two com‐
pounds at 28 mol % BaBi2B4O10, with a melting point of 660°C.

Figure 8. Phase diagrams of the pseudo-binary system BaBi10B6O25 -BaBi2B4O10.

3.1.2.6. Phase diagram of the pseudo-binary BaBi2B4O10 – 50BaO•50Bi2O3 section

This pseudo-binary section consists of two ternary compounds BaBi2B4O10, BaBi2B2O7 and two
eutectics Е7, Е8 dividing fields primary crystallisations these compounds. Initial composition
is BaBi2B4O10 (Fig.9). The introduction of 20 mol% 50%BaO•50%Bi2O3 in the pseudo-binary
140 Advances in Ferroelectrics

system BaBi2B4O10 – 50BaO•50Bi2O3 reduced the melting point of initial BaBi2B4O10, and result‐
ed in the formation of a simple pseudo-binary eutectic, E7, with melting point 680°C (Fig.9). A
maximum of the liquidus with melting point of 725°C is seen at 33.33 mol% of 50%BaO•50%Bi2O3,
which indicates the formation of the new congruently melting ternary compound BaBi2B2O7.
Further increase of the 50%BaO•50%Bi2O3 content (52.5 mol%) leads to a second pseudo-
binary eutectic, E8, with melting point 700°C. Increasing of the liquidus temperature is ob‐
served in the post eutectic region of composition (more than 52.5mol% of 50BaO•50Bi2O3). Un
identified phase is in the post eutectic (E8) region of composition (Fig.9).

Figure 9. Phase diagram of the pseudo-binary section BaBi2B4O10 – 50BaO•50Bi2O3.

3.1.2.7. Phase diagram of the pseudo-binary BaB2O4–Bi2O3 section

BaB2O4 - Bi 2O3 section consist of two pseudo-binary BaB2O4- BaBi 2B2O7, BaBi2B2O7- Bi 2O3 sys‐
tems (Fig.10). There are two eutectics: Е9 between BaB2O4 and BaBi2B2O7, Е10 between Ba‐
Bi2B2O7 and BaBi8B2O16, and peritectic point P1 between BaBi8B2O16 and Bi2O3 (Fig.10). The
introduction of 26 mol% Bi2O3 in the pseudo-binary system BaB2O4 – Bi2O3 sharp reduced
the melting point of initial BaB2O4 on 4450C, and resulted in the formation of a simple eutec‐
tic, E9, with melting point 685°C (Fig.10). A maximum of the liquidus with melting point of
725°C is seen at 33 33 mol% of Bi2O3, which indicates the formation of the new congruently
melting ternary compound BaBi2B2O7.
Further increase of the Bi2O3 content (42 mol%) leads to a second eutectic, E10, formation
with melting point 690°C. Increasing of the liquidus temperature is observed in the post eu‐
tectic region of composition (more than 42mol% of Bi2O3) and formation of new incongruent
melted at 725 °C BaBi8B2O16 ternary compound (Fig.10). It is very difficult determined of Ba‐
Bi8B2O16 X-ray characteristics, because they very closed to Bi2O3 characteristics.
Constructed by us this section’s diagram essentially differs from that constructed by Russi‐
an researches Egorisheva & Kargin [30] because they could not find out two new com‐
pounds revealed by us: congruent melted at 725°C BaBi2B2O7 and incongruent melted at
725°C BaBi8B2O16(Fig.10). At repeated, even more detailed studies they also could not find
out these compounds [31].
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Figure 10. Phase diagram of the BaB2O4 – Bi2O3 section.

3.1.2.8. Phase diagram of the pseudo-binary Bi3B5O12 – BaBi2B4O10 system

It is very simple system with pseudo-binary eutectic Е11 between two congruent melted
Bi3B5O12 and BaBi2B4O10 compounds. Eutectic Е11 content 38 mol% of BaBi2B4O10 and has
melting point 680°C (Fig.11).

Figure 11. Phase diagram of the pseudo-binary system Bi3B5O12 – BaBi2B4O10

3.1.2.9. Phase diagram of the pseudo-binary BaBi2B4O10 – BaBiB11O19 pseudo-binary system

Initial BaBi2B4O10 has a melting point of 730°C. The second maximum in the liquidus curve
(Fig.12) of 807°C is connected with the formation of the ternary compound BaBiB11O19. There
is a simple pseudo-binary eutectic, E12, between these two compounds at 65.5 mol% Ba‐
Bi2B4O10, with a melting point of 695°C.
142 Advances in Ferroelectrics

Figure 12. Phase diagram of the pseudo-binary system BaBi2B4O10 – BaBiB11O19.

3.1.2.10. Phase diagram of the pseudo-binary Bi3B5O12 – BaBiB11O19 system

Pseudo-binary system Bi3B5O12 -BaBiB11O19 has simple eutectic Е13 formed between two con‐
gruent melted BaBiB11O19 and Bi3B5O12 compounds. According to DTA eutectic Е13 has melt‐
ing point 705°C and content 28 mol% BaBiB11O19 (Fig.13).

Figure 13. Phase diagram of the pseudo-binary system Bi3B5O12 - BaBiB11O19.

3.1.2. 11. Phase diagram of the pseudo-binary BaBiB11O19 – Ba2B10O17 system

Pseudo-binary system BaBiB11O19 – Ba2B10O17 has simple eutectic Е14 formed between two
congruent melted compounds Ba2B10O17 and BaBiB11O19. According to DTA eutectic Е14 has
melting point 780°C and content 26 mol% Ba2B10O17(Fig.14).
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Figure 14. Phase diagram of the pseudo-binary system BaBiB11O19 – Ba2B10O17.

3.1.2. 12. Phase diagram of the pseudo-binary BaBi2B4O10 – Ba2B10O17 system

It is very simple system with eutectic Е15 formed between two congruent melted Ba2B10O17
and BaBi2B4O10 compounds. Pseudo-binary eutectic Е15 content 24 mol% of Ba2B10O17 and has
melting point 710°C (Fig. 15).

Figure 15. Phase diagram of the pseudo-binary system BaBi2B4O10 – Ba2B10O17.

3.1.2. 13. Phase diagram of the pseudo-binary BaBi2B4O10 – BaB4O7 system

The same picture is observe for BaBi2B4O10 – BaB4O7 system: simple eutectic Е16 is formed be‐
tween two congruent melted compounds. Pseudo-binary eutectic Е16 content 24 mol% of
BaB4O7 and has melting point 715°C (Fig. 16).
144 Advances in Ferroelectrics

Figure 16. Phase diagram of the pseudo-binary system BaBi2B4O10 – BaB4O7.

3.1.2. 14. Phase diagram of the pseudo-binary BaBiB11O19 – BaB8O13 system

It is simple system with pseudo-binary eutectic Е17 between two congruent melted Ba‐
BiB11O19 and BaB8O13 compounds. Eutectic Е17 content 38 mol% of BaB8O13 and has melting
point 770°C (Fig. 17).

Figure 17. Phase diagram of the pseudo-binary system BaBiB11O19 – BaB8O13.

3.1.2.15. Phase diagram of the the BaO-Bi2O3-B2O3 ternary system

As result of huge work under project the phase diagram in the ternary BaO-B2O3-Bi2O3 sys‐
tem has been constructed for the first time and presented on Fig.18. Three new compounds
BaBi2B2O7, BaBi10B6O25 and BaBi8B2O16 have been revealed and characterized.
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Fields of binary bismuth and barium borates as well as all ternary barium bismuth borates
compounds crystallizations have been determined and outlined and sixteen ternary eutectic
points E1-E16 have been revealed as result of phase diagram construction (Fig. 18, table 3).
The phase diagram evidently represents interaction of binary and ternary compounds tak‐
ing place in the pseudo-ternary systems. The ternary eutectic E1 with m.p 590°C has been
determined among BiBO3, F and Bi4B2O9 compounds; ternary eutectic E2 with m.p. 585°C has
been formed among BiBO3, F and C compounds; ternary eutectic E3 with m.p. 640°C has
been formed among F, E and C compounds; ternary eutectic E4 with m.p. 622°C has been
formed among C, BaB2O4 and E compounds; ternary eutectic E5 with m.p. 610°C has been
formed among BiBO3, C and Bi3B5O12 compounds; ternary eutectic E6 with m.p. 675°C has
been formed among C, Bi3B5O12 and D compounds; ternary eutectic E7 with m.p. 680°C has
been formed among Bi3B5O12, D and BiB3O6 compounds; ternary eutectic E8 with m.p. 675°C
has been formed among BiB3O6, D and Bi2B8O15 compounds; ternary eutectic E9 with m.p.
680°C has been formed among Bi2B8O15, D and B2O3 compounds; ternary eutectic E10 with
m.p. 730°C has been formed among BaB8O13, D and B2O3 compounds; ternary eutectic E11
with m.p. 750 °C has been formed among Ba2B10O17-D- BaB8O13 compounds; ternary eutectic
E12 with m.p. 680°C has been formed among C, Ba2B10O17 and D compounds; ternary eutectic
E13 with m.p. 690°C has been formed among Ba2B10O17, C and BaB4O7 compounds; ternary
eutectic E14 with m.p. 700°C has been formed among BaB4O7, C and BaB2O4 compounds; ter‐
nary eutectic E15 with m.p. 645 °C has been formed among G, F and C compounds; ternary
eutectic E16 with m.p. 615°C has been formed among Bi24B2O39, F and Bi4B2O9 compounds
(Fig18, Table 3).

Figure 18. Phase diagram of the BaO-Bi2O3-B2O3 system

146 Advances in Ferroelectrics

Point Composition, mol% Tm, °C

BaO B2O3 Bi2O3

E1 4.5 40.5 55 590

E2 7.3 45.1 47.6 585

E3 15 38 47 640

E4 32.4 41.3 26.3 622

E5 5.4 52 42.6 610

E6 9 63 28 675

E7 3 71 26 680

E8 3.5 78 18.5 675

E9 3.2 81.8 15 680

E10 15 81.2 3.8 730

E11 18.9 77.5 3.6 750

E12 22.4 63.2 14.4 680

E13 26.6 54.7 18.7 690

E14 28.8 52 19.2 700

E15 20 32 48 645

E16 4.5 30 65.5 615

Table 3. The temperature and compositions for ternary eutectic points in the BaO-Bi2O3-B2O3 system

3.2. DTA and X-ray characterisation of ternary stoichiometric glasses and glass ceramics
from the BaO-Bi2O3-B2O3 system

The glasses corresponding to known sixth stoichiometric compounds in the BaO-Bi2O3-

B2O3 system examined in the present study and following glass compositions (mol%) have
been melted: 14.28BaO•7.14Bi2O3•78.57B2O3 (BaBiB11O19), 25BaO•25Bi2O3•50B2O3(Ba‐
Bi2B4O10), 33.33BaO•33.33Bi2O3•33.33B2O3(BaBi2B2O7), 11.11BaO•55.55Bi2O3•33.33B2O3 (Ba‐
Bi10B6O25), 50BaO• 25Bi2O3• 25B2O3 (BaBiBO4) and 60BaO•10Bi2O3•30B2O3 (Ba3BiB3O9). These
glasses DTA curves are shown in Fig. 19, giving the peaks due to the glass transition,
crystallization, melting, and liquidus temperatures. The glass characteristics points Tg (glass
transition), Ts(glass softening), Tc (peak of exothermal effects connected with crystalline
phases crystallizations) and Tm (minimum of endothermic effects associated with these phas‐
es melting) observed on DTA curves (Fig. 19, curves 1-6) of all tested powder samples
summarized on table 4.
 Phase Diagram of The Ternary BaO-Bi2O3-B2O3 System: New Compounds and Glass Ceramics Characterisation 147
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Figure 19. DTA curves (heating rate 10K/min) of glasses corresponding to ternary compounds in the BaO-Bi2O3-B2O3
system: 1-BaBiB11O19, 2-BaBi2B4O10, 3-BaBi2B2O7, 4-BaBi10B6O25,5-BaBiBO4, 6-Ba3BiB3O9.

## Glass compositions, Dilatometric characteristics DTA characteristics

correspoding to stoichometric TEC(α
20-300)∙10 K Tg,ºC Ts ,ºC Tg, ºC Tcr, ºC Tm, °С TL, °С
7 -1

compounds

1 BaBiB11O19 (glass) 72 498 535 485 640; 770 807 807

BaBiB11O19 (615°C 24h) 49.8

2 BaBi2B4O10 (glass) 96 445 475 450 545; 640 730 730

BaBi2B4O10 (640°C 24h) 77.9

3 BaBi2B2O7 (glass) 108 415 455 420 570; 645 725 725

BaBi2B2O7 (640°C 24h) 96

4 BaBi10B6O25 (glass) 99 350 380 340 460; 620 690 690

BaBi10B6O25(590°C 24h) 97

5 BaBiBO4 (glass) 120 400 450 390 450 680 760

BaBiBO4 (570°C 24h) 110.8

6 Ba3BiB3O9 (glass) 127 460 490 460 540; 670 827 865

Ba3BiB3O9 (690°C 24h) 109.8

Table 4. Chemical compositions, DTA ( glass transition -Tg, crystallization peak -Tcr, melting -Tm, liquidus- TL) and
dilatometric characteristics (glass transition temperature -Tg, softening point - TS, thermal expansion coefficient -TEC)
of BaO-Bi2O3-B2O3system glasses and crystallaised glasses.

Two exothermic effects were observed on DTA curve of 14.28BaO•7.14Bi2O3•78.57B2O3 (mol

%) glass composition: first weak effect at 640°C and second strong effect at 770°C(Fig.19,
148 Advances in Ferroelectrics

curve1). The melting temperature (Tm) is equal to 807°C and corresponding to Egorisheva
and Kargin’s data [30]. X-ray patterns of this glass crystallization products show one Ba‐
BiB11O19 crystalline phase presence [30], which formed at powder samples crystallization in
an temperature interval 640-770°C (Fig.20, curve1). It is possible to assume, that weak exo‐
thermic effect at 640°C apparently is connected with pre-crystallisation fluctuations taking
place in glass matrix [50]. Diffuse character of second exothermic effect at 770°C testifies
about dominating surface crystallisation of the given glass particles.

One sharp exothermic effect at 640°C and sharp endothermic effect at 730°C were observed
on DTA curve of BaBi2B4O10 glass composition (Fig. 19, curve2). The melting temperature
(Tm) is equal to 730°C and corresponding to Egorisheva’s data [30]. X-ray diffraction patterns
of this glass crystallization products show one BaBi2B4O10 crystalline phase crystalliza‐
tion[30], which formed at glass powder samples crystallization at temperature 640°C (Fig.
20, curve2) and its melting. Tm is equal to 730°C and corresponding to Egorisheva’s data
[30]. Hardly visible pre-crystallisation fluctuation exothermal effect is observed also at 545°C
(Fig. 19, curve2).

Figure 20. XRD-patterns of the crystallized glasses corresponding to ternary BaBiB11O19 (1- 760 °C 24h,cooling in the
muffle) and BaBi2B4O10 (2- 640°C 24h,cooling in the muffle) compounds

On the DTA curves of stoichiometric BaBi2B2O7 and BaBi10B6O25 glass compositions observed
two exothermal effects at 570 and 645°C for BaBi2B2O7 and at 460 and 620°C for BaBi10B6O25
(Fig. 19, curves 3,4). But both compositions have one endothermic effect of melting at 725
and 690°C respectively for BaBi2B2O7 and BaBi10B6O25 testifying to one formed crystalline
phase melting (Fig. 19, curves 3,4). X-ray data of these samples confirmed monophase crys‐
tallizations in each samples (Fig. 21, curves 1,2; Fig.22, curves 1,2).

According to [34] the X-ray powder diffraction patterns of formed BaBi2B2O7 crystalline
phase at stoichiometric glass composition (33.33BaO•33.33Bi 2O3• 33.33B2O3 mol%) at second
 Phase Diagram of The Ternary BaO-Bi2O3-B2O3 System: New Compounds and Glass Ceramics Characterisation 149
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exothermic peaks temperature (640°C 24h) was indexed on an orthorhombic cell with fol‐
lowing lattice parameters: a=11.818Å, b=8.753 Å, c=7.146Å, cell volume V=739.203 Å, Z=4
(Fig. 21, curve2). XRD-patterns of products of same glass crystallization at 570°C 24h keeps
all diffraction lines of its analogue obtained at 640°C 24h (Fig. 21, curve1). Difference is ob‐
served only in sharp increasing of intensity (I/Io) of [030] diffraction line from 4 to 43 at high
temperature crystallization. That leads to reorientation of crystal structure, decreasing [030]
diffraction line and accompanied with occurrence of the second exothermal effect on DTA
curve (Fig. 19, curve 3).

Figure 21. XRD-patterns of the crystallized glasses corresponding to ternary BaBi2B2O7 composition:

1-570°C 24h, cooling in the muffle; 2-640°C 24h, casting in the cold water

X-ray powder diffraction patterns of BaBi10B6O25 single crystals was indexed on an ortho‐
rhombic cell with following lattice parameters: a=6.434Å, b=11.763 Å, c=29.998Å, cell volume
V=2270.34 Å, Z=8 [34]. XRD-patterns of products of same compositions (11.11BaO•
55.55Bi2O3• 33.33B2O3 mol%) glass crystallization at both exothermal effects (420°C 24h and
620°C 24h) have all diffraction lines of the BaBi10B6O25 single crystals (Fig. 22, curves1-3).
Naturally, BaBi10B6O25 single crystal has well generated planes and clear observed diffrac‐
tion lines on XRD-patterns in contrast to crystalline phases formed at same composition
glasses crystallization. However, the most intensive diffraction line (I/Io=100) of single crys‐
tals is [133], whereas products of glass crystallizations have [203] strongest diffraction line
and [133] diffraction line became 5-10 times less (Fig. 22, curves1-3). Now it is difficult to us
only on the basis of XRD-patterns analysis of glass crystallizations products to assume the
nature of the second exothermal effect at 620°C on DTA curve of BaBi10B6O25 of glass compo‐
sition (Fig.19, curve 4). Their XRD-patterns are identical each other and to single crystals,
150 Advances in Ferroelectrics

but contain slightly quantity of not indexed reflexes, which are absent in X-ray powder dif‐
fraction patterns of BaBi10B6O25 single crystals (Fig. 22, curves1-3).

Figure 22. XRD-patterns of the crystallized glasses corresponding to ternary BaBi10B6O25 composition:(1-460°C
24h,cooling in the muffle; 2-620°C 24h, casting in the cold water) and BaBi10B6O25 single crystals (3).

The DTA curve of 50BaO• 25Bi2O3• 25B2O3 mol% (BaBiBO4) glass composition contain
exothermal effect of glass crystallization at 450°C and endothermic effect of this crystal‐
line phase melting at 680°C (Fig. 19, curv.5). X-ray diffraction patterns of this glass crystal‐
lization products show one BaBiBO4 crystalline phase formation at glass powder samples
crystallization at temperature interval 450-640°C(Fig. 23, curve 1), which completely corre‐
spond to Barbier with co-authors data [29]. A second endothermic effect within the inter‐
val of 745-775°C with minimum at 760°C is associated with BaBiBO4 incongruent melting
(Fig. 19, curve 5).

We have revealed also, that the crystalline BaBiBO4 compound is melted incongruently at
680°C with the melt and crystalline BaBiO3 formation (Fig. 23, curve 2). The BaBiO3 crystal‐
line phase was observed on XRD-patterns of thermal treated at 720 °C and fast freeze in cold
 Phase Diagram of The Ternary BaO-Bi2O3-B2O3 System: New Compounds and Glass Ceramics Characterisation 151
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water products and identified according to X-ray database [43, fail # 01-074-7523]. The disso‐
lution of this BaBiO3 phase in a melt leads to the appearance on a DTA curve the second
endothermic effect in an interval 745-775°C (Fig. 19, curve 5). Above 775°C we have glass-
forming BaBiBO4 composition melt without presence of any crystalline phase.

Figure 23. XRD-patterns of the crystallized glasses corresponding to ternary BaBiBO4 composition:

1-450°C 24h, cooling in the muffle; 2-720°C 3h, casting in the cold water

Two exothermal effects of glass crystallization at 540 and 670°C and one endothermic effect
of crystalline phase melting at 827°C are seen on the DTA curve of the
60BaO•10Bi2O3•30B2O3 mol% (Ba3BiB3O9) glass composition (Fig. 19, curve 6). X-ray diffrac‐
tion patterns of this glass crystallization products at 540 and 670°C show one Ba3BiB3O9 crys‐
talline phase formation (Fig. 24, curves 1,2) at glass powder samples crystallization at 540
and 670°C and fully correspond to Egorisheva with co-authors data, which synthesized for
the first time and have describe Ba3BiB3O9 compound [31]. However, we didn’t indicate pol‐
ymorphic transition of Ba3BiB3O9 at 850°C as reported in [31]. Presence of second endother‐
mic effect within the interval of 840-890°C with minimum at 865°C is associated with
Ba3BiB3O9 incongruent melting (Fig. 19, curve 6). We have revealed that the crystalline
Ba3BiB3O9 compound is melted incongruently at 827°C with the glass forming melt and crys‐
talline phase formation (Fig. 24, curve 3). The Ba2B2O5 crystalline phase was observed in
amorphous matrix on XRD-patterns of thermal treated at 830 °C and fast freeze in cold wa‐
ter products and identified according to X-ray database [43, fail # 024-0087]. For clear
Ba2B2O5 observation on XRD-patterns the preliminary crystallized at 670°C 24h sample have
been exposed at 830°C 3 h (Fig. 23, curve3). Dissolution of this Ba2B2O5 phase in a melt leads
to the appearance on a DTA curve the second endothermic effect in an interval 840-890°C
(Fig. 19, curve 6). Above 890°C we have glass-forming Ba3BiB3O9 composition melt without
presence of any crystalline phase at cooling rate 102 K/s.
152 Advances in Ferroelectrics

Figure 24. XRD-patterns of the crystallized glasses corresponding to ternary 6BaBi3BO4 composition:1.540°C 24h,
cooling in the muffle; 2-670°C 24h, casting in the cold water; 3-670°C 24h+830°C 3 h, casting in the cold water

3.3. TEC study of the stoichiometric compositions glasses in the BaO-Bi2O3-B2O3 system

The isolines diagram of BaO-Bi2O3-B2O3 system glasses TEC values is given on Fig. 25. It is
clear observed common regularity, that the increase of barium and bismuth oxides amounts
in glasses of binary BaO-Bi2O3 and Bi2O3-B2O3 systems leads to increase TEC of glasses. The
same tendency is observed for glasses of ternary system: joint presence of BaO and Bi2O3 and
increase their amounts leads to increase glasses TEC values from 70 to 127•10-7К-1 (Fig. 25).

Figure 25. BaO-Bi2O3-B2O3 system’s glasses TEC (α20-300•10-7К-1) values isolines

 Phase Diagram of The Ternary BaO-Bi2O3-B2O3 System: New Compounds and Glass Ceramics Characterisation 153
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The high boron content glass composition corresponds to BaBiB11O19

(14.28BaO•7.14Bi2O3•78.57B2O3 mol %) have TEC=72•10-7К-1 and Tg=498°C calculated from
dilatometric curve (Table 4). Reduction the B2O3 amount together with increasing of BaO
and Bi2O3 amounts in glass compositions leads to increase TEC and reduction Тg values: for
glass composition 25BaO•25Bi2O3•50B2O3 mol % (BaBi2B4O10) TEC=96•10-7К-1 and Тg= 445°C;
33.3BaO•33.3 Bi2O3•33.3B2O3 mol %(BaBi2B2O7) TEC=108•10-7К-1 and Тg=415°C; 11.1BaO•
55.5Bi2O3•33.3B2O3 mol %(BaBi10B6O25) TEC=97•10-7К-1 and Тg=350°C;
16.67BaO•66.67Bi2O3•16.67B2O3 mol%(BaBi8B2O16) TEC=110•10-7К-1 and Тg=415°C. However,
for 50BaO•25 Bi2O3•25B2O3 mol % (BaBiBO4) and 60BaO•10Bi2O3•30B2O3 mol % (Ba3BiB3O9)
glass compositions simultaneous increase both TEC and Тg values were observed:
TEC=120•10-7К-1 and Тg=400°C; TEC=127•10-7 К-1 and Тg=460°C respectively for BaBiBO4 and
Ba3BiB3O9 (Fig. 25, table4).

TEC values of crystallized glasses corresponding to the ternary barium bismuth borates giv‐
en in Table 4. Crystallized barium bismuth borate glass samples have TEC values lower,
than initial glasses and equals to: 49•10-7К-1 for BaBiB11O19 sample (750°C 24h), 78•10-7К-1 for
BaBi2B4O10 sample (630°C 24 h), 96•10-7 К-1 for BaBi2B2O7 sample (640°C 24h), 97•10-7К-1 for
BaBi10B6O25 sample (610°C 24h), 110•10-7 К-1 for BaBiBO 4 sample (450°C24h) and 109•10-7 К-1
for Ba3BiB3O9 sample (690°C 24h). The same tendency, as well as for their glassy analogues,
is observed for crystallized glass samples: increase of barium and bismuth oxides amounts
in ternary compounds leads to their TEC values increase.

4. Ferroelectric properties of new ternary BaBi2B2O7 and BaBi10B6O25

stoichometric compositions glass ceramics.

The ferroelectric (polarization - electric field) hysteresis, is a defining property of ferroelec‐

tric materials. Thus, the most widely studied characteristics of ferroelectric hysteresis were
those of interest for this particular application: the value of the switchable polarization (the
difference between the positive and negative remanent polarization, P R − (−P R ), depend‐
ence of the coercive field Ec on sample thickness, decrease of remanent or switchable polari‐
zation with number of switching cycles, polarization imprint, endurance, retention [51].

Electric field induced polarization (P) and remanent polarization(Pr) were measured at room
temperature for BaBi2B2O7 and BaBi10B6O25 glass tape samples crystallized using various re‐
gimes (Fig. 26).
a. BaBi2B2O7 glass tape sample of 0.07 mm in thickness crystallized at 450°C 24h, 2Pr = 0.15
μC/cm2;

b. BaBi10B6O25 glass tape sample of 0.06 mm in thickness crystallized at 380 °C 12h, 2Pr =
0.32 μC/cm2;

c. BaBi10B6O25 glass tape sample of 0.06 mm in thickness crystallized at 410°C 12h, 2Pr =
0.62 μC/cm2;
154 Advances in Ferroelectrics

d. BaBi10B6O25 glass tape sample of 0.05 mm in thickness crystallized at 410°C 24h, 2Pr = 0.9
μC/cm2

Figure 26. Dependence of polarization (P) on electric field (E) for crystallized stoichiometric glass compositions:

Linear P–E curves are observed up to fields of 40-120 kV/cm for all measured samples with
thickness 0.05-0.07mm. The polarization becomes nonlinear with increasing of applied elec‐
tric field, and at 140-380 kV/cm the remanent polarization 2Pr values were found 0.15
μC/cm2 for the BaBi2B2O7 (Fig. 26, A). The remanent polarization 2Pr value for BaBi10B6O25
crestallized glass tape samples encreasing with termal treatment temperature from 0,32 to 0,
64 μC/cm2 (Fig. 26, B & C) and time (Fig. 26, D). The highest remanent polarization value
(2Pr=0.9 μC/cm 2 ) has BaBi10B6O25 glass tape sample crystallized at 410°C 24h (Fig.26, D). Ac‐
cording to obtained results it is possible to conclude that samples are ferroelectrics.

5. Discussion

The pricipial diference of our methodology from traditional is a glass samples using as ini‐
tial testing substance for phase diagram of very complex ternary BaO-Bi2O3-B2O3 system
construction. It is a very effective method, due possibility to indicate temperature intervals
of all processes taking place in glass samples: glass transition, crystallization, quantity of
formed crystalline phases and their melting. Whereas, samples prepared by traditional solid
phase synthesis are less informative and often lose a lot of information. Super cooling tech‐
nique created by our group allowed us both to expand borders of glass formation and to
have enough quantity samples for DTA and X-ray investigations and BaO-Bi2O3-B2O3 sys‐
tem phase diagram construction (Fig.2).

The region of stable glasses includes the binary compounds BaB4O7, Ba2B10O17, BaB8O13,
Bi4B2O9, BiBO3, Bi3B5O12, BiB3O6, and Bi2B8O15 in the BaO–B2O3 and Bi2O3–B2O3 systems (Fig.
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2). Binary BaB4O7, Ba2B10O17, and BaB8O13 barium borates have melting temperatures (Tm) of
910, 905, and 890°C and can be found between the eutectics e7, e8, e9, and e10 with Tm = 878,
869, 895, and 899°C, respectively. The transition to a crystallization field of barium metabo‐
rate is accompanied by a sharp increase of liquidus temperature (TL) and a decrease of the
glass forming ability of the melts. The final compound, forming a stable glass, contains ~43
mol %BaO and has TL = 950°C. Compounds BaB2O4 and Ba2B2O5, having higher Tm, which
are 1095 and 1050°C, respectively [18, 21, 22], are found in the region of the compounds ob‐
tained in the form of glasses with a cooling rate of (103–104) K/s. Glass formation in the BaO–
B2O3 binary system is limited by the eutectic e12 with Tm = 1025°C (Fig. 2) because of the
sharp increase of the liquidus temperature during the transition to a field of crystallization
of the Ba3B2O6 compound (Tm = 1383°C). BaB2O4 (Tm = 1095°C) is the dominating com‐
pound in the system and does not form stable glasses. Its considerable crystallization field
narrows the region of stable glasses in the ternary system, which is only restricted by com‐
pounds with TL ~ 950°C (Fig. 2).

Binary bismuth borates Bi4B2O9, BiBO3, Bi3B5O12, BiB3O6, and Bi2B8O15 have Tm 675, 685, 722,
708, and 715°C can be found between the eutectics e1, e2, e3, e4, e5, e6 with a Tm of 622, 646,
665, 698, 695, and 709°C, respectively [2, 34]. The region of stable glasses in the Bi2O3–B2O3
system is limited by a compound containing ~70%mol Bi2O3 and having TL = 670°C. Com‐
pounds that are found in the range of 70–80mol% Bi2O3 (before the e1 point) are obtained in
the form of glasses during cooling at a rate of ~102 K/s. During the transition to the crystalli‐
zation field of Bi24B2O3 and Bi2O3, TL increases to 825°C (Tm of Bi2O3). Glasses in this part of
the system are obtained during melt cooling at a rate of (103–104) K/s. These compounds
have a low liquidus temperature; however, the structure factor essentially influences their
glass forming ability, not allowing glass formation at low melt cooling rates.

Six ternary compounds are known in the BaO–Bi2O3–B2O3 system: Ba3BiB3O9, BaBiBO4, Ba‐
Bi2B4O10, and BaBiB11O19 synthesized by Barbie and Egorysheva in 2005–2006, and BaBi2B2O7
and BaBi10B6O25 revealed by our research group in 2008–2009. BaBi2B4O10, BaBiB11O19, Ba‐
Bi2B2O7, and BaBi10B6O25 melt congruently at 730, 807, 725, and 695°C respectively, and BaBi‐
BO4 melts incongruently at 680°C and has TL = 760 °C. All these five ternary compounds
along with the eutectics formed between each other and with binary barium and bismuth
borates form a “plateau” with low TL, which is responsible for the formation of the region of
stable glasses in the ternary system BaO–Bi2O3–B2O3.

Compounds joining low temperature eutectic e1 (622°C) [2] in the Bi2O3–B2O3 binary system
and the eutectics e13 (~790°C) and e14 (~750°C) in the BaO–Bi2O3 binary system [26 - 28] form
glasses only at higher cooling rates of their melts (103–104) K/s. Glass formation in the BaO–
Bi2O3 binary system stops at 45 mol% BaO content (TL ~930°C) [26 - 28]. Along with the fac‐
tor of the liquidus temperature [52], a considerable contribution to the glass formation of the
pointed compositions is made by the structural factor of the melt. The combination of the
structural factors of the melt and the liquidus temperature is also considerable during the
transition to the vitreous state of the compositions, which are found in the crystallization
fields of BaB2O4 and Ba2B2O5, where they show the tendency towards glass formation only at
high rates of melt cooling.
156 Advances in Ferroelectrics

There are very stable congruent melted binary BaB2O4 and ternary BaBi2B4O10, BaBiB11O19,
and BaBi10B6O25 compounds in the studied ternary BaO-Bi2O3-B2O3 system. They have domi‐
nating positions in ternary diagram and occupied the biggest part of it (Fig.18). Mutual in‐
fluence of these compounds and other binary and ternary compounds (BaB4O7, Ba2B10O17,
BaB8O13, Bi4B2O9, BiBO3, Bi3B5O12, BiB3O6, Bi2B8O15, BaBi2B2O7, and BaBi8B2O16) lead to forma‐
tion of sixteen revealed at present time ternary eutectics (Fig.18& Table 3), which have es‐
sential influence on liquidus temperature decrease and to assist in glass formation. Ternary
BaBi2B4O10 compound forms eight eutectics with binary and ternary compounds, its neigh‐
bors: E4(622°C), E3(640°C), E2(585°C), E5(610°C), E6(675°C), E12(680°C), E13 (690°C), and E14
(700°C) (Fig.18& Table 3). BaBiB 11O19 compound forms seven eutectics with its neighbors: E6
(675°C), E7 (680°C), E8 (675°C), E9 (680°C), E10 (730°C), E11 (750°C),and E12 (680°C) (Fig.18&
Table 3). BaBi10B6O25 compound forms five eutectics with its neighbors: E1 (590°C), E2
(585°C), E3 (640°C), E15 (645°C), and E16 (615°C) (Fig.18& Table 3). Determined ternary eutec‐
tics together with binary eutectics e1, e2, e3, e4, e5, and e6 of Bi2O3-B2O3 system have allowed to
outline the fields of binary Bi4B2O9, BiBO3, Bi3B5O12, BiB3O6, and Bi2B8O15 bismuth borates
crystallisation, as well as together with binary eutectics e7, e8, e9, and e10 of BaO-B2O3 system
have allowed to outline the fields of binary BaB4O7, Ba2B10O17, BaB8O13 barium borates and
partly BaB2O4 crystallization on the BaO-Bi2O3-B2O3 system phase diagram (Fig.18).

The clear correlation between glass forming and phase diagrams has been observed in stud‐
ied system. The glass melting temperature and level of glass formation depending on the
cooling rate of the studied melts are in good conformity with boundary curves and eutectic
points (Fig.2& 18).

The phase diagram of the well known binary Bi2O3–B2O3 system has been corrected in the
interval between the Bi4B2O9 and Bi3B5O12 compounds. The eutectic composition,
48.5Bi2O3•51.5B2O3 (mol%), between BiBO3 and Bi3B5O12, with m.p. 665±5°С, has been deter‐
mined. It is shown that the compound BiBO3 is congruently melting with a m.p. of 685±5°С.

The next unexpected results were obtained at phase diagram construction: two new ternary
BaBi2B2O7 and BaBi10B6O25 compounds have been revealed at the same glass compositions
crystallisation. X-ray characteristics of the new ternary compound BaBi2B2O7, synthesized at
the 33.33BaO•33.33Bi2O3•33.33B2O3 (mol%) glass composition crystallization at 640°C, 20 h.
The x-ray powder diffraction patterns of BaBi2B2O7 could be indexed on an orthorhombic
cell with lattice parameters as follows: BaBi2B2O7 a=11.818 Å, b=8.753 Å, c=7.146 Å, cell vol‐
ume V=739.203 Å3, Z=4.

Single crystals of BaBi10B6O25 were obtained by cooling of a melt with the stoichiometric
composition. Glass powder of composition 11.11BaO•55.55Bi2O3•33.33B2O3 (mol%) was
heated in a quartz glass ampoule up to 750°C at a rate 10 K/min. After 2 h at high tempera‐
ture, the melt was cooled at a rate 0.5 K/h. Single crystals with sizes up to 1.66×0.38×0.19
mm3 were grown. The x-ray powder diffraction patterns of BaBi10B6O25 could be indexed on
an orthorhombic cell with lattice parameters as follows: a=6.434 Å, b=11.763 Å, c=29.998 Å,
cell volume V=2270.34 Å3, Z=8.
 Phase Diagram of The Ternary BaO-Bi2O3-B2O3 System: New Compounds and Glass Ceramics Characterisation 157
http://dx.doi.org/10.5772/52405

Common regularities of bulk glass samples TEC changes in studied BaO-Bi2O3-B2O3 system
have been determined: the increase of barium and bismuth oxides amounts in glasses of binary
BaO-Bi2O3 and Bi2O3-B2O3 systems leads to increase TEC of glasses. The same tendency is
observed for glasses of ternary BaO-Bi2O3-B2O3system: joint presence of BaO and Bi2O3 and
increase their amounts leads to increase glasses TEC values from 70 to 127•10-7К-1 (Fig. 25).
Crystallized barium bismuth borate glass samples have TEC values lower, than initial
glasses and equals to: 49•10-7К-1 for BaBiB11O19 sample (750°C 24h), 78•10-7К-1 for BaBi2B4O10
sample (630°C 24 h), 96•10-7 К-1 for BaBi2B2O7 sample (640°C 24h), 97•10-7К-1 for BaBi10B6O25
sample (610°C 24h), 110•10-7 К-1 for BaBiBO4 sample (450°C24h) and 109•10-7 К-1 for
Ba3BiB3O9 sample (690°C 24h). The same tendency, as well as for their glassy analogues, is
observed for crystallized glass samples: increase of barium and bismuth oxides amounts in
ternary compounds leads to their TEC values increase.
Electric field induced polarization (P) and remanent polarization (Pr) were measured at
room temperature for BaBi2B2O7 and BaBi10B6O25 glass tape samples crystallized at various
regimes. All tested samples shown loop of hysteresis.
Linear P–E curves are observed up to fields of 40-120 kV/cm for all measured samples with
thickness 0.05-0.07mm. The polarization becomes nonlinear with an increase of applied elec‐
tric field, and at 140-400 kV/cm the remanent polarization 2Pr values were found 0.15
μC/cm2 for the BaBi2B2O7 (Fig.26, A), and 0.32- 0.9 μC/cm2 for the BaBi10B6O25 (Fig.26, B-D),
crystallized glass tape samples. According to obtained results it is possible to conclude that
all tested samples are ferroelectrics.

5. Conclusion

Effective way of new system investigation and new compounds and characteristic points re‐
vealing via simultaneous glass forming and phase diagrams construction have been shown.
Phase diagram of the ternary BaO-Bi2O3-B2O3 system have been constructed for the first time
us result of fourteen pseudo-binary systems and sections phase diagrams investigations.
The phase diagram of the well known binary Bi2O3–B2O3 system has been corrected in the
interval between the Bi4B2O9 and Bi3B5O12 compounds. The eutectic composition,
48.5Bi2O3•51.5B2O3 (mol%), between BiBO3 and Bi3B5O12, with m.p. 665±5°С, has been deter‐
mined. It is shown that the compound BiBO3 is congruently melting with a m.p. of 685±5°С.
Two new ternary BaBi2B2O7 and BaBi10B6O25 compounds have been revealed at the same
glass compositions crystallisation. The new ternary compound BaBi2B2O7 synthesized at the
33.33BaO•33.33Bi2O3•33.33B2O3 (mol%) glass composition crystallization at 640°C, 20 h. The
x-ray powder diffraction patterns of BaBi2B2O7 could be indexed on an orthorhombic cell
with lattice parameters as follows: BaBi2B2O7 a=11.818 Å, b=8.753 Å, c=7.146 Å, cell volume
V=739.203 Å3, Z=4.
Single crystals of BaBi10B6O25 were obtained by cooling of a melt with the stoichiometric
composition. Glass powder of composition 11.11BaO•55.55Bi2O3•33.33B2O3 (mol%) was
158 Advances in Ferroelectrics

heated in a quartz glass ampoule up to 750°C at a rate 10 K/min. After 2 h exposition at high
temperature, the melt was cooled at a rate 0.5 K/h. Single crystals with sizes up to
1.66×0.38×0.19 mm3 were grown. The x-ray powder diffraction patterns of BaBi10B6O25 could
be indexed on an orthorhombic cell with lattice parameters as follows: a=6.434 Å, b=11.763
Å, c=29.998 Å, cell volume V=2270.34 Å3, Z=8.
Ternary BaBi2B4O10, BaBiB11O19, and BaBi10B6O25 compounds have dominating positions in
ternary diagram and occupied the biggest part of it. Mutual influence of these and other bi‐
nary and ternary compounds (BaB4O7, Ba2B10O17, BaB8O13, Bi4B2O9, BiBO3, Bi3B5O12, BiB3O6,
Bi2B8O15, BaBi2B2O7, and BaBi8B2O16) lead to formation of sixteen ternary eutectics, which
have essential influence on liquidus temperature decrease and to assist in glass formation.
The clear correlation between glass forming and phase diagrams has been observed: glass
melting temperature and level of glass formation depending on the cooling rate of the stud‐
ied melts are in good conformity with boundary curves and eutectic points.
Common regularities of bulk glass samples TEC changes in studied BaO-Bi2O3-B2O3 system
have been determined: the increase of barium and bismuth oxides amounts in glasses of bi‐
nary BaO-Bi2O3 and Bi2O3-B2O3 systems and their joint amounts increasing in ternary com‐
positions leads to increase glasses TEC values from 70 to 127•10-7К-1.
Crystallized barium bismuth borate glass samples have TEC values lower, than initial
glasses. Increase of barium and bismuth oxides amounts in ternary compounds leads to
their TEC values increasing from 49 to 109•10-7К-1.
Electric field induced polarization (P) and remanent polarization (Pr) were measured at
room temperature for BaBi2B2O7 and BaBi10B6O25 glass tape samples crystallized at various
regimes. The remanent polarization 2Pr values were found 0.15 μC/cm2 for the BaBi2B2O7,
and 0.32- 0.9 μC/cm2 for the BaBi10B6O25 crystallized glass tape samples. According to ob‐
tained results it is possible to conclude that all tested samples are ferroelectrics.

Acknowledgements

This work was supported by the International Science and Technology Center (Projects #
A-1591). Author is very gratefull to all project team and to Dr. Rafael Hovhannisyan , Dr.
Nikolay Knyazyan and Prof. Heli Jantunen for effective cooperation and fruitful discussions.

Author details

Martun Hovhannisyan*

Address all correspondence to: [email protected]

Address all correspondence to: [email protected]

 Phase Diagram of The Ternary BaO-Bi2O3-B2O3 System: New Compounds and Glass Ceramics Characterisation 159
http://dx.doi.org/10.5772/52405

Address all correspondence to: [email protected]

«ENI» Institute of Electronic Materials LTD, Armenia

References

[1] The American Ceramic Society & National Institute of Standards and Technology
[ACerS & NIST]. (2004). Phase Equilibria Diagrams. CD-ROM Database, Version 3.0,
157498215.
[2] Levin, E. M., & Mc Daniel, C. L. (1962). The System Bi2O3-B2O3. J. Am.Cer.Soc, 45(8),
355-360.
[3] Masurin, O. V., et al. (1979). Properties of Glasses and Glass-Forming Melts. Hand‐
book., In Russian, v.III, part 2, L.,, Nauka Press.
[4] Muehlberg, M., Burianek, M., Edongue, H., & Poetsch, C. (2002). Bi4B209 crystal
growth and some new attractive properties. J. Cryst. Growth, 237, 740-744.
[5] Becker, P., & Bohaty, L. (2003). Linear electro-optic properties of bismuth triborate,
BiB3O6 (BIBO). Phys. Chem. Glasses, 44, 212-214.
[6] Ihara, R., Honma, T., Benino, Y., Fujiwara, T., & Komatsu, T. (2004). Second-order op‐
tical nonlinearities of metastable BiBO3 phases in crystallized glasses. Optical Materi‐
als, 27, 403-408.
[7] Oprea, I. I. (2005). Optical Properties of Borate Glass- Ceramic. Dissertation zur Erlan‐
gung des Grades Doktor der Naturwissenschaften, Osnabruck University, Germany.
[8] Pottier , M. J. (1974). Mise en evidence d’un compose BiBO3 et de son polymor‐
phisme par spectroscopie vibrationnelle. Bull. Soc. Chim. Belg., 83, 235-238.
[9] Becker, P., Liebertz, J., & Bohatý, L. (1999). Top-seeded growth of bismuth triborate,
BiB3O6. J.Cryst.Growth, 203, 149-155.
[10] Becker, P., & Froehlich, R. (2004). Crystal growth and crystal structure of metastable
bismuth ortoborate BiBO3. Z. Naturforsch. B, 59, 256-258.
[11] Zargarova, M. I., & Kasumova , M. F. (2004). Liquidus surface of the system ZnO -
Bi2O3-B2O3 projection. Zh. Neorg. Mater, In Russian, 26(8), 1678-1681.
[12] Kargin, Yu. F., Zhereb, V. P., & Egorysheva, A. V. (2002). Phase diagram of metasta‐
ble stats of the Bi2O3-B2O3 system. Zh. Neorg. Khim, 47(8), 1362-1364, In Russian.
[13] Barbier, J., Penin, N., & Cranswick, L. M. (2005). Melilite-Type Borates Bi2ZnB2O7 and
CaBiGaB2O7. Chem. Mater., 17, 3130-3136.
[14] Barbier, J., & Cranswick, L. M. (2006). The Non-Centrosymmetric Borate Oxides,
MBi2B2O7(M=Ca,Sr). Solid State Chem, 179, 3958-3964.
160 Advances in Ferroelectrics

[15] Egorisheva, A. V., Skorikov, V. M., & Volodin, V. D. (2008). Calcium Bismuth Borates
in the CaO-Bi2O3-B2O3 system. Zh.Nerg.Mater. In Russian)., 44(1), 76-81.

[16] Kargin, Yu. F., Ivicheva, S. N., Komova, M. G., & Krut’ko, V. A. (2008). Subsolidus
Phase Relation in the SrO-Bi2O3-B2O3 system. Zh.Nerg.Khim, 53(3), 474-478, In Russi‐
an.

[17] Barbier, J., Davis, L. J. M., Goward, G. R., & Cranswick, L. M. D. (2009). Ab initio
structure determination of SrBi2OB4O9 by powder X-ray/neutron diffraction and
NMR spectroscopy. Powder Diffr, 24(1), 35-40.

[18] Levin, E. M., & Mc Murdie, H. F. (1949). The System BаO-B2O3. J. Res.Nat.Bur.Stand‐
ards, 42(2), 131-138.

[19] Levin, E. M., & Ugrinic, G. M. (1953). The System Barium Oxide-Boric Oxide-Silica. J.
Res. Nat.Bur. Stand, 51, 37-56.

[20] Green, C. H., & Wahler, R. L. (1969). Crystallization of Barium Aluminum Borate
Glasses-Rhodium as a Specific Catalyst. In:Kinetics of reactions in ionic systems. Proc.
Intern. Symp. 18-23 IV, New York, 545-553.

[21] Hubner, K. H. (1969). Ueber die Borate 2BaO•5B2O3, tief-BaO•B2O3, 2BaO•B2O3 und
4BaO•B2O3. Neues Jahrb. Mineral., Monatsch, 335-343.

[22] Hovhannisyan, R. M. (2006). Binary alkaline-earth borates: phase diagrams correc‐

tion and low thermal expansion of crystallized stoichiometric glass compositions.
Phys.Chem.Glasses: Eur. J.Glass Sci. Technol. B, 47(4), 460-465.

[23] Crichton, S. N., & Tomozawa, M. (1997). Prediction of phase separation in binary bo‐
rate glasses. J. Non-Crystalline Solids, 215, 244-251.

[24] Hageman, V. B. M., & Oonk, H. A. J. (1987). Liquid immiscibility in the B2O3-MgO,
B2O3-CaO, B2O3-SrO and B2O3-BаO systems. Physics and Chemistry of Glasses, 28,
183-187.

[25] Klinkova, L. A., Nikolaychik, V. I., Barkovskiy, N. V., & Fedotov, V. K. (1999). Phase
relations in the system Bа-Bi-O (20-80 mol% BiO1.5) at pO2=0.01, 0,21 and 1 atmos‐
phere. Zh.Neorg. Khim In Russian)., 44(11), 1774-1782.

[26] Mueller, K., Meen, J. K., & Elthon, D. (1999). System BaO-Bi2O3 in O2. In ACerS &
NIST, 2004.

[27] Shevchuk, A. V., Skorikov, V. M., Kargin, Yu. F., & Konstantinov, V. V. (1985). The
system BаO-Bi2O3. Zh.Neorg. Khim, 30(6), 1519-1522, In Russian.

[28] Witler, D., & Roth, R. S. (2004). System BaO-Bi2O3 in Air,. in Phase Equilibria Dia‐
grams, CD-ROM Database, A CerS-NITS.

[29] Barbier, J., Penin, N., Denoyer, A., & Cranswic, L. M. D. (2005). BaBiBO4, a novel non-
centrosymmetric borate oxide. Solid State Science, 7, 1055-1061.
 Phase Diagram of The Ternary BaO-Bi2O3-B2O3 System: New Compounds and Glass Ceramics Characterisation 161
http://dx.doi.org/10.5772/52405

[30] Egorysheva, A.V, & Kargin Yu, F. (2006). Phase equilibrium in the sub-solidus parts
of the Bi2O3-BaB2O4-B2O3 system. Zh.Neorg. Khim ,In Russian, 51(7), 1185-1189.

[31] Egorysheva, A.V, Skorikov, V.M, Volodin, V.D, Myslitskiy, O.E, & Kargin, Yu, F.
(2006). Phase equilibrium in the BаO-B2O3-Bi2O3 system. Zh.Neorg. Khim ,In Russian,
51(12), 2078-2082.

[32] Bubnova, R. S., Krivovichev, S. V., Filatov, S. K., Egorysheva, A. V., & Kargin, Y. F.
(2007). Preparation, crystal structure and thermal expansion if a new bismuth barium
borate, BaBi2B4O10. Journal of Solid State Chemistry, 180, 596-603.

[33] Elwell, D., Morris, A. W., & Neate, B. W. (1972). The flux system BаO-B2O3-Bi2O3. J. of
Crystal Growth, 16, 67-70.

[34] Hovhannisyan, M. R., et al. (2009). A study of the phase and glass forming diagrams
of the BaO-Bi2O3-B2O3 system. Phys. Chem.Glasses: Eur. J.Glass Sci. Technol. B, 50(6),
323-328.

[35] Hovhannisyan, M. R. (2009). Development of low melting sealing glasses on the bis‐
muth borate and tellur molibdate systems basis. PhD Thesis. State Engineering Uni‐
versity of Armenia, Yerevan.

[36] Hovhannisyan, M. R. (2008). Synthesis of new BaBi10B6O25 compond in BaO-Bi2O3-

B2O3 system. Chemical J. of Armenia, 62(2), 28-29.

[37] Hovhannisyan, R. M., et al. (2008). Mutual influence of barium borates, titanates and
boron titanates on phase diagram and glass formation in the BaO-TiO2-B2O3 system.
Phys.Chem.Glasses: Eur. J.Glass Sci. Technol. B, 49(2), 63-67.

[38] Hovhannisyan, R. M. (2010). Melts supercooling-effective way of inorganic systems

glassforming and phase diagrams construction. Proceedings of the II International con‐
ference of inorganic chemistry and chemical technology, 13-14th Sept., Yerevan, 37-39,
978-9-99412-450-3.

[39] Hovhannisyan, R. M. (2011). New generation highly effective electro-and light-active

nonlinear oriented tape glass ceramic on the basis of stoichiometric three-coordinat‐
ed borates. Final Technical Report of ISTC project # A-1486, Moscow.

[40] Hovhannisyan, R. M., et al. (2011). Phase diagram, crystallization behavior and ferro‐
electric properties of stoichiometric glass ceramics in the BaO-TiO2-B2O3 system. in:
Ferroelectrics- Physical Effects, InTech publishing, Croatia, 49-76.

[41] Hovhannisyan, R. M. (2012). New Lead & Alkali Free Low Melting Sealing Glass
Frits & Ceramic Fillers. Final Technical Report of ISTC project # A-1591, Moscow.

[42] Barseghyan, A. H., Hovhannisyan , R. M., Petrosyan , B. V., Aleksanyan , H. A., &
Toroyan , V. P. (2012). Glass formation and crystalline phases in the ternary CaO-
Bi2O3-Bi2O3 and SrO-Bi2O3-B2O3 systems. Phys.Chem.Glasses: Eur. J.Glass Sci. Technol.
B, in press.
162 Advances in Ferroelectrics

[43] International Center for Diffraction Data [ICDD]. (2008). Powder Diffraction Fails,
PDF-2 release database,. Pennsylvania, USA, 1084-3116.

[44] Sawyer, C. B., & Tower, C. H. (1930). Rochelle Salt as a Dielectric. Phys. Rev, 35(3),
269-273.

[45] Imaoka, M., & Yamazaki, T. (1972). Glass-formation ranges of ternary systems. III.
Borates containing b-group elements, Rep. Inst. Ind. Sci. Univ. Tokyo, 22(3), 173-212.

[46] Janakirama-Rao, Bh. V. (1965). Unusual properties and structure of glasses in the sys‐
tem BаO-B2O3-SrO, BаO-B2O3-Bi2O3, BаO-B2O3-ZnO, BаO-B2O3-PbO, Compt. Rend. VII
Congr. Intern. Du Verre, Bruxelles, 1(104-104).

[47] Izumitani, T. (1958). Fundamental studies on new optical glasses,. Rep. Governm. Ind.
Res. Inst. Osaka [311], 127.

[48] Kawanaka, Y, & Matusita, K. (2007). Various properties of bismuth oxide glasses for
PbO free new solder glasses. Proc.XXIth Intern.Congr.on Glass (in CD-ROM), Stras‐
bourg [I23].

[49] Milyukov, E. M., Vilchinskaya, N. N., & Makarova, T. M. (1982). Optical constants
and some other characteristics of glasses in the systems BaO-Bi2O3 and La2O3-Bi2O3-
B2O3. Fizika i Khimiya Stekla in Russian)., 8(3), 347-349.

[50] Sarkisov, P. D. (1997). The Directed Glass Crystallization- Basis for Development of
Multipurpose Glass Ceramics,. Mendeleev Russian Chemical Technological University
Press, Moscow(In Russian.

[51] Damjanovic, D. (2005). Hysteresis in Piezoelectric and Ferroelectric Materials,. In:

The Science of Hysteresis, Mayergoyz, I & Bertotti, G Elsevier, 0-12480-874-3 , 3,
337-465.

[52] Rawson, H. (1967). Inorganic glass-forming systems. Academic Press, London & New
York, 312.
 Chapter 8

Optical Properties of Ferroelectrics

and Measurement Procedures

A.K. Bain and Prem Chand

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52098

1. Introduction

It is well known that the optical properties of ferroelectric materials find wide ranging appli‐
cations in laser devices. Particularly in the recent years, there has been tremendous interest
in the investigation of the nonlinear optical properties of ferroelectric thin films [1-5] for pla‐
nar waveguide and integrated –optic devices. A new class of thin film waveguides has been
developed using BaTiO3 thin films deposited on MgO substrates [6]. Barium strontium tita‐
nate Ba1-xSrxTiO3 (BST) is one of the most interesting thin film ferroelectric materials due to
its high dielectric constant, composition dependent Curie temperature and high optical non‐
linearity. The composition dependent Tc enables a maximum infrared response to be ob‐
tained at room temperature. The BST thin films in the paraelectric phase, have
characteristics such as good chemical and thermal stability and good insulating properties,
due to this nature they are often considered the most suitable capacitor dielectrics for suc‐
cessful fabrication of high density Giga bit (Gbit) scale dynamic random access memories
(DRAMs). Compositionally graded ferroelectric films have exhibited properties not previ‐
ously observed in conventional ferroelectric materials. The most notable property of the
graded ferroelectric devices or graded Functionally Devices (GFDs) is the large DC polariza‐
tion offset they develop when driven by an alternating electric field. Such GFDs can find ap‐
plications as tunable multilayer capacitors, waveguide phase shifters and filters [7].
Recently, BST thin films were used in the formation of graded ferroelectric devices by de‐
positing successive layers of BST with different Ba/Sr ratios [8].

In our work, the Barium strontium titanate (Ba0.05Sr0.95TiO3) ferroelectric thin films were pre‐
pared on single crystal [001] MgO substrates using the pulsed laser deposition method. The
refractive index of BST (Ba0.05Sr0.95TiO3) thin films is determined in the wavelength range be‐
tween 1450-1580 nm at the room temperature. The dispersion curve is found to decrease

© 2012 Bain and Chand; licensee InTech. This is an open access article distributed under the terms of the
Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
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164 Advances in Ferroelectrics

gradually with increasing wavelength. The average value of the refractive index is found to
be 1.985 in the wavelength range between 1450-1580 nm which is important for optoelec‐
tronic device applications [9].
1: Present address: Director, PM College of Engineering, Kami Road, Sonepat-131001.
2: Present Address: 99 Cyril Road, Small Heath, Birmingham B10 0ST.
Lithium heptagermanate Li2Ge7O15 (LGO) is regarded as a weak ferroelectric and its curie
point Tc is 283.5K [10,11]. Due to its intermediate behaviour between order-disorder and dis‐
placive types in a conventional grouping of ferroelectric materials LGO remains a subject of
interest from both the theoretical and the application point of view. The paraelectric phase
above Tc is orthorhombic D14 2h ~ pbcn and below Tc the ferroelectric phase is C5 2v ~ pbc21
with four formula units in a unit cell in both the phases. Below Tc LGO shows dielectric hys‐
teresis loop and the permittivity shows a sharp peak at Tc [10-12]. Below Tc the spontaneous
polarization appears along the c-axis. Many interesting physical properties of LGO such as
birefringence [13], elastic behaviour [14], thermal expansion [11], dielectric susceptibility
[12,15, 16] and photoluminescence [17] exhibit strong anomalies around Tc. The optical
properties, however vary only to such a small degree that the transition could not be detect‐
ed with the aid of a standard polarization microscope [13]. Employing a high resolution po‐
larization device, Kaminsky and HaussÜhl [13] studied the birefringence in LGO near Tc
and observed anomalies at the phase transition.
The study of piezo-optic dispersion of LGO (un-irradiated and x-irradiated) in the visible re‐
gion of the spectrum of light at room temperature (RT=298 K) shows an optical zone/
window in between 5400Å and 6200Å with an enhanced piezo-optical behavior [18]. The
temperature dependence of the photoelastic coefficients of the ferroelectric crystals
Li2Ge7O15 (both un-irradiated and x-irradiated) in a cooling and a heating cycle between
room temperature and 273K shows an interesting observation including the lowering of the
Tc under uniaxial stress contrary to the increase of Tc under hydrostatic pressure and obser‐
vation of thermal photoelastic hysteresis similar to dielectric behavior [19]. The study of flu‐
orescence spectra of the crystals Li2Ge7O15:Cr3+ in the temperature interval 77-320 K shows
the sharply decrease of intensities of the R1 and R2 lines (corresponding to the Cr3+ ions of
types I and II) during cooling process near the temperature Tc = 283.5 K[16].
The present chapter includes optical properties of the ferroelectric BST thin films and
the Lithium heptagermanate (Li2Ge7O15) single crystals, fabrication methods, measure‐
ment procedures of the refractive index of BST thin films on MgO substrates, the fluo‐
rescence spectra and the photoelastic coefficients of LGO single crystals (un-irradiated
and x-irradiated) at different wave lengths and temperatures around the phase transi‐
tion temperature Tc. The potential of these materials for practical applications in the op‐
to-electronic devices will also be discussed.

1.1. Optical property of Barium strontium titanate thin films

The Barium strontium titanate (Ba0.05Sr0.95TiO3) ferroelectric thin films were prepared on sin‐
gle crystal MgO substrates using the pulsed laser deposition (PLD) method at a substrate
 Optical Properties of Ferroelectrics and Measurement Procedures 165
http://dx.doi.org/10.5772/52098

temperature of 780 oC and then annealed at 650 oC for 55 min. The x-ray diffraction (XRD)
analysis revealed that the films are oriented with [001] parallel to the substrate [001] axis
and thus normal to the plane of the films [9]. The films were grown to a thickness of 430 nm.

Figure 1. Schematic diagram of the experimental setup for the measurement of refractive index of the Ba0.05Sr0.95TiO3
thin films at room temperature. He-Ne Laser for alignment (1), Lenses (2), Polarizer (3), sample holder (4), BST sample
(5), Agilent light wave measurement system (6) and Tunable Laser (7).

Figure 1 shows the schematic diagram of the experimental setup for the measurement of the
refractive index of Ba0.05Sr0.95TiO3 thin films on MgO substrates through a reflection method.
The He-Ne laser beam is used as a source of light to setup the alignment of the reflected
beam of light from the samples to the detector. The incident beam is allowed to pass
through a polarizer onto the sample. The reflected light is then passed through the same po‐
larizing beam splitter oriented at 45o relative to the incident light and finally allowed to fall
on the detector that is at 90o to the reflected/incident beam of light. The reflectivity measure‐
ment of the black metal, mirror, MgO substrate and Ba0.05Sr0.95TiO3 thin films were carried
using the Agilent 8164A Light Wave Measurement system in the wavelength region of
1450-1580 nm at room temperature.

The refractive index of substrate MgO is taken to be 1.7 [9]. The reflectivity of Ba0.05Sr0.95TiO3
film is then normalized with respect to the mirror. The value of refractive index is derived
from model described in ref. [20]. The fitting is done with the calculated data of the reflectiv‐
ity of Ba0.05Sr0.95TiO3 in the wavelength range between 1450-1580 nm. Figure 2 shows the re‐
fractive index of Ba0.05Sr0.95TiO3 thin films as a function of wavelength at room temperature.
The refractive index of Ba0.05Sr0.95TiO3 with BaxSr1-xTiO3 (BST) and other materials of ferro‐
electric thin films at different wavelengths are presented in table 1.
166 Advances in Ferroelectrics

Figure 2. The variation of refractive index of Ba0.05Sr0.95TiO3 thin films as a function of wavelength.

Sample Name Refractive index Wavelength Remarks

BaxSr1-xTiO3(x=0%) 2.37 600 nm (RT) Ref. [21]

BaxSr1-xTiO3(x=30%) 2.42 600 nm (RT) Ref. [21]

BaxSr1-xTiO3(x=50%) 2.37 600 nm (RT) Ref. [21]

BaxSr1-xTiO3(x=70%) 2.34 600 nm (RT) Ref. [21]

BaxSr1-xTiO3(x=50%) 2.45 470 nm (RT) Ref. [22]

BaxSr1-xTiO3(x=80%) 2.27 430 nm (RT) Ref. [23]

PbZr1-xTixO3 (PZT) 2.87 400 nm (300 0C) Ref. [24]

PbZr1-xTixO3 (PZT) 2.82 400 nm (50 0C) Ref. [24]

PbZr1-xTixO3 (PZT) 2.66 500 nm (300 C) 0

Ref. [24]

PbZr1-xTixO3 (PZT) 2.67 500 nm (50 C)0

Ref. [24]

PbTiO3 3.10 470 nm (RT) Ref. [25]

PbTiO3 2.80 490 nm (RT) Ref. [25]

PbTiO3 2.75 550 nm (RT) Ref. [25]

SrxBa1-xNb2O6 (x=61%) 2.35 400 nm (RT) Ref. [26]

Table 1. The refractive index of BST and other ferroelectric thin films.

As shown in Figure 2, the dispersion curve decreases gradually with increasing wavelength.
The average value of the refractive index is found to be ~ 1.985 in the wavelength range of
1450-1580 nm which is important for optoelectronic device (optical waveguide) applications.
The variation of refractive index is attributed predominantly to the changes of electronic
 Optical Properties of Ferroelectrics and Measurement Procedures 167
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structure associated with the larger lattice parameter and variations in atomic co-ordination
[27] that is local relaxations.

1.2. Growth and structure of Li2Ge7O15 Crystals

Single crystals of Li2Ge7O15 are grown in an ambient atmosphere by Czochralski method

from stoichiometric melt, employing a resistance heated furnace. Stoichiometric mixture of
powdered Li2CO3 and GeO2 in the ratio of 1.03 and 7.0 respectively was heated at 1100 K for
24 hours to complete the solid state reaction for the raw material for the crystal growth. The
crystals were grown by rotating the seed at the rate of 50 rpm with a pulling rate of 1.2 mm/
hour. The cooling rate of temperature in the process of growth was 0.8-1.2 K/hour. The crys‐
tals grown were colourless, fully transparent and of optical quality. The crystal axes were
determined by x-ray and optical methods.

Figure 3. Schematic diagram of the experimental setup for the measurement of fluorescence spectra of the crystals
Li2Ge7O15:Cr3+. He-Ne Laser for radiation (1), Glen prism (2), crystal sample (3), condenser (4), polarizer (5), spectro‐
graph (6) Multichannel analyzer(7) and computer (8).

The desired impurities such as Cr+3, Mn+2, Bi+2, Cu2+ and Eu+2 etc are also introduced in de‐
sired concentration by mixing the appropriate amount of the desired anion salt in the
growth mixture. The crystal structure of LGO above Tc is orthorhombic (psedohexagonal)
with the space group D14 2h (Pbcn). The cell parameters are a: 7.406 Å, b: 16.696 Å, c: 9.610 Å,
Z = 4 and b~√3c. Below Tc a small value of spontaneous polarization occurs along c-axis and
the ferroelectric phase belongs to C5 2v (Pbc21) space group. The crystal structure contains
strongly packed layers of GeO4 tetrahedra linked by GeO6-octahedra to form a three dimen‐
sionally bridged frame work in which Li atoms occupy the positions in the vacant channels
extending three dimensionally [14, 28, 29]. The size of the unit cell (Z = 4) does not change at
168 Advances in Ferroelectrics

the phase transition and ferroelectric phase transition is associated with a relaxational mode
as well as the soft phonon [30]. Activation of the pure crystals with impurity ions will de‐
mand charge compensating mechanism through additional defects in the pure lattice.

Figure 4. Fluorescence Spectra of the crystals Li2Ge7O15:Cr3+ at T=77 K.

Figure 5. Temperature dependence of intensity of R1 and R2 Lines of fluorescence in Li2Ge7O15:Cr3+ crystals near the
phase transition temperature Tc.

1.3. Study of fluorescence spectra of Li2Ge7O15:Cr3+ crystals

The fluorescence spectra of the crystals Li2Ge7O15:Cr3+ were studied in the temperature inter‐
val 77-320 K including the phase transition temperature Tc = 283.5 K. The experimental set to
record the fluorescence spectra of the crystals Li2Ge7O15:Cr3+ is shown in fig.3. A laser with
the pair of mode (λ1=510.6 nm, λ2=578.2 nm) was used as a source of excitation of the crystal
 Optical Properties of Ferroelectrics and Measurement Procedures 169
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sample. The recording of fluorescence spectra were carried out by the optical multichannel
analyzer in combination with the polychromator. The radiation beam was initially polarized
with glen prism. The plane Polaroid was used as an analyzer that was placed before the in‐
put aperture of the polychromator.

The fluorescence spectra consist of narrow intensity lines referred to R1 and R2 with frequen‐
cies γ1~14348 cm-1 and γ2 ~14572 cm-1. These lines split further into two components each R1 /
and R2 / respectively at lowering the temperature towards 77 K. Besides this, a wide long
wavelength region/zone is observed in the spectra. It may be related with the effect of elec‐
tron-photon interaction. It is known that Cr3+ doping ions in the structure of Li2Ge7O15:Cr3+
crystals substitute the Ge4+ host ions within oxygen octahedral (GeO6) complexes [31-36].
The optical spectra of Cr3+ ions shows the existence of two types of Cr3+ centre (type I and II
with different values of effective g-factor) as observed in EPR (Electron Paramagnetic Reso‐
nance) spectra of Cr3+ ions in ferroelectric phase of the crystals Li2Ge7O15:Cr3+ [32, 33]. Two
pair of R lines 4A2 - 2E (at T=77 K, its positions are R1=14348 cm-1, R1 /=14402 cm-1, R2=14572
cm-1 and R2 /=14593 cm-1) are observed at low temperature region (T<190 K) in the optical
spectra of the crystals Li2Ge7O15:Cr3+ as shown in Fig. 4. Actually the two different types of
Cr3+ centers (R and R/) with pretty different positions below Ē and above 2Ᾱ levels of the
excited E2 level are duplicate [37, 38] and conform to the EPR observations.

Figure 6. Part of EPR spectrum of Cr3+ doped LGO crystal in an arbitrary orientation at RT. The four EPR signals are
attributed to four distinct Cr3+ sites per unit cell of LGO.

The intensity of fluorescence of the R 1 and R2 lines of the crystals Li2Ge7O15:Cr3+ were studied
near the phase transition temperature Tc at the direction E┴[001]. It is observed that the in‐
tensity of R1 and R 2 lines are decreased sharply near the phase transition temperature Tc but
at high temperature region (T>Tc) the intensity again increases as shown in figure 5. Such
170 Advances in Ferroelectrics

nature of suppression of R1 and R2 lines was not observed previously and it may be related
with the mechanism of interaction of excitation spectra of light in the crystals Li2Ge7O15:Cr3+
near the phase transition temperature Tc[17].

The Crystals doped with chromium impurity give EPR (Electron Paramagnetic Resonance)
signals characteristics of the trivalent chromium ions [Fig.6]. It is known that impurity Cr3+
ions substitute the Ge4+ host ions within oxygen octahedral in the basic structure of (LGO)
crystal [31-36]. Incorporation of tri-positive chromium ions into GeO6-octahedra changes the
local symmetry of the lattice site from monoclinic C2 group to triclinic C1 group. The local
symmetry lowering is attributed to the effect of the additional Li+ defect required for com‐
pensating the charge misfit of Cr3+ ion at the Ge4+ site. Taking into account a weak coupling
of lithium ions with the germanium – oxygen lattice framework, the interstitial Li+ is consid‐
ered to be the most probable charge compensating defect, located within the structural cavi‐
ty near the octahedral CrO6 complex (Fig.7). Subsequent measurements of optical spectra
have confirmed the model of Cr3+– Li+ pair centers in the LGO crystal structure [32, 33].

Figure 7. Physical model of Cr3+ centers in Li2Ge7O15:Cr3+ crystals and its dipole moment d.

The available data make it possible to assume that electric dipole moments of Cr3+– Li + pairs
are directed along the crystal axis “a” of the crystal. Interstitial Li+ ions locally break the
symmetry axis C2 of the sites within the oxygen octahedral complexes [34]. As a result, there
are two equivalent configurations of the pair centers which are conjugated by broken C2 axis
and have dipole moments with opposite orientations. It may be assumed that pair centers
can reorient due to thermal activation. Reorientation of the pair centers should be accompa‐
nied by: i) shortening of the configuration life time and ii) switching of defect dipole mo‐
ments [35]. This is reflected in the typical temperature dependence of the imaginary part of
dielectric permittivity of chromium doped LGO single crystals [35] along the a-axis of the
crystal shown in fig.8.
 Optical Properties of Ferroelectrics and Measurement Procedures 171
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Figure 8. Temperature dependence of Imaginary part ε’’of permittivity ε=ε’-je’’ of LGO:Cr3+, measured along crystal a -
axis at the following frequencies : 0.5 kHz (1); 1 kHz (2); 5 kHz (3); 10 kHz (4). Distinct peak is observed in ε’’ in the
temperature range 350-450 K and the peak is observed to shift to higher temperature for higher frequencies. In con‐
trast no such peak is observed for the real part ε’ of the permittivity. The typical behavior is observed only along crystal
a –axis which incidentally coincides with the proposed Cr3+- Li+ centers.

1.4. Principle of Photoelasticity

If a rectangular parallelepiped with edges parallel to x[100], y[010] and z[001] axes is
stressed along z-axis and observation is made along y-axis, as shown in Fig.9, then the path
retardation δzy introduced per unit length due the stress introduced birefringence is given by

δzy = (Δnz – Δnx) = CzyPzz (1)

where Δnz and Δnx are the changes in the corresponding refractive indices, (Δnz – Δnx) is the
corresponding stress induced birefringence, Pzz is the stress along z-axis and Czy is a con‐
stant called the Brewster constant or the relative photoelastic coefficient. In general the
Brewster constant is related to the stress optical and strain optical tensors of forth rank [39]
and is a measure of the stress induced (piezo-optic) birefringence. It is conveniently ex‐
pressed in the unit of 10-13 cm2/dyne per cm thickness along the direction of observation is
called a Brewster [39].

1.5. Measurement procedure of photoelastic constants

To study the piezo-optical birefringence the experimental set up consists of a source of light
(S), a lens (L) to render the rays parallel, a polarizer (P), an analyzer Polaroid (A), a Babinet
compensator (B) and a detector (D), as shown in Fig.10. The P and A combination are adjust‐
ed for optimal rejection of light. The sample with stressing arrangement and a Babinet com‐
pensator are placed between P and A. A monochromator and a gas flow temperature
controlling device are used to obtain the piezo-optic coefficients (Cλ) at different wave‐
lengths and temperature. The subscript λ in the symbol Cλ denotes that the piezo-optic coef‐
172 Advances in Ferroelectrics

ficient depends on the wavelength of light used to measure it. The experiments are carried
out for different wavelengths using white light and a monochromator and the monochro‐
matic sodium yellow light. An appropriate stress along a desired direction of the sample is
applied with the help of a stressing apparatus comprising a mechanical lever and load.

Figure 9. A solid under a linear stress of stress-optical measurements (Pzz is the applied stress and LL is the direction of
light propagation and observation).

Figure 10. A schematic diagram of the experimental setup for the measurement of photoelastic constants of the crys‐
tals at room temperature. Source of light (S), Lense (L), Polarizer (P), Crystals (C) under stress, Babinet Compensator (B),
Analyzer (A) and Detector (D).

To start with, the Babinet compensator is calibrated and the fringe width is determined for
different wavelengths of light in the visible region. The crystal specimen is placed on the
stressing system so that the stress could be applied along vertical axis and observation made
along horizontal axis. A load on the crystal shifts the fringe in the Babinet compensator and
this shift is a measure of the piezo-optic behavior. The piezo-optic coefficients (Cλ) are now
calculated using the calibration of the Babinet compensator. The experiment is repeated for
other orientations of the crystals and the results are obtained.
 Optical Properties of Ferroelectrics and Measurement Procedures 173
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1.6. Piezo-optic Dispersion of Li2Ge7O15 Crystals

The experimental procedure for the piezo-optic measurements is described in section 1.5.
The polished optical quality samples worked out to dimensions i) 5.9 mm, 9.4 mm and 5.0
mm; ii) 3.17 mm, 5.88 mm and 6.7 mm, along the crystallographic a, b and c axes respective‐
ly. The stress was applied with an effective load of ~23 kg in each case [40].

The values of Cλ thus obtained at different wavelengths are given in Table 2 and the results
are plotted in Fig. 11. Here Cpq is the piezo-optic coefficient with the stress direction being p
and observation direction being q. The results show an interesting piezo-optic behavior. A
survey of literature indicates that the piezo-optic behavior of materials studied till now
shows a reduction of Cλ with increasing wavelength in the visible region [39]. In the present
case, Cλ decreases with wavelength up to a certain wavelength as in other normal materials
and then suddenly shows a peak and later on the usual behavior of reduction in the values
of piezo-optic coefficients is observed.

Wavelengths

Obs. Cpq 4358Å 4880Å 5390Å 5890Å 6140Å

1 Cxy 4.024 3.819 3.722 4.328 3.677

2 Cxz 5.243 4.895 4.770 5.552 4.451

3 Cyx 4.084 3.525 3.092 3.562 2.913

4 Cyz 4.353 4.118 3.946 4.261 3.866

5 Czy 4.179 2.814 3.177 3.713 3.172

6 Czx 3.312 2.991 2.650 4.190 2.618

Table 2. Stress optical coefficients cpq (in Brewster) for Li2Ge7015 at different wave lengths.

To the best knowledge of the authors this behavior is unique to the LGO crystals. For the
sake of convenience we denote Cλ measured at λ = 5890 Å as C5890 and so on. The results
show that sometimes the value of C5890 is even higher than that at C4400, the value of piezo-
optic coefficient obtained at the lowest wavelength studied here. This is the case with Cxy,
Czx and Cxz. For other orientations the value is lower than that at 4400 Å. Further, Cλ is found
to have increased to more than 50% in the case of stress along [001] and observation along
[100]. Also, it is interesting to note that the value of C6140, is less than that of C5390, in tune
with usual observation of piezo-optic dispersion. Thus one can see an “optical window” in
between 5400 Å and 6200 Å. The height of this optical window is different for various orien‐
tations, though the width seems approximately the same. The maximum height of about 1.5
Brewster was found for Czx followed by Cxz with about 0.9 Brewster. It should be noted here
that z-axis is the ferroelectric axis for LGO. It is also interesting to note that the change in
height is more in the former while the actual value of Cλ, is less compared to that of the lat‐
ter. The percentage dispersion also is different for various orientations. It is very high, as
high as 25% for Czy, while it is just 10% for Cxy.
174 Advances in Ferroelectrics

Figure 11. Stress optical dispersion of Li2Ge7015 crystals with wavelength at room temperature (298 K).

Figure 12 shows the variation of Czx(λ) at the temperatures ranging from 298K to 283K on
cooling process of the sample LGO. It is clear from the figure that the distinct peak of Czx(λ)
appears only at the sodium yellow wavelength of 5890 Å for the whole range of tempera‐
tures (298 K–283 K) investigated. It is also interesting to note that a temperature anomaly is
also observed around 283 K. LGO undergoes a second order phase transition at 283.5 K from
the high temperature paraelectric phase to the low temperature ferroelectric phase. So this
anomaly is related to this phase transition of the LGO crystal.

The observed peculiarity of piezo-optic behavior could be due to many factors, viz., i) anom‐
alous behavior of refractive index or birefringence ii) anomalous ferroelastic transformation
at some stage of loading iii) shift of absorption edge due to loading. The following have
been done to identify the reasons for this peculiar behaviour.

Birefringence dispersion has been investigated in the visible region and no anomalies in its
behavior has been observed. This rules out the first of the reasons mentioned. The reason
due to ferroelastic behavior also is ruled out since the effect would be uniform over all the
wavelengths investigated. It was not possible to investigate the effect of load on the absorp‐
tion edge. Hence an indirect experiment has been performed. If there is a shift in the absorp‐
tion edge due to loading the sample, the peak observed now at sodium yellow light would
shift with load. No clear shift of the peak could be observed within the experimental limits.
Another interesting experiment was done to identify the source of the anomaly. It is well
known that Tc of LGO changes under uniaxial stress. The measurements were made near Tc
under different stress (loads). Although Tc was found to shift a little with load the dispersion
peak did not show any discernible shift. No particular reason could be established as to why
a dispersion peak appears around sodium yellow region. Another interesting work in this
 Optical Properties of Ferroelectrics and Measurement Procedures 175
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direction is on Gd2(Mo04)3 — where an anomalous peak was recorded in spontaneous bire‐

fringence at 334.7 nm [41], an observation made for the first time.

Figure 12. The variation of Czx(λ) at the temperatures ranging from 298 K to 283 K on cooling process of the sample
Li2Ge7015.

It is well known that the photoelasticity in crystals arises due to change in number of oscilla‐
tors, effective electric field due to strain and the polarisability of the ions. In the present case,
as the wavelength approaches around 5400 Å, the ionic polarisability seems to be changing
enormously. There is no optical dispersion data available on LGO. We have conducted an
experiment on transmission spectra of LGO along x, y and z-axes, which shows a strong ab‐
sorption around 5400 Å. The observed anomaly in the piezo-optic dispersion may be attrib‐
uted to the absorption edge falling in this region. This explanation needs further
investigation in this direction. It is also known that the strain optical dispersion arises due to
the shift in absorption frequencies and a change in the oscillator strength caused by the
physical strain in the crystal.

1.7. Irradiation Effect on Piezo-optic Dispersion of Li2Ge7O15 Crystals

The ferroelectric single crystals Li2Ge7O15 was irradiated by x-ray for one hour and the ex‐
perimental processes described in section 1.5 were repeated for the crystal (irradiated) LGO
in order to understand the radiation effect on piezo-optical birefringence dispersion [18].
The values of Cλ of the crystal (irradiated) LGO thus obtained at different wavelengths are
given in Table 3 and the results are plotted in Fig. 13.
176 Advances in Ferroelectrics

Wavelengths

Obs. C /
pq 4358Å 4880Å 5390Å 5890Å 6140Å

1 C /
xy 4.08 3.87 3.72 4.33 3.73

2 C/ xz 5.35 5.00 4.88 5.59 4.55

3 C/ yx 4.02 3.47 3.01 3.50 2.83

4 C /
yz 4.39 4.19 4.01 4.26 3.90

5 C /
zx 4.63 4.46 4.41 4.66 4.29

6 C /
zy 3.71 3.26 2.97 3.43 2.72

Table 3. Stress Optical Coefficients Cpq (in Brewsters) for Li2Ge7015 (irradiated) at different wavelengths.

Some interesting results are obtained in the case of irradiated crystal LGO. The peak value
of C/ zx has decreased about 18% and that of C/ zy has increased about 25% at the wave length
λ= 5890 Å. Also, it is interesting to note that the value of C6140, is less than that of C5390 for the
un-irradiated and irradiated sample of LGO crystal, in tune with usual observation of piezo-
optic dispersion.

Irradiation of crystals can change physical properties of the crystals. Irradiation brings about
many effects in the crystal such as creating defects, internal stress and electric fields etc.
These irradiation effects in turn are supposed to affect the physical properties of the irradiat‐
ed crystal as compared to un-irradiated crystal. While there was no appreciable change in
the lattice parameters, a significant drop in the value of dielectric constant and tan δ was ob‐
served upon x-irradiation of ferroelectric glycine phosphate. An appreciable shift in the
phase transition temperature towards the lower temperature was observed. These changes
are attributed to the defects produced in it by irradiation [42]. The studies of triglycine sul‐
phate (TGS) showed that very small doses of x-irradiation can give large changes of the fer‐
roelectric properties. The direct evidence of domain clamping by defects was obtained from
optical studies. With increasing dosage the dielectric constant peak and polarization curve
broaden and move to lower temperatures. In our present studies, the x-irradiation is be‐
lieved to produce internal stress and electric fields inside the crystals LGO due to defects
that can change the values of piezo-optic constants [43].

1.8. Piezo-optic Birefringence in Li2Ge7O15 Crystals

The temperature dependence of the photoelastic coefficients of the ferroelectric crystals

Li2Ge7O15 in a cooling and heating cycle between 298 K and 273 K was carried out with the
experimental procedure described in section 1.5 [19]. A special arrangement was made to
vary the temperature of the sample. The temperature was recorded with a digital tempera‐
ture indicator and a thermocouple sensor in contact with the sample.
 Optical Properties of Ferroelectrics and Measurement Procedures 177
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Figure 13. Stress optical dispersion of Li2Ge7015 crystals (un-irradiated and irradiated) with wavelength at room tem‐
perature (298 K).

Figure 14. Temperature dependence of the piezo-optic coefficients Cxy, Cxz, Cyz and Cyx of the crystals LGO in a cooling
(0) and heating (Δ) cycle.

The temperature dependence of piezo-optic coefficients Cpq of the crystals Li2Ge7O15 between
298 K and 273 K were determined and are shown in Fig. 14 and Fig. 15. The values of Cpq at
178 Advances in Ferroelectrics

291 K and 278 K were reported in paper [44] and it was observed that there were large
changes in the values of Czy and Cyz at 278 K and 291 K as compared to other components
and Czy did not show a peak in its temperature dependence between 291K and 278 K.

Figure 15. Anomalous temperature dependence of the piezo-optic coefficients Czx and Czy of the crystals LGO in a
cooling (0) and heating (Δ) cycle.

Here in contrast we observed a peak in the temperature dependence of both Czy and Czx at
279 K. The temperature dependence of Cpq are quite interesting, for example the piezo-optic
coefficients Cyz, Cyx and Cxz have negative temperature derivatives but Cxy has a positive
temperature derivative. In complete contrast both Czy and Czx have both positive and nega‐
tive temperature derivatives at different temperature intervals between 298 K and 273 K (Ta‐
ble: 4). Besides a clear thermal hysteresis is observed in Czy and Czx in a complete cooling
and heating cycle (Fig. 15) whereas no discernible hysteresis is observed in rest of the piezo-
optic coefficients (Fig. 14). The two distinct anomalies in the temperature dependence of Czy
and Czx are characterized by a valley at Tm (∼289 K) and a peak at Tc (∼279 K). Anomalous
temperature dependence of Czx at different wave lengths is also shown in Fig. 16. The tem‐
 Optical Properties of Ferroelectrics and Measurement Procedures 179
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perature dependence of the dielectric permittivity along the c-axis of LGO shows a sharp
peak at Tc (283.5 K) and the Curie-Weiss law holds only for a narrow range of temperature
(Tc ± 4 K) [11,15, 16]. The peak for piezo-optic coefficient is attributed to the paraelectric to
ferroelectric phase transition of LGO at Tc. To check the curie-Weiss law like dependence
near Tc the following relation is used.

CT – C0 = Kpq (T – Tc)
pq pq / (2)

Where CT pq and C0 pq denote the value of the corresponding piezo-optic coefficients at tem‐
perature T and 273 K respectively and Kpq is a constant. Fig. 17 shows the (CT pq – C0 pq)−1 vs
(T−Tc) curve for Czx and Czy. It is clear from these curves that like dielectric constant the rela‐
tion fits well only within a narrow range of temperature near Tc(Tc± 4 K). The solid lines de‐
note the theoretical curves with the following values Kzx = 1.05; Kzy = 0.92 for T > Tc , Kzx =
−0.40; Kzy = −0.34 for T < Tc and Tc = 279 K.

Cpq Value of Derivative Temperature Range Ratio

(Brewster/K)

Czx 0.013 296K-289K -1.69

-0.022 289K-283K
-0.090 282K-279K -2.0
0.181 279K-276K
~0 276K-273K

Cxz -0.003 293K-273K

Czy 0.020 296K-289K -0.75

-0.015 289K-283K
-0.095 282K-279K -1.9
0.179 279K-276K
~0 276K-273K

Cyz -0.026 293K-273K

Cxy 0.007 293K-273K

Cyz -0.023 293K-273K

Table 4. The temperature derivative [dlnCpq /dT] of the piezo-optic coefficients of Li2Ge7O15.

Furthermore the magnitudes of the ratio of the temperature derivatives below and above Tm
and Tc are given in Table 4 and we can see that the ratio near Tc comes out to be about 2.
Therefore it satisfies the law of two for the ratio of such derivatives of quantities which are
coupled with the spontaneous polarization in second order ferroelectric phase transition
such as in the case of triglycine sulphate [45] and LGO. Therefore the peak around Tc is [ 13,
15, 16] attributed to the paraelectric to ferroelectric phase transition of LGO. The smallness
180 Advances in Ferroelectrics

of Kpq and the applicability of relation (2) above only in a narrow range of temperature sug‐
gest that LGO may be an improper ferroelectric. The law of two does not hold for the ratio at
Tm (Table 4). Therefore this anomaly is not related to the spontaneous polarization.

From the behaviour that only Czx and Czy show anomalous it is obvious that birefringence
(Δnz–Δny) and (Δnz–Δnx) show steep increase around Tc and below Tc show a (T–Tc )1/2 be‐
haviour correlated to the spontaneous polarization which is parallel to the z-axis (crystallo‐
graphic c-axis). From the behaviour of Cxy and Cyx which do not show any temperature
anomaly we may say that only nz is responsible for the anomaly in accordance with the be‐
haviour of the dielectric properties where only ε 33 is strongly affected by the phase transi‐
tion. These observations are in accordance with the results of Faraday effect and
birefringence in LGO [13].

Figure 16. Anomalous temperature dependence of piezo-optic coefficient Czx of the crystals LGO at different wave
lengths in a cooling (0) and heating (Δ) cycle.

As mentioned by Lines and Glass [43], under an external pressure Tc of a ferroelectric phase
transition may be shifted. This shift may be to the higher or the lower side of normal Tc. Wa‐
da et al. [46] studied the pressure effect on the ferroelectric phase transition in LGO through
the dielectric and Raman scattering measurements and found a positive pressure coefficient
dTc /dp = 14.6 K/kbar. Preu and HaussÜhl [12] studied the dependences of dielectric con‐
stants on hydrostatic and uniaxial pressure as well as temperature. They observed a shift of
Tc at a rate of 14.02 K/kbar for the hydrostatic pressure and ∼7 K/kbar for the uniaxial pres‐
sure. In the present case the position of the peak of Czy is found to depend on the stress ap‐
plied. If the peak position is believed to represent the Tc, it appears to shift to the lower side
under the uniaxial stress. To see whether Tc shifts linearly with uniaxial stress similar to the
earlier observations [12, 46], we used different stresses within the elastic limits of LGO for
 Optical Properties of Ferroelectrics and Measurement Procedures 181
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Czx and found a linear relationship (Fig. 18). However, a negative stress coefficient dTc /dp ∼
−22 K/kbar is obtained in this case which agrees only in magnitude with the hydrostatic
pressure coefficient. The linear curve (Fig. 18) extrapolates to a Tc = 281.5 K in the unstressed
state instead of 283.5K as determined by dielectric measurements [11, 15, 16]. This may be
due to a non linear dependence of shift of Tc under stress near 283.5 K.

Figure 17. Plots of (CTpq – Co pq )-1 vs (T-Tc) curve for Czx and Czy.

Figure 18. The stress dependence of the shift of Tc for Czx.

Now we turn to the anomaly around Tm. Morioka et al. [47] proposed that there is an inter‐
action between the soft phonon mode and a relaxational mode in the paraelectric phase in
the temperature interval 300 K to Tc. The critical slowing down of the relaxational mode
182 Advances in Ferroelectrics

near Tc is expected to cause the increase of the fluctuation of the spatially homogeneous po‐
larization and thereby the increase of the fluctuation of the hyperpolarizability with kc = 0.
Wada et al. [48] measured the soft phonon mode with the help of their newly designed FR-
IR spectrometer and proposed that as Tc is approached from above soft phonon mode be‐
comes over damped and transforms to a relaxational mode.

On the other hand there may exist a relaxational mode with an independent degree of free‐
dom as well as the soft phonon mode and the character of the softening transfers from the
phonon to the relaxational mode. This is an important problem in determining the dynamics
of the peculiar ferroelectric phase transition of LGO, where both the dielectric critical slow‐
ing down characteristic of the order-disorder phase transition and the soft phonon mode
characteristic of the displacive phase transition are observed [11, 14]. In the light of the
above discussion we may say that the change up to Tm is caused by the softening of mode
and the softening character transforms to the relaxations mode near Tm causing a change in
the trend below Tm and near Tc the relaxational mode becomes dominant. The valley around
Tm is perhaps caused by the interplay between the competitive relaxational mode and the
soft phonon mode. It has been observed that softening of the velocity and rise of the damp‐
ing of acoustic phonon occur in the paraelectric phase of LGO even quite far from Tc, i.e.(T-
Tc) ∼ 30 K and the effect is attributed to the fluctuation induced contributions [49].

Obs. Cpq Paraelectric (PE) At Tc = 279 K

phase (RT)

1 Cxy 4.38 3.85

2 Cxz 5.55 5.85

3 Cyx 3.60 4.46

4 Cyz 4.26 5.50

5 Czy 3.71 4.83

6 Czx 4.19 5.45

Table 5. Stress optical coefficients cpq (in Brewster’s) of Li2Ge7015 at RT=298 K and at Tc = 279 K.

Another interesting aspect is the observation of a significant thermal photoelastic hysteresis

(Fig. 15). Although the peak position does not shift in the heating cycle the values of the
photoelastic constants get reduced significantly in the heating cycle as compared to the cor‐
responding values in a cooling cycle. A similar kind of hysteresis was observed in the dielec‐
tric behaviour of LGO and the appearance of the dielectric hysteresis is attributed to the
internal space charge (electrets state) effects which produce an internal electric field in LGO
on heating from the ferroelectric phase [15-17]. It was possible to compensate the internal
electric field effects in dielectric measurements by an external electric field [15-17]. It is sus‐
pected that the photoelastic hysteresis also occurs due to similar effects. Although it was not
possible to try to compensate the electric field effects in the present investigation, it is possi‐
 Optical Properties of Ferroelectrics and Measurement Procedures 183
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ble to attempt experiment under the simultaneous application of a suitable electric field and
stress along z-direction.

Obs Cpq Rochelle SaltKDP ADP Remarks

(RS)

1 Cxz 3.74 0.28 1.25 Ref. [50] for RS

2 Cyz 4.29 0.28 1.25 a- polar axis

3 Cyx 3.56 1.04 4.30 Ref. [51] for KDP

4 Czx 0.85 1.54 3.50 Ref. [52] for ADP

5 Czy 2.61 1.54 3.50

6 Cxy 3.04 1.04 4.30

Table 6. Piezo-optic coefficients cpq (in Brewsters) for some ferroelectric crystals in their paraelectric (PE) phases.

The Stress optical coefficients Cpq of the crystals Li2Ge7O15 at paraelectric phase (RT = 298 K)
and at Tc = 279 K are presented in Table 5. It is important to compare the values of Cpq for
Li2Ge7O15 with other ferroelectric crystals given in Table 6 particularly with Rochelle-salt
(RS) which belongs to the orthorhombic class like LGO [44]. The values of Cpq are signifi‐
cantly higher for LGO as compared to these ferroelectric systems. So, the large photoelastic
coefficients and the other properties like good mechanical strength, a transition temperature
close to room temperature and stability in ambient environment favour LGO as a potential
candidate for photoelastic applications.

The EPR (Electron Paramagnetic Resonance) spectroscopy of the transition metal ion doped
crystals of LGO (Mn2+, Cr3+) has also been studied both in Paraelectric (PE) and ferroelectric
(FE) phases in the temperature interval from 298 K to 279 K during cooling and heating cy‐
cles [17, 36, 53]. It is observed that on approaching Tc in a cooling cycle, the EPR lines are
slightly shifted to the high field direction and undergo substantial broadening. At the tem‐
perature Tc ( ≈ 283.4 K), the EPR lines are splitted into two components which are shifted to
the higher and lower field directions progressively as a result of cooling the sample below Tc
as shown in Fig.19.

During heating cycle (i.e. approaching Tc from below), the phenomena occurred were just
opposite to the above processes observed in the cooling cycle. However, the EPR line width
(peak to peak ∆Hpp) for H║c, H┴a was found to decrease to about one third of its value at Tc
in a heating cycle as compared to its value in the cooling cycle. The shape of the EPR reso‐
nance lines far from Tc has a dominant Lorentzian character (a Lorentzian line shape) but
very near to Tc, the line shape has been described mainly by Gaussian form of distribution (a
Gaussian line shape). All the peculiarities observed are attributed to the PE ↔ FE phase
transition of the LGO crystals. The line width reduction near Tc is attributed to the internal
space charge (electret state) effects which produce an internal electric field inside the crystals
184 Advances in Ferroelectrics

on heating process from the ferroelectric phase. This observation is similar to the photoelas‐
tic hysteresis behavior of the crystals LGO near Tc.

Figure 19. Temperature dependence of EPR lines of Li2Ge7O15:Cr+3 crystals for |M|= ½ ↔3/2, H║a, H┴c near Tc during
cooling process.

Figure 20. Temperature dependence of photoelastic coefficients Cxy, Cxz, Cyz, Cyx, Czx and Czy of the crystal (x-irradiated)
LGO in a cooling (0) and heating (∆) cycle.
 Optical Properties of Ferroelectrics and Measurement Procedures 185
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1.9. Irradiation Effect on piezo-optic Birefringence in Li2Ge7O15 Crystals

The photoelastic coefficients Cpq of the ferroelectric crystals Li2Ge7O15 (x-irradiated) in a cool‐
ing and heating cycle between 298 K and 273 K was carried out with the experimental proce‐
dure described in section 1.5 and are shown in Fig. 20 [54]. The results show an interesting
photoelastic behaviour.

Peaks are observed in the temperature dependence of the photoelastic coefficients Czy and Czx
at temperature ~ 279 K in a complete cooling and heating cycle whereas no discernible hystere‐
sis is observed in rest of the photoelastic coefficients. Anomalous temperature dependence of
Czx of the crystal (x-irradiated) LGO at different wave lengths are shown in Fig.21.

It is observed that the peak value of Czy has increased about 25% and that of Czx has de‐
creased about 18% at the wave length λ=5890 Å during cooling process of the crystal (Fig.15
and Fig.20). The peak value of Czx of the crystal (un-irradiated and x-irradiated) LGO thus
obtained at different wave lengths (Fig.16 and Fig.21) are given in Table 7 and the results are
plotted in Fig.22.

Figure 21. Temperature dependence of photoelastic coefficient Czx of the crystal (x-irradiated) LGO at different wave
lengths in a cooling (0) and heating (∆) cycle.

It has been observed that the changes in the value of photoelastic coefficients Czy and Czx of
the crystal (x-irradiated) LGO in a cooling and heating cycle occur only if the crystal is
stressed along the polar axis (z-axis). It is known that the irradiation of crystals can change
physical properties of the crystals.
186 Advances in Ferroelectrics

Wave lengths Czx (un-irradiated) Czx (x-irradiated)

(Å) Cooling Heating Cooling Heating

4880 4.8 4.0 4.05 3.3

5390 4.7 3.9 3.95 3.2

5890 5.6 4.8 4.6 3.7

6140 4.5 3.6 4.3 3.4

Table 7. The peak value of Czx (in Brewster) for the Crystal (un-irradiated and x-irradiated) LGO at different wave
lengths in the cooling and heating cycles.

Figure 22. The peak value of Czx for the un-irradiated (black colour) and x-irradiated (ash colour) crystal LGO at differ‐
ent wave lengths in a cooling (0) and heating (∆) cycle.

Irradiation brings about many effects in the crystal such as creating defects, internal stress
and electric fields etc [43]. In our present studies, the x-irradiation is believed to produce in‐
ternal stress and electric fields inside the crystals Li2Ge7O15 due to defects that can change
the values of photoelastic coefficients.

2. Summary

It is known that the Barium strontium titanate Ba1-xSrxTiO3(BST) is one of the most interest‐
ing thin film ferroelectric materials due to its high dielectric constant, composition depend‐
ent curie temperature and high optical nonlinearity. The wavelength dependence of
refractive index of BST (Ba0.05Sr0.95TiO3) thin films has shown a nonlinear dependence in the
1450-1580 nm wavelength range at room temperature as described in section 1.1. The disper‐
sion curve decreases gradually with increasing wavelength. The average value of the refrac‐
 Optical Properties of Ferroelectrics and Measurement Procedures 187
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tive index is found to be 1.985 in the 1450-1580 nm wavelength range which is considered to
be important for optoelectronic device applications.

The study of fluorescence spectra of the crystals Li2Ge7O15:Cr3+ in the temperature interval
77-320 K shows the sharply decrease of intensities of the R1 and R2 lines (corresponding to
the Cr3+ ions of types I and II) during cooling process near the temperature Tc = 283.5 K as
described in section 1.3. Such nature of suppression of R1 and R2 lines was not observed pre‐
viously and it may be related with the mechanism of interaction of excitation spectra of light
in the crystals Li2Ge7O15:Cr3+ at the temperature Tc. The doping of chromium in LGO is be‐
lieved to create Cr3+- Li+ defect pairs in the host LGO lattice at Ge4+ sites creating dipoles in
two conjugate directions. The EPR, optical, dielectric and fluorescence studies conform each
other and pose more scope for further studies.

The high optical quality, good mechanical strength and stability in ambient environment
and large photoelastic coefficients in comparison with other ferroelectric crystals like Ro‐
chelle-salt, KDP and ADP favour the crystals LGO as a potential candidate for photoelastic
applications. The piezo-optic dispersion of the crystals (un-irradiated and x-irradiated) LGO
in the visible region of the spectrum of light at room temperature (298 K) have been descri‐
bed in sections 1.6 and 1.7. It shows an “optical zone or optical window” in between the
wavelengths 5400 Å and 6200 Å with an enhanced piezo-optical behavior. This peculiar op‐
tical window can have a technical importance for example this window region can act as an
optical switch for acousto-optical devices. From the studies undertaken it may be concluded
that LGO is an attractive acousto-optic material which deserves further probe. It may be
possible to understand the observed behavior if extensive piezo-optic and refractive index
data become available over an extended range of wavelengths.

The temperature dependence of the photoelastic coefficients of the crystals (un-irradiated

and x-irradiated) LGO in a cooling and heating cycle between room temperature (298 K) and
273 K have shown an interesting observations: lowering of the Tc under uniaxial stress con‐
trary to the increase of Tc under hydrostatic pressure and observation of thermal photoelas‐
tic hysteresis similar to dielectric hysteresis behavior as described in sections 1.8 and 1.9. In
our studies, the x-irradiation is believed to produce internal stress and electric fields inside
the crystals LGO due to defects that can change the values of photoelastic coefficients, as de‐
scribed in sections 1.7 and 1.9.

Author details

A.K. Bain* and Prem Chand

Department of Physics Indian Institute of Technology Kanpur, Kanpur-208016, INDIA

188 Advances in Ferroelectrics

References

[1] Lepingard, F. A., Kingston, J. J., & Fork, D. K. (1996). Second harmonic generation in
LiTaO3 thin films by modal dispersion and quasi phase matching. Appl. Phys. Lett.,
68, 3695-3697.

[2] Hewing, G. H., & Jain, K. (1983). Frequency doubling in a LiNbO3 thin film deposited
on sapphire. J. Appl. Phys., 54, 57-61.

[3] Lee, S. H., Kim, D. W., Noh, T. W., Lee, J. H., Lim, M. J., & Lee, S. D. (1996). Non-
linear optical properties of epitaxial LiNbO3 film prepared by pulsed laser deposi‐
tion. J. Korean Phys. Soc., 29, S628-S631.

[4] Moon, S. E., Back, S. B., Kwun, S. I., Lee, Y. S., Noh, T. W., Song, T. K., & Yoon, J. G.
(2000). Orientational Dependence of Electro-optic Properties of SrBi2Ta2O9 Ferroelec‐
tric Thin Films. Jpn. J. Appl. Phys., 39, 5916-5917.

[5] Reitze, D. H., Haton, E., Ramesh, R., Etemad, S., Leaird, D. E., & Sands, T. (1993).
Electrical and Electro-optic Properties of Single Crystalline, Epitaxial Thin Films
Grown on Silicon Substrates. Appl. Phys. Lett., 63(5), 596-598.

[6] ORNL’s. Thin film Waveguide and the Information Highway by Carolyn Krause.

[7] Varadam, V. K., Varadam, V. V., Selmi, F., Ounaise, Z., & Jose, K. A. (1994). Multilay‐
er Tunable Ferroelectrci Materiasl and Thin Films. SPIE-Int. Soc. Opt. Eng., 2189,
433-447.

[8] Mohammed, M. S., Naik, R., Mantese, J. V., Schubring, N. W., Micheli, A. L., & Cata‐
lan, A. B. (1996). Microstructure and ferroelectric properties of fine-grained
BaxSr1−xTiO3 thin films prepared by metalorganic decomposition. J. Mater. Res., 11,
2588-2593.

[9] Bain, A. K., Jackson, T. J., Koutsonas, Y., Cryan, M., Yu, S., Hill, M., Varrazza, R., Ror‐
ison, J., & Lancaster, M. J. (2007). Optical Properties of Barium Strontium Titanate
(BST) Ferroelectric Thin Films. Ferroelectric Letters, 34, 149-154.

[10] Wada, M., Swada, A., & Ishibashi, Y. (1981). Ferroelectricity and Soft Mode in
Li2Ge7O15 . J. Phys. Soc. Jpn., 50(6), 1811-1812.

[11] Wada, M., & Ishibashi, Y. (1983). Ferroelectric Phase Transition in Li2Ge7O15 . J.Phys.
Soc. Jpn ., 52(1), 193-199.

[12] Preu, P., & Hauss Ühl , S. (1982). Dielectric Properties and Phase Transition in
Li2Ge7O15. Solid State Commun, 41(8), 627-630.

[13] Kaminsky, W., & Hauss, Ühl. S. (1990). Faraday effect aid birefringence in ortho‐
rhombic Li2Ge7O15 near the ferroelectric phase transition. Ferroelectrics Lett., 11(3),
63-67.
 Optical Properties of Ferroelectrics and Measurement Procedures 189
http://dx.doi.org/10.5772/52098

[14] Hauss, Ühl. S., Wallrafen, F., Recker, K., & Eckstein, J. (1980). Growth, Elastic Proper‐
ties and Phase Transition of Orthorombic Li2Ge7O15. Z.krist., 153, 329-337.
[15] Kudzin, A., Yu, Volnyanskii M. D., & Bain, A. K. (1994). Temperature Hysteresis of
the Permittivity of Li2Ge7O15 . Phys. Solid State, 36(2), 228-230.
[16] Kudzin, A., Yu, Volnyanskii M. D., & Bain, A. K. (1995). Influence of Space Charges
on Ferroelectric Property of Weak Ferroelectric Li2Ge7O15 . Ferroelectrics, 164(1),
319-322.
[17] Bain, A.K. (1994). Study of Pecularities of Ferroelectric Phase Transition of the Crys‐
tals Li2Ge7O15 (Ph.D. Thesis). Dniepropetrovsk State University, Ukraine, 128.
[18] Bain, A. K., Chand, P., Rao, K. V., Yamaguchi, T., & Wada, M. (2008). Irradiation Ef‐
fect on Piezo-optic Dispersion of Li2Ge7O15 Crystals. Ferroelectrics, 377(1), 86-91.
[19] Bain, A. K., Chand, P., Rao, K. V., Yamaguchi, T., & Wada, M. (2009). Anomalous
Temperature Dependence of Piezo-optic Birefrigence in Li2Ge7O15 Crystals. Ferroelec‐
trics, 386(1), 152-160.
[20] O’Mahony, M.J. (1988). Semiconductor laser optical amplifers for use in future fiber
systems. J. Light wave Technology, 6(4), 531-544.
[21] Miranda, F. A., Vankeuls, F. W., Romanofsky, R. R., Mueller, C. H., Alterovitz, S., &
Subramanyam, G. (2002). Ferroelectric thin-film based technology for frequency and
phase agile microwave communication applications. Integrated Ferroelectrics, 42,
131-149.
[22] Tian, H. Y., Luo, W. G., Pu, X. H., Qiu, P. S., He, X. Y., & Ding, A. L. (2001). Synthesis
and characteristics of strontium-barium titanate graded thin films at low temperature
using a sol-gel technique. Solid State Communications, 117, 315-319.
[23] Pontes, F. M., Leite, E. R., Pontes, D. S. L., Longo, E., Santos, E. M. S., Mergulhao, S.,
Pizani, P. S., Lanciotti Jr, F., Boschi, T. M., & Varela, J. A. (2002). Ferroelectric and op‐
tical properties of Ba0.8Sr0.2TiO3 thin film. J. Appl. Phys., 91(9), 5972-5978.
[24] Deineka, A., Jastrabik, L., Suchaneck, G., & Gerlach, G. (2002). Optical Properties of
Self-Polarized PZT Ferroelectric Films. Ferroelectrics, 273, 155-160.
[25] Gu, Y. Z., Gu, D. H., & Gan, F. X. (2001). Optical Nonlinearity in PbTiO3 Thin Film
Deposited on Al2O3 with RF-Sputtering System. Nonlinear Optics, 28(4), 283-289.
[26] Fernandez, F. E., Gonzalez, Y., Liu, H., Martinez, A., Rodriguez, V., & Jia, W. (2002).
Structure, morphology, and properties of strontium barium niobate thin films grown
by pulsed laser deposition. Integrated Ferroelectrics, 42, 219-233.
[27] Wohlecke, M., Marrello, V., & Onton, A. (1977). Refractive index of BaTiO3 and
SrTiO3 films. J. Appl. Phys., 48, 1748-1750.
[28] Wada, M., Swada, A., & Ishibashi, Y. (1984). The Oscillator Strength of the Soft Mode
in Li2Ge7O15 . J. Phys. Soc. Jpn., 53(10), 3319-3320.
190 Advances in Ferroelectrics

[29] Iwata, Y., Shibuya, I., Wada, M., Sawada, A., & Ishibashi, Y. (1987). Neutron Diffrac‐
tion study of structural Phase Transition in Ferroelectric Li2Ge7O15 . J. Phys. Soc. Jpn.,
56(7), 2420-2427.
[30] Wada, M. (1988). Soft Mode Spectroscopy Study of Ferroelectric Phase Transition in
Li2Ge7O15 . Ind. J. Pure and Appl. Phys., 26, 68-71.
[31] Galeev, A. A., Hasanova, N. M., Bykov, A. B., Vinokurov, B. M., Nizamutdinov, N.
M., & Bulka, G. R. (1990). EPR of Cr3+ and Fe3+ in Li2Ge7O15 single crystal. In: Spectro‐
scopy, a crystal chemistry and a realstructure of minerals and their analogues. Kazan’
state university, 77-87, in Russian).
[32] Basun, S. A., Kaplyanski, A. A., & Feofilov, S. P. (1994). Dipolar centres in Li2Ge7O15
crystal activated with (3d3) ions: a microstructure and spectroscopic effects of an in‐
ternal and external electric field. Solid State Phys., 36(11), 3429-3449.
[33] Kaplyanski, A. A., Basun, S. A., & Feofilov, S. P. (1995). Ferroelectric transition in‐
duced dipole moments in probe ions in Li2Ge7O15 crystals doped with Mn4+ and Cr3+ .
Ferroelectrics, 169, 245-248.
[34] Iwata, Y., Koizumi, H., Koyano, N., Shibuya, I., & Niizeki, N. (1973). Crystal struc‐
ture determination of ferroelectric phase of 5PbO3GeO2 . J. Phys. Soc. Jap., 35(1),
314-315.
[35] Volnianskii, M. D., Trubitsyn, M. P., & Obaidat, Yahia A. H. (2007). EPR and dielec‐
tric spectroscopy of reorienting Cr3+- Li+ pair centres in Li2Ge7O15 Crystal. Condensed
Matter Physics, 10(49), 75-78.
[36] Trubitsyn, M. P., Volnianskii, M. D., & Busoul, I. A. (1998). EPR study of the ferro‐
electric phase transition in Li2Ge7O15:Cr3+ crystal. Solid State Phys., 40, 6, 1102-1105.
[37] Powell, R.C. (1968). Temperature Dependence of the Widths and Positions of the R
Lines in Li2Ge7O15:Cr3+ . J. Appl. Phys., 39, 4517-4521.
[38] Powell, R.C. (1968). Energy Transfer between Chromium Ions in Nonequivalent Sites
in Li2Ge7O15. Phys. Rev., 173, 358-366.
[39] Narsimhamurty, T.S. (1981). Photoelastic and Electro-optic properties of Crystals.
New York: Plenum Press., 514.
[40] Bain, A. K., Chand, P., Rao, K. V., Yamaguchi, T., & Wada, M. (2008). Piezo-optic Dis‐
persion of Li2Ge7O15 Crystals. Ferroelectrics, 366(1), 16-21.
[41] Saito, K., Ashahi, T., Takahashi, N., Hignao, M., Kamiya, I., Sato, Y., Okubo, K., &
Kobayashi, J. (1994). Optical activity of Gd2(MoO4)3. Ferroelectrics, 152(1), 231-236.
[42] Vanishri, S., & Bhat, H. L. (2005). Irradiation Effects on Ferroelectric Glycine Phos‐
phite Single Crystal. Ferroelectrics, 323(1), 151-156.
[43] Lines, M. E., & Glass, A. M. (2004). Principles and Applications of Ferroelectrics and
Related Materials. Oxford: Clarendon press, 680.
 Optical Properties of Ferroelectrics and Measurement Procedures 191
http://dx.doi.org/10.5772/52098

[44] Bain, A. K., Chand, P., Rao, K. V., Yamaguchi, T., & Wada, M. (1998). Determination
of the Photoelastic Coefficients in Lithium heptagermanate Crystals. Ferroelectrics,
209(1), 553-559.

[45] Hauss, Ühl. S., & Albers, J. (1977). Elastic and thermoelastic constants of triglycine
sulphate (TGS) in the paraelectric phase. Ferroelectrics, 15(1), 73-75.

[46] Wada, M., Orihara, H., Midorikawa, M., Swada, A., & Ishibashi, Y. (1981). Pressure
Effect on the Ferroelectric Phase Transition in Li2Ge7O15. J. Phys. Soc. Jpn., 50(9),
2785-2786.

[47] Morioka, Y., Wada, M., & Swada, A. (1988). Hyper-Raman Study of Ferroelectric
Phase Transition of Li2Ge7O15 . J. Phys. Soc. Jpn., 57(9), 3198-3203.

[48] Wada, M., Shirawachi, K., & Nishizawa, S. (1991). A Fourier Transform Infrared
Spectrometer with a Composite Interferometer for Soft Mode Studies. Jpn. J. Appl.
Phys., 30(5), 1122-1126.

[49] Sinii, I. G., Fedoseev, A. I., & Volnyanskii, M. D. (1990). Relaxation- and fluctuation-
induced damping of hypersound in the presence of dispersion. Sov. Phys. Solid State,
32(10), 1817-1818.

[50] Narasimamurty, T. S. (1969). Piezooptical constants of Rochelle salt crystals. Phys.

Rev., 186, 945-948.

[51] Veerabhadra, Rao K., & Narasimamurty, T. S. (1975). Photoelastic behavior of KDP. J.
Mat. Sci., 10(6), 1019-1021.

[52] Narasimamurty, T. S., Veerabhadra, Rao. K., & Petterson, H. E. (1973). Photoelastic
constants of ADP. J. Mat. Sci., 8(4), 577-580.

[53] Trubitsyn, M. P., Kudzin, A., Yu, Volnyanski. M. D., & Bain, A. K. (1992). Critical
Broadening of EPR lines near the Ferroelectric Phase Transition in Li2Ge7O15:Mn2+ .
Sov. Phys. Solid State , 34(6), 929-932.

[54] Bain, A. K., & Chand, P. (2011). Irradiation Effect on Photoelastic Coefficients in Fer‐
roelectric Li2Ge7O15 Crystals. Integrated Ferroelectrics, 124, 10-18.
 Chapter 9

Ferroelectric Domain Imaging Multiferroic Films

Using Piezoresponse Force Microscopy

Hongyang Zhao, Hideo Kimura, Qiwen Yao,

Lei Guo, Zhenxiang Cheng and Xiaolin Wang

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52519

1. Introduction

Recently, multiferroic materials with the magnetoelectric coupling of ferroelectric (or anti‐
ferroelectric) properties and ferromagnetic (or antiferromagnetic) properties have attracted a
lot of attention.[1-4] Among them, BiFeO3(BFO) and YMnO3has been intensively studied.
For such ABO3perovskite structured ferroelectric materials, they usually show antiferromag‐
netic order because the same B site magnetic element except BiMnO3 is ferromagnet. While
for the A2BB’O6 double perovskite oxides, the combination between B and B’ give rise to a
ferromagnetic coupling. They are also expected to be multiferroic materials. Several bis‐
muth-based double perovskite oxides (BiBB’O6) have aroused great interest like Bi2NiMnO6,
La2NiMnO6, BiFeO3-BiCrO3. But as we know, few researches are focused on Bi2FeMnO6. We
believe it is particular interesting to investigate Bi2FeMnO6 (BFM). The origin of the ferro‐
magnetism in these compounds has been discussed in many reports. According to Goode‐
nough-Kanamori’s (GK)rules, many ferromagnets have been designed through the coupling
of two B site ions with and without eg electrons.In BFM, the 180 degree -Fe3+-O-Mn3+- bonds
is quasistatic, partly because the strong Jahn-Teller uniaxial strain in an octahedral site.Be‐
cause the complication of the double perovskite system, there are still some questions about
the violation of GK rules in some cases and the origin of the ferromagnetism or antiferro‐
magnetism.The other problem is the bad ferroelectric properties. In order to characterization
of their ferroelectric/piezoelectric properties, scanning probe microscopy (SPM) techniques
were used.
Multiferroic materials can be classified into two categories: one is single-phase materials; the
other is multilayer or composite hetero-structures that contain more than one ferroic phases
[5]. The most desirable multiferroic material is the intrinsic single-phase material, which is

© 2012 Zhao et al.; licensee InTech. This is an open access article distributed under the terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
194 Advances in Ferroelectrics

still rarely produced although significant advancements had been made recently. Therefore,
it is essential to broaden the searching field for new candidates of multiferroics. This work
focuses on both typesmultiferroic materials: Single-phase Bi2FeMnO6 and multilayered YM‐
nO3/SnTiO3. Scanning probe microscopy (SPM) techniques were used for ferroelectric do‐
main imaging of these multiferroic materials.

As we know, most piezoelectric/ferroelectric materials with good performances are based on

the perovskite-type oxides of ABO3, among them, the most extensively studied ones should
be PbTiO3 and Pb(ZrTi)O3 based materials due to their high dielectric constants and good
piezoelectric/ferroelectric properties. However, these materials containing lead which leads
to environmental problems. Thus, it is desirable to develop new lead-free piezoelectric mate‐
rials to replace PZT based piezoelectrics for environmental protection. Through first princi‐
ple calculations, SnTiO3 containing Sn2+ ions was estimated to have excellent ferroelectric
properties [6, 7]. The calculated results indicated that the spontaneous polarization and pie‐
zoelectric coefficients of SnTiO3 is comparable with those of PbTiO3. Moreover, the most sta‐
ble structure is tetragonal perovskite with a=b=3.80Å and c=4.09Å [6, 7]. The metastable
SnTiO3 phase is very difficult to obtain, a good way to stabilize the SnTiO3 phase is to mix it
with other compounds. Several studies have been focused on the synthesis of Sn-doped ce‐
ramics in BaTiO3 system, such as (Ba0.6Sr0.4)(Ti1-xSnx)O3 [8], (Ba1-x-yCaxSny)TiO3 [9]. However,
it is difficult to obtain Sn2+ by traditional bulk synthesis techniques. On the other hand, it is
easier to fabricate SnTiO3 using pulsed laser deposition method (PLD). Our interest was to
find out whether the SnTiO3 phase can be stabilized through the layer-by-layer deposition
using PLD, and whether it is possible to obtain such metastable materials in non-equilibri‐
um conditions.

The hexagonal manganite YMnO3, which shows an antiferromagnetic transition at TN = 75 K,

and a ferroelectric transition TC = 913 K, is one of the rare existing multiferroics [10-12]. It
was chosen as the basic composition to sandwich SnTiO 3+x phase and to form YST multilayer
film. In this work, we reported the effect of substrate orientation and layer numbers of YM‐
nO3 and SnTiO3+x on the piezoelectric/ferroelectric and magnetic properties in the designed
layered YST system. It was hoped that our method would serve as a model system to intro‐
duce the use of PLD techniques in the growth of multilayer multiferroic materials and meta‐
stable materials. Such techniques could be promising for device design and the searching in
fabricating new materials.

2. SPM system

SPM has emerged as a powerful tool for high-resolution characterization of ferroelectrics

for the first time providing an opportunity for non-destructive visualization of ferroelec‐
tric domain structures at the nanoscale. [13]These nanostructures can be used for studying
the intrinsic size effects in ferroelectrics as well as for addressing such technologically im‐
portant issues as processing damage, interfacial strain, grain size, aspect ratio effect, edge
effect, domain pinning and imprint. [14] The system composes of a conducting tip in con‐
 Ferroelectric Domain Imaging Multiferroic Films Using Piezoresponse Force Microscopy 195
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tact with the dielectric surface on a conductive substrate can be considered as a capacitor.
SPM is a well-established field offering multiple opportunities for new discoveries and
breakthroughs. [15-17]

Piezoelectric materials provide an additional response to the applied ac electric field due to
the converse piezoelectric effect: ∆l=d33V, whereΔl is the displacement, d33 is the effective
longitudinal piezoelectric coefficient. [18, 19] If follows that both electrostatic and piezoelec‐
tric signals are linear with the applied voltage and thus contribute to the measured PFM re‐
sponse. These measurements are referred to as out-of-plane (OP) measurement.
Measurements of local hysteresis loops are of great importance in inhomogeneous or poly‐
crystalline ferroelectrics because they are able to quantify polarization switching on a scale
significantly smaller than the grain size or inhomogeneity variation. Macroscopically, the
switching occurs via the nucleation and growth of a large number of reverse domains in the
situation where the applied electric field is uniform. Therefore, the d33 hysteresis reflects the
switching averaged over the entire sample under the electrode. [20, 21] In the PFM experi‐
mental conditions, the electric field is strongly localized and inhomogeneous; therefore, the
polarization switching starts with the nucleation of a single domain just under the tip.

3. Material designation and characterization

Multiferroic materials have been attracting considerable attention especially in the last ten
years. [22-25] One of the most appealing aspects of multiferroics is their magnetoelectric
coupling. Among them, the most studied is the provskite BiFeO3(BFO) with room tempera‐
ture multiferroic properties and YMnO3. Based on BFO and YMnO3, we designed new mul‐
tiferroics and fabricated the films using pulsed laser deposition (PLD) method. The material
system includes double perovskitemultiferroic Bi2FeMnO6 (BFM) and multilayered YMnO3/
SnTiO3+x (YST). Compared to BFO, the magnetic properties of BFM and YST were greatly
improved. However, until now there is no report about their ferroelectric properties because
the difficulty of obtaining well-shaped polarization hysteresis loops. It is important to study
ferroelectric properties because the possible coupling between ferroelectric and antiferro‐
magnetic domains and its lead-free nature. As is well known, the ferroelectric property is
mainly determined by the domain structures and domain wall motions. The most exciting
recent developments in the field of multiferroics and the most promise for future discoveries
are in interfacial phenomena. [26] The interfaces include those that emerge spontaneously
and those that are artificially engineered. Therefore, the domain structure and polarization
switching were studied in these three new multiferroic films using piezoresponse force mi‐
croscopy (PFM).

The emerging technique of PFM is proved to be a powerful tool to study piezoelectric and
ferroelectric materials in such cases and extensive contributions have been published In
PFM, the tip contacts with the sample surface and the deformation (expansion or contrac‐
tion of the sample) is detected as a tip deflection. The local piezoresponse hysteresis loop
and information on local ferroelectric behavior can be obtained because the strong coupling
196 Advances in Ferroelectrics

between polarization and electromechanical response in ferroelectric materials. In the

present study, we attempts to use PFM to study the ferroelectric/piezoelectric properties in
films of BFM and YST. PFM response was measured with a conducting tip (Rh-coated Si
cantilever, k~1.6 N m-1) by an SII Nanotechnology E-sweep AFM. PFM responses were
measured as a function of applied DC bias (Vdc) with a small ac voltage applied to the bot‐
tom electrode (substrate) in the contact mode, and the resulting piezoelectric deformations
transmitted to the cantilever were detected from the global deflection signal using a lock-in
amplifier.

3.1. Characterization of BFM film

Magnetism and ferroelectricity exclude each other in single phase multiferroics. It is difficult
for designing multiferroics with good magnetic and ferroelectric properties. Our interest is
to design new candidate multiferroics based on BiFeO3. BiFeO 3 is a well-known multiferroic
material with antiferromagntic Neel temperature of 643K, which can be synthesized in a
moderate condition. [22, 23, 25] In contrast, BiMnO3 is ferromagnetic with Tc = 110K and it
needs high-pressure synthesis. [27, 28] The possible magnetoelectric coupling has motivated
a lot of studies on the ferroelectric and antiferromagnetic domains. The ferroelectric domain
structures of BFO in the form of ceramics, single crystals and thin films have been intensive‐
ly studied using PFM, TEM and other techniques.

Single phase BFM ceramics could be synthesized by conventional solid state method as the
target. For BFM ceramics, the starting materials of Bi2O3, Fe3O4, MnCO3 were weighed ac‐
cording to the molecular mole ratio with 10 mol% extra Bi2O3. They were mixed, pressed in‐
to pellets and sintered at 800 °C for 3 h. Then the ceramics were crushed, ground, pressed
into pellets and sintered again at 880 °C for 1 h. BFM films were deposited on SrTiO3(STO)
substrate by pulsed laser deposition (PLD) method at 650°C with 500 ~ 600mTorr dynamic
oxygen. [29, 30]

The structure of BFM was calculated [31] and it is connected with the magnetic configura‐
tions as shown in Figure 1. It has three possible space groups of Pm3m, R3 and C2 and the
magnetic configurations were presumedfor each structure symmetry to be G-type antiferro‐
magnetic (G-AFM) and ferromagnetic (FM) structures. The most stable structure of BFM is
monoclinic with C2 space group. Mn tends to show 3+ valence which will induce a large dis‐
tortion because it is Jahn-Teller ion. The valence of Mn and Fe has been studied in the for‐
mer work. [30, 32]

Figure 2 shows the results of the PFM images of BFM film. Several features could be ob‐
served: firstly, the obvious contrast could be seen and the grains in PFM and topography are
correspondence; secondly, the existence of contrasts on both OP and IP indicates multiple
orientations of domains; thirdly, the IP contrast is not so clear as OP contrast, that is to say,
the suppression of the in-plane response for heterostructures suggesting a constrained ferro‐
electric domain-orientation along the OP direction. In the former paper, the ferroelectric do‐
main switching and typical butterfly loops were observed. [32]
 Ferroelectric Domain Imaging Multiferroic Films Using Piezoresponse Force Microscopy 197
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Figure 1. Calculated six structures of BFM.

The domains in BFO films have been analyzed in detail in Ref [19]: the bigger spontaneous
ferroelectric domains were observed in BFO than in other ferroelectrics without multiferroic
properties; the domains were irregular but the the model was predicted and consistent with
the experimental results. According to the present results of BFM, further study is needed to
obtain the domain morphology and do the calculation.
198 Advances in Ferroelectrics

Figure 2. PFM images of BFM film

 Ferroelectric Domain Imaging Multiferroic Films Using Piezoresponse Force Microscopy 199
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3.2. Characterization of YST film

Polycrystalline YMnO3 and TiO2 ceramics were synthesized by conventional solid state
method as the targets. On addition the SnO and SnO2 commercial targets were also used at
the same time in our process. The deposition of these films includes the following major
steps. YST films were deposited on (100) and (110) Nb: SrTiO3 (STO) substrate using a
pulsed laser deposition (PLD) system at 700°C with 10-1 ~10-5Torr dynamic oxygen. The tar‐
gets were alternately switched constantly and the films were obtained in a layer-by-layer
growth mode. After deposition, the films were annealed in the same condition for 15 mi‐
nutes at 700°C and then cooled to room temperature. [33]

In YST multilayered films, one layer is defined to be comprised of two sub-layers: (1) YM‐
nO3 and (2) SnTiO3+x. The films deposited on (100), (111) and (110) STO are expressed as
YST100, YST111 and YST110, respectively. The film YST110-4 denotes the films deposited on
(110) STO with four layers, as shown clearly in Figure 3. The total deposition time for YM‐
nO3 and SnTiO3+x is the same of 40 and 20 minutes, respectively.

XRD patterns for the five films of YST100-2, YST100-4 were shown in Figure 4. The peaks
were identified using the XRD results of SnTiO3 (◎), YMnO3 (Y) (shown in Figure 9, FeTiO3
(▽) [34, 35]. SnTiO3 is metastable and it showed two combined phases, one is FeTiO3, and
the other is the good ferroelectric phase which has tetragonal structure. XRD patterns of
SnTiO3 (◎) were shown in Figure 5 in supplementary materials, which is obtained using the
calculated data[6, 7]. The symbol of “?” represents the phase which we cannot identify so
far, it could be a peak from the (111) TiO2 phase.

Figure 3. Schematic explanation of films with two, four and eight layers, each layer contains two sublayers of YMnO3
and SnTiO3.
200 Advances in Ferroelectrics

Figure 4. XRD patterns for the five films of YST100-2, YST100-4. [31]

Figure 5. XRD patterns of calculated SnTiO3 and YMnO3 targets. [33]

 Ferroelectric Domain Imaging Multiferroic Films Using Piezoresponse Force Microscopy 201
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Many reports about the YMnO3 films can be found but most of them without ferroelectric
characterization provided. This is mainly ascribed to the difficulty in obtaining a satisfactory
ferroelectric measurement result. Figure 6 shows the electrical polarization hysteresis loops
(P-E loops) of YST110-4 film. The ferroelectric type hysteresis loop was observed. It is obvious
that the P-E loop is significantly different for different layer-number films, as well as for differ‐
ent substrate orientations. For the same STO orientation, the P-E loops were improved as the
layer number increase, and the film fabricated on (110) STO shows improved properties com‐
pared to the film on (100) STO with the same layer number. As for the same deposition time for
the four samples, it is found that more layers of SnTiO3 in the YST system shows much better
ferroelectric properties. It is suggested that the SnTiO3 phase can exist only in ultra-thin thick‐
ness and can be stabilized by YMnO3 sub-layers. That is to say, SnTiO3 is indeed a ferroelectric
materials but it is a great challenge [36] to obtain stable single phase SnTiO3 films that is with
good ferroelectric performance (it will be tried in our future works). Although the electric
charge in the interface may affect its ferroelectric properties, the improved properties of
YST110-4 proved that its effect was not significant. While the P-E loops were not improved in
YST111-4, all the observations showed the anisotropy of the films.

Figure 6. Ferroelectric polarization loop of YST films. [31]

Although well developed P-E loops were observed for YST100-8 and YST110-4, the loops
still show the rounded features, indicating that contributions to the hysteresis loop from
movable charges was significant. In addition, the P-E loops of the four films have revealed
that the polarization is rather small (just a few μC/cm2) and they do not exhibit saturation.
The fatigue properties were shown in Figure 7 for YST110-4. The polarization measurement
was at 21V, the switching voltage was 14V and the frequency was 5k Hz. The remnant po‐
larization decreased about 40% after 107 read/write cycles for YST110-4. From all the com‐
parisons, YST110-4 sample shows the comparable ferroelectric properties with YST100-8.
202 Advances in Ferroelectrics

Figure 7. Fatigue measurement of YST110-4 film. [31]

Figure 8 shows TEM results of the YST110-4 film. It clearly shows four layers and one layer
which is close to the substrate seems have some reaction with the substrate. The other three
layers are homogeneous and we could see the domain structures through this image. The
surface of the film was studied using AFM as shown in Figure 9. As expected, Figure 10
displays contrast over the polarized square after poled by positive and negative 10 V volt‐
age, due to the different phases of the PFM response for the up and down domains. The ob‐
vious change of the contrast in YST110-4 film confirms that the polarization reversal is
indeed possible and that the film is ferroelectric at room temperature.

Figure 8. TEM image of YST110-4 film.

 Ferroelectric Domain Imaging Multiferroic Films Using Piezoresponse Force Microscopy 203
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Figure 9. AFM topography image of YST110-4 film.

Figure 10. PFM image of YST110-4 film after poled using ± 10 V voltage
204 Advances in Ferroelectrics

As seen in Figure 11, when a direct current voltage up to 10 V was applied on the samples,
the sample exhibited ‘‘butterfly’’ loop. The loops were not symmetrical due to the asymme‐
try of the upper (tip) and bottom (substrate) electrodes. In addition, the substrate may also
affect the d33. According to the equation d33=Δl/V, where Δl is the displacement, the effective
d33 could be calculated. At the voltage of 10 V, both samples show the maximum effective
d33of about 6.21 pm/V for YST110-4 sample.

Figure 11. Butterfly and local piezoresponse hysteresis loops of YST110-4 film.

4. Conclusions

The novel multiferroic films of BFM and multilayered YST were successfully produced us‐
ing PLD method. Both of them were characterized using PFM method. The special or excel‐
lent properties can often be found in the metastable materials. Through calculation, s4ix
structures are presumed in BFM with two magnetic configurations of G-AFM and FM. In
YST films, the metastable SnTiO3 phase was obtained. The improved ferroelectric properties
were observed through increasing the layer numbers and more SnTiO3 phase was stabilized,
moreover, the change in contrast after bias is applied indicates a change in polarization di‐
rection and hence ferroelectric switching. Although it is a great challenge in obtaining the
SnTiO3 thin films, we believe that through the optimization of fabrication process and condi‐
tions, the single phase SnTiO3 or multilayer films, or composite materials containing SnTiO3
could become a new generation lead-free piezoelectric/ferroelectric material. For a thorough
understanding of the mechanisms of the films, knowledge of the domain structures is a pre‐
requisite, which is of crucial importance to increase and tune the functionality of multiferro‐
ic films.
 Ferroelectric Domain Imaging Multiferroic Films Using Piezoresponse Force Microscopy 205
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Acknowledgements

The authors gratefully acknowledge Dr. Minoru Osada, Dr. Kazuya Terabe in NIMS and
Prof. H. R. Zeng in Shanghai Institute of Ceramics for their experimental help and discus‐
sions. Part of this work was supported by JST ALCA and MEXT GRENE.

Author details

Hongyang Zhao1,2*, Hideo Kimura1, Qiwen Yao1, Lei Guo1, Zhenxiang Cheng3 and
Xiaolin Wang3

*Address all correspondence to: [email protected]

1 National Institute for Materials Science, Sengen 1-2-1, Tsukuba, Japan

2 Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai, China

3 Institute for Superconducting and Electronics Materials, University of Wollongong, Inno‐

vation Campus, Fairy Meadow, Australia

References

[1] Hill N. A., Why are there so few magnetic ferroelectrics? J. Phys. Chem. B 2000; 104:
6694.

[2] Fiebig M., T. Lottermoser, D. Frohlich, A. V. Goltsev, R. V. Pisarev, Observation of

cou-pled magnetic and electric domains.Nature 2002; 419: 818.

[3] Eerenstein W., Mathur N. D. and Scott J.F., Multiferroic and magnetoelectric materi‐
als. Nature 2006; 442: 759-765.

[4] Singh M. K., Prellier W., Singh M. P., Katiyar R. S., Scott J. F., Spin-glass transition in
single-crystal BiFeO3. Phys. Rev. B 2008; 77: 144403.

[5] J. Das, Y.Y. Song, M.Z. Wu, Electric-field control of ferromagnetic resonance in mon‐
olithic BaFe12O19–Ba0.5Sr0.5TiO3heterostructures. J. Appl. Phys. 2010; 108: 043911.

[6] Konishi Y., Ohasawa M., Yonezawa Y., Tanimura Y., Chikyow T., Wakisaka T., Koi‐
numa H., Miyamoto A., Kubo M., Sasata K., Mater. Res. Soc. Symp. Proc. 2003; 748
U3.13.1.

[7] Uratani Y., Shishidou T., Oguchi T., First-Principles Study of Lead-Free Piezoelectric
SnTiO3.Jpn. J. Appl. Phys. 2008; 47 (9), 7735-7739.
206 Advances in Ferroelectrics

[8] Ha J. Y., Lin L. W., Jeong D. Y., Yoon S. J., Choi J. W., Improved Figure of Merit of
(Ba,Sr)TiO3-Based Ceramics by Sn Substitution.Jpn. J. Appl. Phys. 2009; 48 011402.
[9] Suzuki S., Takeda T., Ando A., Takagi H., Ferroelectric phase transition in Sn2+ ions
doped (Ba,Ca)TiO3 ceramics.Appl. Phys. Lett. 2010; 96: 132903.
[10] Marin L.W., Crane S.P., Chu Y-H., Holcomb M.B., Gajek M., Huijben M., Yang C-H.,
Balke N., Ramesh R., Multiferroics and magnetoelectrics: thin films andnanostruc‐
tures.J. Phys.: Condens. Matter 2008; 20: 434220.
[11] Yakel H.L., Koehler W.C., Bertaut E.F., Forrat E.F., On the crystal structure of the
manganese(III) trioxides of the heavy lanthanides and yttrium. ActaCrystallogr.
1963; 16: 957-962.
[12] Bertaut E. F., Pauthenet R., Mercier M., Proprietesmagnetiqueset structures du man‐
ganite d'yttrium. Phys. Lett. 1963; 7: 110-111.
[13] Gruverman A, Kholkin A, Nanoscale Ferroelectrics: Processing, Characterization and
Future Trends. Rep. Prog. Phys. 2006; 69: 2443-2474.
[14] Catalan G., Noheda B, McAneney J, Sinnamon L J, Gregg J M Strain gradients in epi‐
taxial ferroelectrics. Phys. Rev. B 2005; 72: 0201102.
[15] Muralt P. J. Micromech. Ferroelectric thin films for micro-sensors and actuatorsMi‐
croeng. 2000;10: 136.
[16] Terabe K, Nakamura M, Takekawa S. Kitamura K, Higuchi S. Gotoh Y, Cho Y Micro‐
scale to nanoscale ferroelectric domain and surface engineering of a near-stoichio‐
metric LiNbO3 crystal. Appl. Phys. Lett. 2003; 82: 433-435.
[17] Fong D D, Stephenson G B, Streigger S K, Eastman J A, Auciello O, Fuoss P H,
Thompson C Ferroelectricity in ultrathin perovskite films Science. 2004; 304: 1650.
[18] Kholkin A L, Bdikin I K, Shvartsman V V, Orlova A, Kiselev D, Bogomolov V, MRS
Proc. E 2005; 838: O7.6.
[19] Catalan G., Bea H., Fusil S., Bibes M., Paruch P., Barthelemy A., Scott J. F., Fractal Di‐
mension and Size Scaling of Domains in Thin Films of Multiferroic BiFeO3. Phy. Rev.
Lett. 2008; 100 027602.
[20] Kalinin S V, Gruverman A and Bonnell D A Quantitative analysis of nanoscale
switching in SrBi2Ta2O9 thin films by piezoresponse force microscopy Appl. Phys.
Lett. 2004; 85: 795-797
[21] Tybell T, Paruch P, Giamarchi T, Triscone J-M Domain wall creep in epitaxial ferro‐
electric Pb(Zr0.2Ti0.8)O3 thin films 2002 Phys. Rev. Lett. 89 097601
[22] Catalan G., Scott J. F., Adv. Mater. Physics and Applications of Bismuth Ferrite.2009;
21, 2643.
[23] Wang J., Neaton B. J., Zheng H., Nagarajan V., Ogale S. B., Liu B., Viehland D., Vai‐
thyanathan V., Schlom D. G.,. Waghmare U. V, Spaldi N. A.n, Rabe K. M., Wutting
 Ferroelectric Domain Imaging Multiferroic Films Using Piezoresponse Force Microscopy 207
http://dx.doi.org/10.5772/52519

M., Ramesh R., Epitaxial BiFeO3 Multiferroic Thin Film Heterostructures. Science
2003; 299: 1719-1722.

[24] Kimura T., Goto T., Shintani H., Ishizaka K., Arima T., Tokura Y., Magnetic Control
of Ferroelectric Polarization. Nature 2003; 55: 426.

[25] Cheng Z. X., Wang X. L., Dou S. X., Ozawa K., Kimura H., Improved ferroelectric
properties in multiferroic BiFeO3 thin films through La and Nbcodoping. Phys. Rev.
B 2008; 77: 092101.

[26] Spaldin N. A., Cheong S. W., Ramesh R.,Multiferroics: Past,present, and future.
Physics Today 2010; 63: 38-43.

[27] T. Atou, H. Chiba, K. Ohoyama, Y. Yamaguchi, Y. Syono, Structure determination of

ferromagnetic perovskite BiMnO3. J. Solid State Chem. 1999: 145(2) 639-642.

[28] T. Kimura, S. Kawamoto, I. Yamada, M. Azuma, M. Takano, Y. Tokura, Magnetoca‐

pacitance effect in multiferroic BiMnO3, Phys. Rev. B 2003: 67 (R), 180401-180404.

[29] Zhao, H.Y.; Kimura, H.; Cheng, Z.X.; Wang, X.L. &Nishida, T. Room temperature
multiferroic properties of Nd:BiFeO3/Bi2FeMnO6 bilayered films.Appl. Phys. Lett.
2009; 95(23)232904

[30] Zhao, H.Y.; Kimura, H.; Cheng, Z.X.; Wang, X.L.; Ozawa, K. &Nishida, T. Magnetic
characterization of Bi2FeMnO6 film grown on (100) SrTiO3 substrate Phys. Status Sol‐
idi RRL 2010; 4(11) 314.

[31] Bi, L.; Taussig, A.R.; Kim, H-S.; Wang, L.; Dionne, G.F.; Bono, D.; Persson, K.; Ceder,
G.&Ross, C.A. Structural, magnetic, and optical properties of BiFeO3 and Bi2FeMnO6
epitaxial thin films: An experimental and first-principles study. Phys. Rev. B 2008; 78
(10) 104106.

[32] ZhaoH Y, Kimura H.; Cheng Z.X.; Wang X.L., New multiferroic materials: Bi2FeM‐
nO6. Ferroelectrics-Material Aspects. InTech; 2011.

[33] Zhao H Y, Kimura H.; Cheng Z.X.; Wang X.L., Yao Q W, Osada M, Li B W, Nishida T
A new multiferroicheterostructure of YMnO3/SnTiO3+x. Scrip. Mater. 2011; 65:
618-621

[34] Harrison R.J., Redfern S.A.T., Smith R.I., Thermodynamics of the R(3)over-bar to
R(3)over-barc phase transition in the ilmenite-hematite solid solution.Am. Mineral.
2000; 85: 1694-1705.

[35] Leinenweber K., Utsmi W., Tsuchida Y., Yagi T., Kuita K., Unquenchable High-Pres‐
sure Perovskite Polymorphs Of MnSnO3 And FeTiO3. Phys. Chem. Miner. 1991; 18:
244.

[36] Venkatesan S., Daumont C., Kooi B.J., Noheda B., J Hossoneff Th.M. De, Nanoscale
domain evolution in thin films of multiferroic TbMnO3. Phys. Rev. B 2009; 80: 214111.
 Chapter 10

Gelcasting of Ferroelectric Ceramics:

Doping Effect and Further Development

Dong Guo and Kai Cai

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/53995

1. Introduction

Ferroelectric ceramics may be seen as the most important type of ferroelectric materials,
which have been used in a wide spectrum of electrical and microelectronic devices, includ‐
ing underwater transducers, micro-pumps and valves, ultrasonic motors, thermal sensors,
probes for medical imaging and non-destructive testing, and accelerometers, etc (Cross LE,
1996; Setter et al., 2000).
Ferroelectric ceramics used in the devices have various shapes. A certain shape formation
technique is required to make ceramics with the desired shapes. Dry pressing is the most
commonly used ceramic forming technique. In this technique, dry powders containing or‐
ganic binder are filled into a solid mold, then dry ceramic green bodies with the shape of the
mold cavity are formed under mechanical or hydraulic compacting presses selected for the
necessary force and powder fill depth. The pressure is around several tens of MPa or higher.
Therefore, large ceramic parts require a much higher compacting force. If the ceramic parts
are unable to have pressure transmit suitably for a uniform pressed density then isostatic
pressing may be used. One of the most serious disadvantages of dry pressing lies in the dif‐
ficulty in fabricating high quality large and complex-shaped ceramics or ceramics with a
fine structure, which are required for various devices.
To resolve the problems associated with the conventional dry pressing, new wet forming
techniques, such as gelcasting (Omatete et al., 1991), electrophoretic casting (Biesheuvel et
al., 1999), hydrolysis assisted solidification (Novak et al., 2002), and direct coagulation cast‐
ing (Graule et al., 1996), etc., are becoming increasingly attractive for advanced ceramic ma‐
terials. Since in these techniques the ceramic powders are dispersed in a liquid medium and
thoroughly mixed, wet forming techniques have the advantages of reducing some structure
defects that are difficult to remove in dry pressed ceramic parts. Among the many wet form‐

© 2012 Guo and Cai; licensee InTech. This is an open access article distributed under the terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
210 Advances in Ferroelectrics

ing techniques, aqueous gelcasting represents the latest improvements. In the technique, a
high solids loading slurry obtained by dispersing the ceramic powders in the pre-mixed sol‐
ution containing monomer and cross-linker is cast in a mold of the desired shape. When
heated, the monomer and cross-linker polymerize to form a three-dimensional network
structure, thus the slurry is solidified in situ and green bodies of the desired shape are ob‐
tained, which consists mainly of ceramic powders with a low polymer content. Gelcasting
may be seen as a milestone in fabricating complex-shaped ceramic parts since it has initiated
a new branch of research in ceramic processing due to its intriguing properties of near-net-
shape forming, high green strength, and low binder concentration, etc. As a pressure free
method, it can also be used in fabricating large ceramic components that have simple
shapes. For example, to make a ceramic disc with a diameter of 20 cm by dry pressing, a
load of hundreds of tons is required. In contrast, such a ceramic disc can be easily made by
gelcasting via a simple ring-shaped mold at much less cost. Furthermore, gelcasting may be
developed to fabricate complex-shaped (Cai et al., 2003) or fine-structured (Guo et al., 2003)
ceramic parts that are rather difficult or even impossible to be formed by the conventional
dry pressing method.

Since its invention in 1991 gelcasting has been widely used for the fabrication of structural
ceramics, including Al2O3 (Young et al., 1991), SiC (Zhou et al., 2000), and Si3N4 (Huang et
al., 2000), etc. Later, it was applied to a number of functional ceramics in a number of ways
including LaGaO3 (Zha et al., 2001), ZnO (Bell et al., 2004), and Sr0.5Ba0.5Nb2O6 (Chen et al.,
2006), etc. The first journal report about the application of gelcasting to piezoelectric ceram‐
ics appeared at 2002 (Guo et al., 2003). Compared to structural ceramics, much less research
about gelcasting of functional ceramics has been conducted so far.

Among the many ferroelectric ceramic materials, lead zirconate titanate (PZT) is the most
widely used one owing to their superior piezoelectric, pyroelectric and dielectric properties.
A fascinating feature of multicomponent ferroelectric ceramics is that their electrical proper‐
ties can be modified by doping with acceptors and donors (Shaw et al., 2000). As a result, a
series of PZT materials with tailored properties are commercially available. Unfortunately,
this feature also leads to the problem of high sensitivity of the electrical properties of PZT to
composition. In addition, PZT is commonly used with a composition close to the morpho‐
tropic phase boundary (MPB) at a Zr/Ti ratio of about 52/48, where properties such as piezo‐
electric coefficients, dielectric permittivity, and coupling factors are maximized and thus
may be more sensitive to the composition (Noheda et al., 2006). On the other hand, since
shape formation in gelcasting is achieved through in situ polymerization, organic additives
are used in the premix solution. Also, addition of commercial surfactants that may have a
complicated composition is indispensable, because successful fabrication of ceramics via gel‐
casting or other colloidal methods requires to prepare high solids loading ceramic slurry
with still a low viscosity. Consequently, in order to apply gelcasting to the formation of fer‐
roelectric ceramics such as PZT, it is necessary to remove the possible influence of the im‐
purities introduced by the various additives on the electrical performance of the final
products. This makes the problems more complicated than that of structural ceramics.
 Gelcasting of Ferroelectric Ceramics: Processing, Doping Effect of Additives and Further Development 211
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2. Colloidal chemistry and rheological properties of PZT suspensions

We first give a short introduction the gelcasting technique. The details are out of the focus of
this chapter, and interested readers can refer to other papers. According to the liquid medi‐
um used, there are two types of gelcasting systems: aqueous and nonaqueous systems. In
aqueous gelcasting deionized water is used as the medium, and acrylamide (C2H3CONH2)
may be seen as a prototype monomer. Generally, N,N-methylenebisacrylamide
((C2H3CONH)2CH2, MBAM) N,N,N0,N0-Tetramethylethylenediamine (TEMED) and
(NH4)2S2O8 are used as the cross-linker, the catalyst and the initiator, respectively. The gel‐
casting process of PZT is similar to that of previous studies. The flowchart of the gelcasting
is shown in Figure 1. First, the PZT powders are added in the premix solution containing
AM and MBAM and thoroughly mixed. After addition of initiator and catalyst, the slurry is
de-aired in vacuum, then the slurry is cast into the mold with desired shape and heated
around 60-80 oC in a oven for several hours for polymerizatoin and drying. After demolding
the green ceramic body is obtained.

Figure 1. The flowchart of gelcasting

212 Advances in Ferroelectrics

The colloidal and rheological properties of the PZT suspension are important issues that
should be addressed first. Homogenous dispersion of the powder in the premix solution
and stability of the suspension are determined mainly by attractive and repulsive forces be‐
tween the particles in the system. The former generally arises from the van der Waals forces
while the latter can arise from electrostatic repulsion or steric repulsion of surfactant materi‐
als absorbed on the particle surfaces (Israelachvili, 1992). Magnitude of the van der Waals
forces is mainly determined by the nature of the particle surface and the solvent. While the
repulsive forces can be modified over a wide range by dispersants.

Commercial Name TAC JN281 SP2 SGA

Producer Beijing Chemical Beijing Pinbao Beijing Tongfang Chemical Beijing Tongfang
Reagent Co. Chemical Co. Co. Chemical Co.

Composition Triammonium citrate Poly (acrylic acid), Poly (acrylic acid-co-maleic Poly (acrylic acid), Na
NH4 + salt solution acid), Na+ salt solution +
salt solution

Table 1. Composition and producer of the dispersants

Figure 2. Effect of dispersants on the zeta potentials of the PZT suspensions at different pH values.

Polyelectrolyte dispersants are well known to be effective for various ceramic slurries due to
both electrostatic and steric repulsions of the macromolecules. Here we show the effects of
 Gelcasting of Ferroelectric Ceramics: Processing, Doping Effect of Additives and Further Development 213
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typical polyelectrolyte dispersants and a widely used organic surfactant triammonium cit‐
rate (TAC). The details are listed in Table 1. Electrostatic repulsion is dependent on the zeta
potential (ζ) of the powders. The higher this value with the same polarity, the stronger the
electrostatic repulsion between the particles. When close to the isoelectric point (IEP), the
particles tend to flocculate. Zeta potentials of various PZT aqueous suspensions (0.06 vol %
solids) at different pH values are shown in Figure 2. The zeta potential of pure PZT suspen‐
sion changes from 33 mV at pH = 1.7 to - 35.1 mV at pH = 11.9 with an IEP at about pH = 7.2,
suggesting that neutral environment is disadvantageous for good dispersion. Addition of
monomer only slightly decreases the relative value of the potential and has little effect on
IEP, indicating that the uncharged AM molecules screen the charge of the PZT particles.
With the addition of TAC, JN281 and SGA the IEP is moved to pH = 2.5, 2.1 and 2.3, respec‐
tively. In the range of neutral environment to pH = 12, the zeta potential is almost constant.
The higher absolute potential values of suspensions with JN281 and SGA than that with
TAC imply that polyelectrolyte dispersants are more effective as far as the electrostatic re‐
pulsion is concerned.

Figure 3 shows the viscosity as a function of the shear rate for different PZT slurries solids
loading. Adjustment of pH values to either acid or basic conditions has little effect, while
addition of dispersants can greatly decrease the viscosity. The high viscosities at the begin‐
ning indicate a ‘Bingham’ type behavior, which is followed by a shear thinning at low shear
rates. Shear-thinning behavior can be attributed to a certain kind of rearrangement of the
relative spatial disposition of the particles. For concentrated suspensions of hard solid parti‐
cles in Newtonian liquids, a flow-induced layered structure has been verified (Ackerson,
1990). Such a structure can provide a low resistance of the particle movement between dif‐
ferent layers under the shear flow. For the systems containing dispersants, when the shear
rates increase to a critical value (γc) a shear-thickening behavior appears, indicating that the
flow-induced structure is destroyed. It is clear that the polyelectrolyte dispersants are much
more effective than TAC. In addition, PZT slurries in the premix solution have almost the
same viscosity values as those in the pure water, suggesting that addition of AM (15 wt.%)
has little effect on the viscosity. These and the zeta potential results indicate that the polye‐
lectrolyte dispersants work by both electrostatic and steric stabilization mechanism.

Generally, there is a complex nonlinear relationship between viscosity and solids volume
fraction, which is closely related to many factors, including the continuous phase viscosity,
particle-size distribution, and particle shape, etc. Influence of solids loading on the apparent
viscosity is shown in Figure 4. At low solids loading the slurries show a low viscosity. The
continuous addition of particles finally three-dimensional contact throughout the suspen‐
sion, making flow impossible. The particular solid phase volume at which this happens is
called the maximum packing fraction Φm (Barnes & Hutton, 1989). Before adding dispersant
the PZT suspension has a measurable viscosity at a solids loading slightly smaller than 32
vol.%. Adding a little more PZT powders leads to a ‘solidified’ slurry whose viscosity is im‐
possible to be measured by the normal rheometer. The Φm is thus determined to be 32 vol.%.
Adding 0.8 and 1.5 wt.% of TAC increase Φm to about 47 and 53 vol.%, respectively. The
lower Φm for a TAC concentration of 2.2 wt.% indicates that excess dispersant is harmful.
214 Advances in Ferroelectrics

The relationship between the viscosity and the solids volume fraction for monodispersed
suspension can be explained by the Krieger–Dougherty (K–D) model:

Figure 3. Influence of dispersants and pH value on the viscosity of the PZT suspensions

Figure 4. Influence of solids loading on the viscosities of the PZT suspensions

 Gelcasting of Ferroelectric Ceramics: Processing, Doping Effect of Additives and Further Development 215
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h = ho (1 - f / f )-[h ]fm (1)

where η and ηo are the viscosity of the suspension and the solvent, respectively. The true
volume fraction of the powder in the suspension is represented by f. The intrinsic viscosity
[η] is a function of particle geometry; a value of 2.5 is suitable for spherical particles. A maxi‐
mum packing fraction of 0.63±0.002 is suitable for random close packing at low shear rate.
The K–D model curve with [η] = 2.5 and Φm=0.63 is plotted in the Figure. Although the ex‐
perimental curves are somewhat deviated from the K–D model, they still show a similar
shape: low viscosity at low solids loading and sharp increase at high solids loading. The dis‐
crepancy may partly be ascribed to the inhomogeneity of the particle size. In addition, parti‐
cle flocculation will lead to a lower Φm because the flocs themselves are not close-packed
(Starov et al., 2002) and they can trap part of the liquid phase, thus, leading to higher ‘effec‐
tive phase volume’ and viscosity than those of the primary particles. The results clearly
show the remarkable effect of dispersants in getting low viscosity ceramic slurry.

3. Electrical characterization and analysis of the doping effects

3.1. Electrical characterization for identifying the doping type

The piezoelectricity of PZT type materials originates from the displacement of Zr and Ti
sublattices and the electrical properties of the materials can be dramastically affected by
doping atoms. There are primarily two types of dopants for PZT, i.e. the donor type (soft
type), and the acceptor type (hard type) (Jaffe et al., 1971). The former is mainly caused by
substitution of higher valence ions for the A site Pb or B site Zr and Ti, and correspondingly
higher piezoelectric coefficient (d33), planar electromechanical coupling factor (Kp), relative
permittivity (εr), loss tangent (tgδ), Pr values and a lower mechanical quality factor (Qm) val‐
ue are obtained. The latter, which is caused by substitution of lower valence ions for the A
or B site atoms, has contrary effects.

Sample Average d33 εr tgδ KP

Dry pressed 469 pC/N 1430 0.0311 0.621

G-TAC 468 pC/N 1369 0.0325 0.633

G-JN281 479 pC/N 1352 0.0401 0.675

G-SP2 403 pC/N 1285 0.0250 0.591

G-SGA 330 pC/N 1244 0.0202 0.541

Table 2. Comparison of densities and some electrical parameters of dry pressed and gelcast PZT samples.
216 Advances in Ferroelectrics

Some electrical parameters of different soft-doped PZT samples are compared in Table 2,
where G-TAC, G-JN281, G-SP2 and G-SGA represent the best available gelcast PZT sam‐
ples with TAC, JN281, SP2 and SGA as the dispersants, respectively. The ε and tgδ are 1
kHz data under room temperature. The dry pressed sample is obtained under a pressure
of ~ 80MPa. G-TAC shows similar electrical properties with those of the dry pressed one.
This indicates that the organic species used in gelcasting, including the dispersant TAC,
the monomer and the cross-linker, etc., have almost no doping effects. Compared to the
dry pressed sample, G-SP2 and G-SGA show higher Qm and decreased d33, Kp, ε, tgδ and
Pr values, while change of these parameters for G-JN281 is to the contrary. Thus, the data
in reveal that SP2 and SGA induced evident ‘hard‘ doped characteristics, while JN281 in‐
duced ‘soft‘ doped characteristics. Except for the dispersant species, the samples were pre‐
pared under the same conditions. Hence, the different properties should be mainly
attributed to the dispersants used. A ‘fingerpint’ of hard doping effect is the increased Qm
(Damjanovic, 1998). Since Na+ is the main metal cation in SP2 and SGA, we neglect other
difference and check the correlation between Na concentration (inspected by X-ray Fluo‐
rescence) and Qm. As shown in Figure 5, Qm roughly shows an increasing trend with Na
mole fraction except for G-JN281. Then we intentionally introduced Na into the G-JN281
by adding NaOH to the corresponding slurry to increase its pH value to ~13. As expect‐
ed, a higher Qm is indeed obtained after adding Na to G-JN281. These reveal that the Na+
ion introduced by the dispersants has a stronge doping effect for gelcast PZT. From the
valence and diameter (1.02Å) of Na+, we deduce that it should substitute for the A site
Pb2+ (1.18Å) as an acceptor dopant.

Figure 5. Illustration of the relationship between Na concentration (mole percentage in total metal elements) and Qm
of various PZT samples.
 Gelcasting of Ferroelectric Ceramics: Processing, Doping Effect of Additives and Further Development 217
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3.2. Complex impedance spectra

Figure 6(a), 6(b), 6(c) and 6(d) show the complex impedance spectra in the temperature
range of 300~540 oC of the dry pressed sample, G-JN281, G-JN281+Na and G-SP2, respective‐
ly. The spectra of G-TAC is very similar with those of the dry pressed sample and thus not
shown. The complex impedance spectra of all samples show only one Cole-Cole semicircle
crossing the origin, which can be assigned with an equivalent circuit composed of a simple
parallel RC element with a impedance that can be expressed as equation (2):

R
Z=
1 + (iw RC )1- n
, (2)

where the parameter n characterizes the distribution width of the relaxation times around a
mean value τ0=RC (West et al., 1997). The semicircles of the samples show no obvious depression,
i.e. the depression angle β (=nπ/2) between the real axis and the line from the high frequency in‐
tercept to the centre of the circle is close to 0. Thus, n is close to 0, indicating a debye-like behavior
with a single relaxation time (West, 1997; Cao, 1990). Then based on equation (2) the following re‐
lationship about the real (Z′) and imaginary (Z″) parts of the impedance can be derived:

( Z¢ - R 2 ) (3)
2
+ Z¢¢2 = ( R 2 ) .
2

The resistance R derived from the diameter of the semicircle, and the capacitance C can be
derived from the angular frequency ω at the peak of the circular arc based on the relation‐
ship ωRC=1. The C values of the samples are in the order of 10-10-10-9 F, which can be associ‐
ated with the intrinsic ferroelectric bulk (or grain) response.

Using the R values, the logarithm of conductivity of different samples as a function of recip‐
rocal temperature is plotted in Figure 6(e). The conductivity σ of the ferroelectric bulk phase
shows an Arrhenius type behavior that can be described by equation (4):

- Es
s = s o exp(
kT
), (4)

where σ0, Eg, k and T are the pre-exponential factor, the activation energy, the Boltzmann’s
constant and the absolute temperature, respectively. The logarithm of equation (4) gives
equation (5):

Es 1
lns T = ln s o - ( ) = -2.30259 log rT ,
k T
(5)

where ρT is the resistivity. Based on the sample geometry, the Eg values associated with the
intrinsic bulk phase conduction of the samples were derived by using equation (5). The data
are compared in Table 3.
218 Advances in Ferroelectrics

Figure 6. Complex impedance spectra of different PZT samples. (a) Dry pressed. (b). G-JN281. (c) G-JN281+Na. (d) G-
SP2. (e) Arrhenius plot for the ferroelectric bulk resistivity of the samples derived from the impedance spectra.

Sample Dry pressed G-JN281 G-JN281+Na G-SP2 G-SGA

Eg 1.24 eV 1.48 eV 1.14 eV 1.08 eV 1.07 eV

Table 3. Comparison of the conductivity activation energies of different PZT samples.

 Gelcasting of Ferroelectric Ceramics: Processing, Doping Effect of Additives and Further Development 219
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Figure 7. (a) Complex impedance spectra of G-SGA. The inset shows the magnified 375oC and 418oC curves. (b) Arrhe‐
nius plot of the ferroelectric bulk phase resistivity of the sample derived from the grain response of its impedance
spectra.

The spectra of G-SGA shown in Figure 7(a), particularly the high temperature curves shown
in the inset, consist of two semicircles, which can be assigned with an equivalent circuit
composed of two parallel RC elements. This indicates the much different ‘electrical micro‐
structure’14 of G-SGA, which has the highest Na concentration. The capacitance obtained by
fitting the first semicircle can also be attributed to the ferroelectric bulk response, while the
second semicircle may be attributed to the grain boundary response due to the higher capac‐
itance. Actually, one semicircle spectrum may also appear if different responses in a sample
overlap as a result of their similar relaxation time. A closer check of Figure 6(d) indicates
that the one semicircle impedance spectra of G-SP2 have a slightly higher depression angle
than other spectra in Figure 6, consistent with its higher Na concentration (see Figure 5).
These imply that the grain boundary response is gradually magnified with increasing Na
concentration. The Arrhenius plot of the conductivity of the bulk phase response of G-SGA
is shown in Figure 7 (b). The derived Eg value is also listed in Table 3.

The loss of PbO through its volatility causes oxygen vacancies in PZT, leading to a p-type
conductivity (Barranco et al., 1999). The acceptor Na+ incorporated by the dispersants can
substitute for Pb2+, which can be expressed as following:

Na 2O=2Na pb ’+Oo +Vo (6)

Thus, Na+ ions replace Pb2+ ions and more oxygen vacancies are simultaneously created for
charge compensation. Oxygen vacancies are the only lattice defects in the perovskite oxides
that have a significant mobility, and the conductivity should be improved by the oxygen va‐
cancy conduction mechanism via hopping of atoms in the oxygen octahedral network (Ray‐
mond & Smyth, 1996). This well explains the lower Eg data of G-SP2 and G-SGA than that of
the dry pressed sample (Table 3), revealing again the hard doping effect of the Na-contain‐
ing dispersants. The relatively higher activation energy of G-JN281 implies the presence of a
certain donor-type impurity in G-JN281. Addition of NaOH into G-JN281 leads to a lower Eg
value and further confirms the doping effect of Na.
220 Advances in Ferroelectrics

3.3. Ferroelectric hysteresis loops

The ferroelectric (polarization-electric field) hysteresis loops of the PZT samples are shown
in Figure 8. In Figure 8(a), G-SP2 and G-SGA show remnant polarization (Pr) of 32.7 μC/cm2
and 16.7 μC/cm2, respectively. Both values are smaller than the value of 39.8 μC/cm2 of the
dry pressed sample. The difference can also be interpreted by increased oxygen vacancies
due to doping of Na. As afore mentioned, oxygen vacancies can move in the oxygen octahe‐
dral network. This may lead to a low stability of the 2Napb’-Vo defect dipoles. The defect di‐
poles tend to orient themselves along the polarization direction, resulting in stabilized
ferroelectric domains. A stabilized domain wall structure in turn give rise to more difficult
poling and depoling (switching) and a smaller Pr (Warren, et al., 1996; Lambeck & Jonker,
1978). The round open loop of G-SP2 implies a higher leakage current. The hysteresis loops
of G-JN281 and G-JN281+Na in Figure 8 (b) also clearly demonstrates the effect of Na: de‐
creased Pr and a loop with a rounder shape.

Figure 8. Ferroelectric hysteresis loops of the PZT samples.

4. Microstructural characterization

The XRD spectra of All samples (Figure 9) show typical perovskite structures (Soares et al.,
2000; Hammer et al., 1998). The XRD patterns of G-TAC, G-SP2 and G-SGA are very similar
to that of the dry pressed sample. While the peaks of the XRD pattern of G-JN281 shift very
slightly to higher diffraction angles, indicating a contracted lattice cell. Considering the soft
doped characteristics of G-JN281, the change in its XRD pattern may again be attributed to a
certain unknown donor impurity ion introduced by the dispersant.
 Gelcasting of Ferroelectric Ceramics: Processing, Doping Effect of Additives and Further Development 221
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Figure 9. XRD patterns of different PZT samples.

As shown in Figure 10, although sintered under the same procedure, the samples exhibit
rather different morphologies. SEM image of G-JN281+Na is not illustrated since it is very
similar to that of G-JN281. Dry pressed sample shows an intergranular fracture surface and
relative uniform grains with a diameter of 3~5 μm. G-JN281 shows a morphology very simi‐
lar to that of the dry pressed one. G-SP2 also shows a basically intergranular fracture sur‐
face, but the grains are much larger with a diameter of 6~10 μm. Much different from other
samples, G-SGA shows a transgranular fracture surface with the largest grains with a diam‐
eter of about 12 μm. Such a transgranular growth may result from chemical inhomogeneity
and presence of intergranular phases or expanded grain boundary region. This is consistent
with the two semicircle impedance spectra of G-SGA shown in Figure 7 (a).
In summary, electrical and structural characterization indicate that the Na+ ion, which is the
main cation in many widely used commercial dispersants (Xu et al., 1996; Tomasik et al.,
2003), shows detrimental hard doping effects, leading to deteriorated electrical performance.
Also, the impurity species introduced by dispersants or other additives may have a compli‐
cated influence on the electrical properties and microstructure of gelcast PZT samples. The
results indicate that the specific doping effect, e.g. the change in electrical performance by
the additives during processing, is a critical issue that should be paid special attention when
applying gelcasting to the formation of electronic ceramics.
222 Advances in Ferroelectrics

Figure 10. SEM images of the fracture surfaces of different PZT samples. (a) Dry pressed sample; (b) G-JN281; (c) G-
SP2; (d) G-SGA.

5. Development of gelcasting for special-shaped PZT ceramics

Application of gelcasting to ferroelectric ceramics is not a mechanical copy of the technique

to a different powder material. In addition to the demonstrated doping effect of the necessa‐
ry additives, there are many other specific issues deserving further investigation. The many
devices require the ferroelectric ceramic components to have various specific shapes (Scott,
2007). The shapes of the gelcast bodies are formed during gelation and drying process with
the confinement of the molds. The two most critical issues about shape formation that have
attracted more and more attention are probably the fracture (or crack growth) and deforma‐
tion of the ceramics. No doubt that the former should be avoided, however, what is interest‐
ing is that the latter may even be used to form shapes that are difficult to formed by the
molds. The two issues are briefly discussed in the following.
 Gelcasting of Ferroelectric Ceramics: Processing, Doping Effect of Additives and Further Development 223
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5.1. Factors affecting fracture and crack growth

Fracture or crack growth results from the competition of the strength of the gelcast body and
the stress developed during gelation and drying. Many factors can affect fracture or crack
growth, including the monomer concentration, monomer/cross-linker ratio, initiator concen‐
tration, initiator/catalyst ratio, gelation temperature and drying condition (humidity), etc (Ma
et al., 2006). It is easy to be understood that too low a monomer concentration is insufficient to
keep the three dimensional polymer network structure. A suitable monomer/cross-linker ratio
is necessary to keep a strong gelcast body with still controllable stresses. Compared to other
factors, initiator and catalyst seem to be more critical in controlling the gelcast body strength
and stresses, since they can determine the ‘joints’ of the gel network. As shown in Figure 11. A
slight decrease of the (NH4)2S2O8 concentration from the normal level causes a seriously broken
green body. In addition to use of optimized premix solution, drying is a complicated process
that should be carried out under contolled humidity (Barati et al., 2003).

Fracture or crack growth may also appear after sintering (Zheng et al., 2008), even if the
shapes of the ceramics are well preserved after drying. During sintering the macromolecular
gel network is destroyed and the stresses developed due to material densification may give
rise to fracture or cracks in the ceramic body with decreased strength.

Figure 11. A fractured PZT-4 type green body caused by a lower initiator concentration
224 Advances in Ferroelectrics

5.2. Deformation controllable gelcasting

Factors that affect crack growth discussed in the forgoing section also affect deformation. In
most cases, deformation should be kept as smaller as possible. However, well controlled defor‐
mation can also be used to fabricate certain devices that use specially-shaped PZT as the active
components. Here we show two examples: spherical PZT shell vibrator and PZT minitube.

As an effective non-invasive surgical tool, High intensity Focused sound (HIFU) has been
used for the treatment of human tissues such as liver, kidney, breast, uterus and pancreas,
and it is receiving growing interest (Wan, et al., 2008; Davies et al., 1998). As shown in Fig‐
ure 12, some therapeutic HIFU transducers require to use spherical piezoelectric PZT shells
as the active components (Saletes et al., 2011). Conventionally, such a spherical plate is fabri‐
cated by grinding both sides of a cylindrical plate. The mechanical method is time-consum‐
ing and wastes a lot of PZT material. Gelcasting of flat PZT plates generally uses a
cylindrical ring mold and a flat bottom plate. During drying, the upper surface of the gelcast
body is exposed to atmosphere while the other side is still berried until the whole body sol‐
idifies. Then we found an interesting phenomenon: the upper part of the gelcast body might
dry and shrink first and a spherical plate was formed. By using suitable premix solution and
under well controlled temperature and humidity, the plate edge bends up and a rather ideal
spherically shaped PZT green plate can be formed. After sintering a spherical PZT plate was
formed, which only needs to be grinded slightly to produce a homogenous spherical vibra‐
tor. Furthermore, because a lower humidity and a higher temperature can give rise to a larg‐
er deformation, the curvature radius can be controlled in a certain range under well
controlled experimental conditions. So far the smallest focal length obtained for a plate with
a diameter of 10 cm without further machining is around 15 cm. A PZT-8 plate with a diam‐
eter of 12 cm is shown in Figure 13.

Figure 12. Schematic illustration of the therapeutic effect of a HIFU transducer

 Gelcasting of Ferroelectric Ceramics: Processing, Doping Effect of Additives and Further Development 225
http://dx.doi.org/10.5772/53995

5.3. Fabrication of hollow spherical PZT shell

Thin-walled hollow sphere Omnidirectional Transducer has been used in hydrophones for
many years (Li et al., 2010), which uses a hollow spherical PZT shell as the active compo‐
nent. Hollow spherical PZT shell is generally fabricated by Cold isostatic pressing, which re‐
quires complicated facilities. We show here that gelcasting can be developed to fabricate
such Hollow spherical PZT shells by using a ball-shaped removable polymeric mold. First,
the polymeric ball mold is fixed in a normal metal mold with a large spherical cavity, then
the aqueous PZT premix slurry is poured into the mold. After gelation and drying, the
whole mold containing the PZT green body and polymeric ball is removed by a careful ther‐
mal treatment. The most critical step in this method is thermal treatment, which solidifies
the PZT slurry and melt the polymeric ball in due time. A PZT-4 hollow spherical shell with
a focal length of ~ 200 mm, a diameter of ~ 120 mm and a wall thickness of 2 mm is also
show in Figure 13.

Figure 13. Illustration of special-shaped gelcast PZT ceramics: spherical PZT plate and hollow spherical PZT shell.

In addition to the above mentioned advanced techniques, other gelcasting based ceramic
fabrication or processing techniques have been developed in the authors’ group, including
spatter laser drilling techniques (Guo, 2004), and Rapid Prototyping of PZT bodies by com‐
bining gelcasting and Selective Laser Sintering (Guo, 2003), etc.

6. Conclusions

Comparison of various electrical properties and microstructures of various gelcast soft PZT
samples with those of the dry pressed PZT one suggests that the Na+ ion, which is the main
cation in many widely used commercial dispersants, shows detrimental hard doping effects,
leading to deteriorated electrical performance. The conclusion may be transferable to other
doping ions like K+, which is also contained in many commercial dispersants. Also due to
the doping ions introduced by dispersants, the performance of the glecast PZT sample may
226 Advances in Ferroelectrics

also be improved as well. Considering that dispersants are indispensible in getting concen‐
trated low viscosity ceramic slurries, the possible doping effect of metal ions or impurities
introduced by the dispersants or other additives should be generally considered when ap‐
plying gelcasting to forming multicomponent electronic ceramic materials whose electrical
properties are sensitive to the composition.
In addition, we also demonstrate some advanced gelcasting techniques, including deforma‐
tion controllable gelcasting of spherical PZT disc and gelcasting based hollow spherical PZT
fabrication technique, etc. Application of gelcasting to PZT is not a mechanical copy of the
technique to a different powder material. The results show that successful application of gel‐
casting to ferroelectric ceramics is not a mechanical copy of the technique to a different pow‐
der material.

Author details

Dong Guo1 and Kai Cai2

1 Institute of Acoustics, Chinese Academy of Sciences, Beijing, China

2 Beijing Center for Chemical and Physical Analysis, Beijing Municipal Science and Technol‐
ogy Research Institute, Beijing, China

References

[1] Crsos, LE. (1996). Ferroelectric materials for electromechanical transducer applica‐
tions. Materials Chemistry and Physics, 43, 108-115
[2] Setter, N.; Waser, R. ( 2000). Electroceramic materials. Acta Materialia, 48, 151-178
[3] Omatete, O.O.; Janney, M.A.; Strehlow, R.A. (1991). Gelcasting: a new ceramic form‐
ing process. American Ceramic Society Bulletin, 70, 1641-1649
[4] Biesheuvel, PM.; Verweij, H. (1999). Theory of Cast Formation in Electrophoretic
Deposition. Journal of the Amarican Ceramic Society, 82, 1451-1455
[5] Novak, S.; Kosmac, T.; Krnel, K.; Drazic, G. (2002). Principles of the hydrolysis assist‐
ed solidification (HAS) process for forming ceramic bodies from aqueous suspen‐
sion. Journal of the European Ceramic Society, 22, 289-295
[6] Graule, TJ.; Gauckler, LJ.; Baader, FH. (1996). Direct coagulation casting–a new green
shaping technique.PT.1. processing principles. Industrial Ceramics, 16, 31-34
[7] Cai, K.; Guo, D.; Huang, Y.; Yang, JL. (2003). Solid freeform fabrication of alumina
ceramic parts through a lost mould method. Journal of the European Ceramic Society,
23, 921-925
 Gelcasting of Ferroelectric Ceramics: Processing, Doping Effect of Additives and Further Development 227
http://dx.doi.org/10.5772/53995

[8] Guo, D.; Li, LT.; Gui, ZL.; Nan, CW. (2003). B-Solid state materials for advanced tech‐
nology. Materials Science and Engineering, 99, 25-28

[9] Young, A.C.; Omatete, O.O.; Janney, M. A.; Menchhofer, P.A.(1991). Gelcasting of
Alumina. Am.Ceram. Soc, 74, 612-618

[10] Zhou, LJ.; Huang, Y.; Xie, ZP.; (2000). Gelcasting of concentrated aqueous silicon car‐
bide suspension. Journal of the European Ceramic Society, 20, 85-90

[11] Huang, Y.; Ma, LG.; Tang, Q.; Yang, JL.; Xie, ZP.; Xu, XL. (2000). Surface oxidation to
improve water-based gelcasting of silicon nitride. Journal of Materials Science, 35,
3519-3524

[12] Zha, SW.; Xia, CR.; Fang, XH.; Wang, HB.; Peng, DK.; Meng, GY. (2001). Processing
and electrical properties of doped-LaGaO by gelcasting. Ceramics Intrernational, 27,
3

649-654

[13] Bell, NS.; Voigt, JA.; Tuttle, BA. (2004). Colloidal processing of chemically prepared
zinc oxide varistors. Part II: Near-net-shape forming and fired electrical properties.
Journal of Materials Research, 19, 1341-1347

[14] Chen, W.; Kinemuchi, Y.; Watari, K.; Tamura, T.; Miwa, K. (2006). Preparation of
Grain-Oriented Sr Ba Nb O Ferroelectric Ceramics by Magnetic Alignment. Journal o
0.5 0.5 2 6

f the American Ceramic Society , 89, 381-384

[15] Guo, D.; Cai, K.; Li, LT.; Gui, ZL. (2003). Application of gelcasting to the fabrication
of piezoelectric ceramic parts. Journal of the European Ceramic Society, 23, 1131-1137

[16] Shaw, TM.; Trolier-McKinstry, S; McIntyre, PC.; (2000). The Properties of Ferroelec‐
tric Films at small dimensions. Annual Review of Materials Science, 30, 263-298

[17] Noheda, B.; Cox, DE. (2006). Bridging phases at the morphotropic boundaries of lead
oxide solid solutions. Phase Transitions, 79, 5-20

[18] Israelachvili, J.; (1992). Intermolecular & Surface Forces, 2nd ed.

[19] Ackerson, B. J. (1990). Shear induced order and shear processing of model hard
sphere suspensions. J. Rheol, 34, 553–590

[20] Barnes, H.A. (1989). Shear-thickening (dilatancy) in suspensions of nonaggregating

solid particles dispersed in Newtonian liquids. J. Rheol, 33, 329–366

[21] Barnes, H.A.; Hutton,J.F.; Walers, K.; (1989). An Introduction to Rheology, Elsevier, Ox‐
ford.

[22] Starov, V.; Zhdanov, V.; Meireles M. et al. (2002) Viscosity of concentrated suspen‐
sions: influence of cluster formation. Advances in Colloid and Interface Science , 96,
279-293

[23] Jaffe, B.; Cook, W. (1971). Piezoelectric Ceramics. Academic Press,London/New York.
228 Advances in Ferroelectrics

[24] Damjanovic, D. (1998). Ferroelectric, dielectric and piezoelectric properties of ferro‐

electric thin films and ceramics. Reports on Progress in Physics,61, 1267.
[25] West, A. R.; Sinclair, D. C. and Hirose, N. (1997). J. Electroceram, 65, 71
[26] Cao, W. Q.; and Gerhardt, R. (1990). Solid State Ionics, 42, 213
[27] Barranco, A. P.; Pinar, F. C.; Martinez, O. P. ; Guerra, J. D. ; and Carmenate,I. G.
(1999). J. Eur. Ceram. Soc, 19, 2677
[28] Raymond, M. V.; Smyth, D. M. (1996). Defects and charge transport in perovskite fer‐
roelectrics. J. Phys. Chem. Solids, 57, 1507-1511
[29] Warren, W.L.; Pike, G.E.; Vanheusden,K.; Dimos, D.; Tuttle, B. A.; Robertson,J.
(1996). Defect-dipole alignment and tetragonal strain in ferroelectrics. J. Appl. Phys,
79, 9250-9257
[30] Lambeck, P. V.; Jonker,G. H. (1978). Ferroelectrics, 22, 729
[31] Soares, MR.; Senos, AMR.; Mantas, PQ. (2000). Phase coexistence region and dielec‐
tric properties of PZT ceramics. J. Eur. Ceram. Soc, 20, 321-334
[32] Hammer, M.; Monty, C.; Endriss, A. (1998). Correlation between surface texture and
chemical composition in undoped, hard, and soft piezoelectric PZT ceramics. Journal
of the American Ceramic Society, 81, 721-724
[33] Xu, ZH.; Ducker, W.; Israelachvili, J. (1996). Langmuir, 12, 2263-2270
[34] Tomasik, P.; Schilling, CH.; Jankowiak, R.; Kim, JC. (2003). The role of organic disper‐
sants in aqueous alumina suspensions. Journal of the European Ceramic Society, 23,
913-919
[35] Scott, J. F. (2007). Science, 315, 954-959
[36] Ma, LG.; Huang, Y.; Yang, JL.; Le, HR.; Sun, Y. (2006). Control of the inner stresses in
ceramic green bodies formed by gelcasting. Ceramics International, 32, 93-98
[37] Barati, A.; Kokabi, M.; Famili, N. (2003). Modeling of liquid desiccant drying method
for gelcast ceramic parts. Ceramics International, 29, 199-207
[38] Zheng, ZP.; Zhou, DX.; Gong, SP. (2008). Studies of drying and sintering characteris‐
tics of gelcast BaTiO -based ceramic parts. Ceramics International, 34, 551-555
3

[39] Wan, Yayun.; Ebbini, Emad S. (2008). Transactions on Ultrasonics Ferroelectrics and
frequency Control. IEEE 55, 1705-1718
[40] Davies, BL.; Chauhan, S.; Lowe, M. (1998). International Conference on Medical Im‐
age Computing and Computer-Assisted Intervention. Lecture Notesin Computer Sci‐
ence, 1496, 386-396
[41] Saletes, Izella.; Gilles, Bruno.; Bera, Jean-Christophe. (2011). Promoting inertial cavi‐
tation by nonlinear frequency mixing in a bifrequency focused ultrasound beam. Ul‐
trasonics,51, 94-101
 Gelcasting of Ferroelectric Ceramics: Processing, Doping Effect of Additives and Further Development 229
http://dx.doi.org/10.5772/53995

[42] Li, XF.; Peng, XL.; Lee, KY. (2010). The static response of functionally graded radially
polarized piezoelectric spherical shells as sensors and actuators. Smart Materials &
Structures, 19, 3

[43] Guo, D.; Li, LT.; Cai, K.; Gui, ZL.; Nan, CW. (2004). Rapid Prototyping of Piezoelec‐
tric Ceramics via Selective Laser Sintering and Gelcasting. Journal of the American Ce‐
ramic Society, 87, 17-22

[44] Guo, D.; Cai, K.; Huang, Y.; Li, LT. (2003). A novel anti-spatter and anti-crack laser
drilling technique: application to ceramics. Applied Physics A:materials Science & Proc‐
essing , 76, 1121-1124
 Chapter 11

Electronic Ferroelectricity in II-VI Semiconductor ZnO

Akira Onodera and Masaki Takesada

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52304

1. Introduction

II-VI semiconductor Zinc oxide (ZnO) is a well-known electronic material [1-3]. Because of
large piezoelectric constant and electromechanical-coupling constant, ZnO has been applied
to ultrasonic transducer, SAW filter, gas sensor etc [3-5]. In addition, ZnO has been used
widely as pigment and UV cut cosmetics extensively, so it is a safe material for our living
environment, compared with heavy metals used in semiconducting process and materials
science. Recently, ZnO has been studied as a material for the solar cell, transparent conduc‐
tors formed on liquid crystal displays, and the blue laser [6]. Then, p-type ZnO was found
by Joseph et al [7].

Ferroelectricity is recognized to appear mainly by the delicate balance between a long-range

dipole-dipole interaction and a short-range interaction. When electrons should be well local‐
ized in dielectrics, the electronic distribution in the unit cell is determined by atomic posi‐
tions of constituent ions. Slight distortion of electronic distribution due to structural changes
in dielectrics gives a rise of dipole moments. From this point of view, the ferroelectric phase
transition should be understood as a structural phase transition from the paraelectric phase
with high symmetry to the ferroelectric phase with low symmetry. The atomic displace‐
ments are generally 0.01~0.1 Å, which are small compared with Bohr radius ( 0.53 Å). There‐
fore ferroelectrics are considered as a group of materials which are sensitive to structural
changes. In this sense, the ferroelectric phase transition is classified into one of the structural
phase transitions.

The basic Hamiltonian is generally given as

H= H(phonon) + H(electron) + H(electron-phonon),

where H(phonon) and H(electron) are due to motions of ion cores and valence electrons,
and H(electron-phonon) presents interactions between ions and valence electrons. In dielec‐

© 2012 Onodera and Takesada; licensee InTech. This is an open access article distributed under the terms of
the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
232 Advances in Ferroelectrics

tric materials, the contribution of electron systems is usually omitted since the band gap is
generally wide. However, it should be necessary to consider the electron-phonon interaction
in the case of ferroelectric semiconductors, since the correlation energy of dipole-dipole in‐
teraction (about 0.2 eV) is comparable with band-gap energy in some narrow-gap and wide-
gap semiconductors. For this type of compounds, the electronic contribution due to bond
charges and conduction electrons should play a key role and must be taken into account for
understanding the nature of ferroelectricity. For long time, the importance of electronic con‐
tribution has been pointed out in the field of ferroelectrics, since the simple superposition of
electronic polarizability does not hold in many ferroelectric substances. Recently, the novel
ferroelectricity was discovered in narrow-gap and wide-gap semiconductors such as Pb1-
xGexTe [8], Cd1-xZnxTe [9] and Zn1-xLixO [10].The appearance of ferroelectricity is primarily
due to electronic origin in Zn1-xLixO. Although the ferroelectric phase transition accompanies
with structural distortions in usual ferroelectrics, only small structural changes of the order
of 10-3 Å are observed in Zn1-xLixO. The change in d-p hybridization caused by Li-substitu‐
tion is responsible for the novel ferroelectricity and dielectric properties. In this chapter, we
summarized recent works mainly onZnO.

2. Zinc oxide

The crystal Structure of ZnO is wurtzite-type (P63mc) as shown in Fig. 1, which belongs to
hexagonal system. It does not have the center of symmetry, and is polar along the c-axis.
Although it has been pointed out that the structure of pure ZnO has the possibility to ex‐
hibit ferroelectricity, the polarization switching does not observed until its melting point
(1975oC) because of large activation energy accompanied by dipole switching process. The
lattice constants are a = 3.249858 Å, c= 5.206619 Å at room temperature (298 K) [11]. Zn and
O ions are bonded tetrahedrally and form ZnO4 groups. This tetrahedron is not perfect: the
apical bond length of Zn-O is 1.992 Å (parallel to the c-axis) and the basal one is 1.973 Å.
Bond length along the c-axis is longer than other three bonds by 0.96%: the ZnO4tetrahedra
distort along the c-axis, which result in dipole moment. According to recent first-principles
studies, it was reported that the hybridization between the Zn 3d-electron and the O 2p-
electron plays an important role for dielectric properties of ZnO [12, 13].The energy gap Eg
is 3.44 eV [14]. Although stoichiometric ZnO is an insulator (intrinsic semiconductor), it ex‐
hibits n-type conductivity because of excess Zn atoms. The resistivity is about 300 Ωcm,
which, however, changes drastically by doping various impurities. By doping of trivalent
ions, such as Al3+, In3+, Ga3+, it reduces to the order of 10-4Ωcm and shows the conductivity
near that of metals [15].

Although p-type conductivity is expected by doping of monovalent Li+ ions, ZnO becomes
an insulator and the resistivity increases to as much as 1010Ωcm [16-18]. It is remarkable that
the change in resistivity reaches over the order of 1014, which covers from metal-like to insu‐
lating region. It suggests that the physical nature in this material changes drastically by a
little amount of dopant.
 Electronic Ferroelectricity in II-VI Semiconductor ZnO 233
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Figure 1. Crystal structure of ZnO (Wurtzite structure).

3. Electronic structure

Electronic structure of ZnO has been studied by LMTO (linear muffin-tin orbital) method
[19] and by LAPW (linearized augmented-plane-wave) method using LDA (local density
approximation). Band structure and the density of states is shown in Figs. 2 and 3 [20].
Around -17 eV, there are two bands originating from the O 2s-states. The narrow bands be‐
tween -6 and -4 eV consist mainly of the Zn 3d-orbitals, and moderately dispersive bands
from -4 to 0 eV consist mainly of the O 2p-orbitals. Figure 4 shows significant d-p hybridiza‐
tion. The 3d derived bands split into two groups, leading to double-peak structure in DOS
(density of states). The lower peak is characterized by a strong d-p hybridization. The sharp
upper peak between -4.8 and -4.2 eV has strong Zn 3d character and the hybridization with
the O 2p-state is very small. Band gap is 0.77 eV. Discrepancy with the experimental value is
larger than that of LMTO. It is due to the LDA gap error [21].

Figure 2. Band structure of ZnO using LAPW.

234 Advances in Ferroelectrics

Figure 3. Density of states of ZnO using LAPW.

4. Ferroelectricity in binary semiconductors

Recently, the novel ferroelectricity was found in Li-doped ZnO [10, 22, 23], although pure
ZnO has not shown any evidence of ferroelectricity. Generally representative ferroelectrics
have complicate crystal structures such as Rochelle salt (KNaC4H4O6 4H2O), TGS (tri-glycine
sulfate, (NH3CH2COOH)3H2SO4) and BaTiO3. Since ZnO is a simple binary compound, it is
very convenient to study the microscopic mechanism and its electronic contribution for the
appearance of ferroelectricity. Besides ZnO, IV-VI narrow-gap semiconductor Pb1-xGexTe
and II-VI wide-gap semiconductor Cd1-xZnxTe, are known as materials of binary crystals ac‐
companying ferroelectricity.

4.1. IV-VI Narrow-gap semiconductor

Among IV-VI semiconductor, Pb1-xGexTe has been investigated extensively about its ferroe‐
lectricity [8]. Pb1-xGexTe has a NaCl (rock-salt) type structure at room temperature. Although
any ferroelectric activities have not been observed in pure PbTe and GeTe crystals, the ferro‐
electric phase transition is induced only in solid solution Pb1-xGexTe. In the low temperature
phase of Pb1-xGexTe, the crystal becomes rhombohedral and exhibits ferroelectric activity. In
the case of x = 0.003, it shows a large dielectric anomaly of the order of 103 at T = 100 K as
shown in Fig. 5 and the softening of TO mode was observed.

The energy gap of Pb1-xGexTe is no more than 0.3 eV, which is 3000 K in temperature. This
value is comparable to the energy of the Lorentz field of dielectrics, (4π/3)P. Therefore, con‐
duction electrons can couple strongly with phonons in this solid solution. The electron-pho‐
non interaction decreases the frequency of TO phonon mode which results in the
ferroelectric phase transition. In Pb1-xGexTe, doped Ge ions displace from the center position
 Electronic Ferroelectricity in II-VI Semiconductor ZnO 235
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of Pb ion by 0.8 Å and behave as off-center ions because of the ionic size-mismatch between
Pb ion (the ionic radius: 1.2 Å) and Ge ion (the ionic radius: 0.73 Å) [24]. The direction of
displacement is the eight equivalent [111] directions, which is spatially vacant and polar in
the rock-salt structure. Above Tc, the ions shift toward any one of these directions at ran‐
dom, but its displacement would be ordered along the trigonal axis below Tc. The ordering
of the off-center ion triggers the softening of TO phonon mode and induces rhombohedral
distortion in the way such as ‧‧‧Pb2+-Te2-‧‧‧Pb2+-Te2-‧‧‧Pb2+-Te2-‧‧‧or ‧‧‧Te2--Pb2+‧‧‧Te2-- Pb2+‧‧‧
Te2--Pb2+‧‧‧. This structural ordering generates spontaneous polarization. However, in Pb1-
xGexTe, the D-E hysteresis loop has not been observed, while it is a direct evidence of the
ferroelectricity. Whereas traditional dielectric measurements are performed on a parallel-
plate capacitor, it is difficult to measure dielectric constant of such lossy Pb1-xGexTe because
of current leaks. Therefore dielectric constant is determined by the C-V measurement or the
optical reflectiveity, which are commonly used in semiconductors. The large dielectric
anomaly and soft mode of Pb1-xGexTe suggest the ferroelectric activity.

Figure 4. Crystal structures of Pb1-xGexTe, Cd1-xZnxTe and Zn1-xLixO. The lower figures are plots along the polar [111]
directions for Pb1-xGexTe and Cd1-xZnxT, and polar [0 0 1] direction for Zn1-xLixO.
236 Advances in Ferroelectrics

Figure 5. Temperature dependence of dielectric constant in Pb1-xGexTe (x=0.003).

4.2. II-VI Wide-gap semiconductor Cd1-xZnxTe

Among many wide-gap semiconductors, the ferroelectricity of Cd1-xZnxTe was discovered

by R. Weil et al in 1988 [9, 25]. The Eg of Cd1-xZnxTe is 1.53 eV. It is a wide-gap semiconductor
unlike the narrow-gap IV-VI Pb1-xGexTe. The crystal structure is cubic zinc-blende-type.
Cd(Zn) ion is surrounded by four Te ions tetrahedrally. The center of symmetry in this com‐
pound does not exist. When x=0.1, the crystal exhibits a dielectric anomaly at 393 K as shoen
in Fig. 6. The peak value of dielectric constant (εpeak) is only 50, which is smaller by about
two orders than that of BaTiO3 (~14000) and that of Pb1-xGexTe (~1000). Because of the large
Eg and the resistivity (~kΩ), a ferroelectric D-E hysteresis loop was successfully observed in
the low-temperature phase. The direction of spontaneous polarization is along the apex of a
tetrahedron, [111], which is reported as Ps= 0.0035 μC/cm2 in their first paper, and 5 μC/cm2
in the second paper. Because the ionic radius of Zn ion (0.83 Å) is smaller than that of Cd ion
(1.03 Å), Zn ion also locates at the off-center position which deviates from the center of tetra‐
hedra toward the apex. According to the result of EXAFS (X-ray absorption fine structure), it
shifts by 0.04 Å [26]. It is considered that the ordering of off-center ions causes rhombohedral
distortion of the cubic lattice by about 0.01 Å, and induces ferroelectricity.

In Cd1-xZnxTe, the soft mode has not been observed and the dielectric anomaly is small.
These dielectric properties are different from those found in Pb1-xGexTe, which are summar‐
ized in Table 1. These facts are consistent each other when one consider the LST (Lyddane-
Sachs-Teller) relation (ωLO2/ωTO2 = ε/ε∞). In Pb1-xGexTe, the existence of soft mode is
responsible for large dielectric anomaly. Although the behavior of off-center ions plays an im‐
portant role in this ferroelectricity like Pb1-xGexTe, the occurrence of phase transition seems
 Electronic Ferroelectricity in II-VI Semiconductor ZnO 237
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to be driven in different way from that of Pb1-xGexTe, because of the different dielectric prop‐
erties described above. Furthermore, the band gap is much larger than that of the narrow-
gap ferroelectric semiconductors, which suggests that the electron-phonon coupling is not
so strong in Cd1-xZnxTe solid solutions.

Figure 6. Temperature dependence of dielectric constant in Cd1-xZnxTe (x=0.1).

4.3. Zn1-xLixO

Dielectric constants of Zn1-xLixO ceramics with x=0.09 show an anomaly at 470 K (Tc) (Fig. 7),
although a high purity of ZnO does not show any anomaly from 20 K to 700 K [27]. The peak
value of dielectric anomaly is 21 ( x=0.1), which is the same order with Cd1-xZnxTe (ε ~ 50), but
much smaller than ordinal ferroelectrics by 2~4 orders. This means that the dipole-dipole cor‐
relation accompanied with this ferroelectric phase transition is not so large in Zn1-xLixO. In the
measurement of D-E hysteresis loop, a small and clear hysteresis curve was observed. The
spontaneous polarization varies by samples from 0.05 μC/cm2 to 0.59 μC/cm2. This is due to
that the preferred orientation of the c-axis, the direction of Ps of the samples varies depending
on samples. Naturally, powder of ZnO has egg-shaped grains which are elongated along the
c-axis due to the anisotropy of elastic constants. Therefore, the orientation of the ceramic sam‐
ple depends on the condition of the pressing process in the sample preparation. After the cor‐
rection of the preferred orientation by using X-ray diffraction, the value of spontaneous
polarizations of each sample converges to 0.9 μC/cm2 as shown in Fig. 8 [28, 29]. The transi‐
tion temperature, Tc, depends on the Li concentration. The phase diagram between Tc and x is
shown in Fig. 9. As temperature increases, Tc becomes higher,which reminds us the phase di‐
agram of quantum ferroelectrics such as KTa1-xNbxO3 and Sr1-xCaxTiO3.
238 Advances in Ferroelectrics

Figure 7. Temperature dependence of dielectric constant of Zn1-xLixO ceramics (x= 0.09).

Figure 8. Temperature dependence of spontaneous polarization of Zn1-xLixO ceramics(x = 0.06). The inset is D-Ehytere‐
sis loop observed below (left) and above Tc (right).
 Electronic Ferroelectricity in II-VI Semiconductor ZnO 239
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Figure 9. The Tc-x phase diagram of Zn1-xLixO.

Specific heat anomaly is small at the ferroelectric-paraelectric phase transition temperature.

The transition entropy ΔS is almost 0. If Li ions which substitute Zn ions occupy the off-center
position and behave an order-disorder motion, ΔS must be about Rln 2. If the nature of the tran‐
sition is displacive type, ΔS≏0. The observed thermal behavior suggests displacive nature, but,
however, no soft mode was observed in Raman scattering measurement [30]. The small dielec‐
tric anomaly and the absence of soft mode are consistent each other, when we consider the LST-
relation. Relaxation mode corresponding to an order-disorder motion has not been found also
by Raman scattering [31]. These peculiar dielectric properties of Zn1-xLixO is resemble to those
of Cd1-xZnxTe. These evidences suggests a new type of ferroelectric phase transition.

Pb1-xGexTe Cd1-xZnxTe Zn1-xLixO

Zinc-blende Wurtzite
Crystal Structure of Paraelectric Rock-salt (NaCl)
- ((P63mc ))
Phase ((Fm3m))
(( F 43m))
Rhombohedral Rhombohedral Wurtzite
Ferroelectric Phase
((R3m)) (( R3m)) ((P63mc ))
Tc (K) (x=0.1) 200 390 470
Eg (eV) 0.3 1.53 3.2
ρ (Ωm) 10 103 1010
Ps (μC/cm2) - 5 0.9
Soft mode ○ × ×
εpeak 103 50 21

Table 1. Dielectric properties of binary ferroelectric semiconductors.

240 Advances in Ferroelectrics

5. Electronic ferroelectricity in ZnO

It is considered that the replacement of host Zn atoms by substitutional Li atoms plays an

primary role for the appearance of ferroelectricity in ZnO. The problem is the effect of Li-
doping. Here we consider the following two models [32].
i. Structural size-mismatch model
Pure ZnO is polar along the c-axis and has dipole moments in crystals. Because of the size-
mismatch between Zn ion (the ionic radius: 0.74 Å) and Li ion (the ionic radius: 0.60 Å), sub‐
stituted Li ions displace from the Zn positions. These displacements may force to induce
extra dipole moments locally. It is considered that these local dipoles couple with dipoles of
the mother ZnO crystal and the structural ordering of local dipoles triggers to induce a fer‐
roelectric phase transition.
ii. Electronic model
According to the first-principle study by Corso et al [10], the hybridization between Zn 3d
electron and O 2p electron plays an important role in dielectric properties of ZnO. As the Li
atom has no d-electrons, it is considered that the partial replacement of Zn ions by Li ions
changes the nature of d the d-p hybridization. Therefore this doping is considered to induce
local extra dipole moments. These extra local dipoles couple with parent dipoles and induce
a new type of ferroelectricity.

To clarify which model is effective in the appearance of ferroelectricity in ZnO, the follow‐
ing structural and dielectric measurements were performed.

5.1. Rietveld analysis of structural changes in Zn1-xLixO ceramics

Structural changes associated with Li-substitution were studied by X-ray powder diffraction
[33]. Ceramic samples of Zn1-xLixO prepared by using a SPS (spark plasma sintering) method
were used in this experiment. The nominal value of x is 0.1 for the first sample. The Tc of the
sample was 470 K which is determined by dielectric constant measurements. The systematic
check of the absence of possible reflections (h-k=3n and l= odd for (hkl), n = integer) suggests
that the space group of the ferroelectric phase still remains P63mc, which is same as pure
ZnO. The obtained pattern was analyzed by the Rietveld method including the Li concentra‐
tion, x, as a refinable parameter. All parameters refined are shown in Table 2. The lattice
constants are a = 3.2487(1) and c = 5.2050(1) Å at 293 K. The actual Li concentration x is deter‐
mined to be 0.09. The final discrepancy factors were Rwp=7.4%, Rp=5.4% and RI=5.9%. The Zn-
O bond lengths are 1.9887 Å along the c-axis and 1.9735Å in the basal plane, respectively.
This means that the bond length along the c-axis shows a decrease by an amount of 0.003 Å
by Li-substitution in Li-doped ZnO. This lattice distortion is the order of 10-3 Å only, while
the displacement of Ti ions is the order of 0.1 Å in well-known ferroelectric BaTiO3. In this
phase transition, the crystal symmetry does not change associated with Li-substitution and
structural change is considerably small compared with the structural phase transition in typ‐
ical ferroelectrics.
 Electronic Ferroelectricity in II-VI Semiconductor ZnO 241
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Atom x y z B Occupation

Zn 1/3 2/3 0.3821(3) 0.52 0.91

Li 1/3 2/3 03821(3) 0.31 0.09

O 1/3 2/3 0 0.40 1.0

Table 2. Positional (x,y,z) and isotropic thermal (B) parameters in Zn1-xLixO at 293K.

5.2. Effect of Be and Mg dopants on Tc

The effect of dopants on Tc was studied based on the two models mentioned above. If the
ionic size-mismatch between the substituted and the host ions is important for ferroelectrici‐
ty, the introduction of Be ions should be more effective than Li and Mg doping. The ionic
radii of Li+, Be2+ and Mg2+ ions are 0.60 Å, 0.3 Å and 0.65 Å, respectively. If the changes in
electronic configuration are important, the Mg2+ ion (1s22s22p6) should play a different role
from the isoelectronic Li+ and Be2+ ions (1s2). Dielectric constant measurements were done on
Mg- and Be-doped ZnO ceramics [32]. A dielectric anomaly of Zn0.9Be0.1O was found at 496
K, which is very similar to those observed in Zn1-xLixO. However, Zn1-xMgxO samples show a
clear decrease of Tc. The dielectric anomaly in 30% Mg-doped ZnO found at 345 K is 150 K
lower than the Li-doped one. The concentration dependence of Tc of Be- and Mg-doped ZnO
is summarized in Fig. 10. The series of dielectric measurements show that the introduction
of Mg2+ suppresses Tc, while isoelectronic Be2+ shows almost the same Tc.

It is considered that the appearance of ferroelectricity in ZnO is primarily due to electronic

origin. The change in d-p hybridization caused by Li-substitution is responsible for this nov‐
el ferroelectricity and dielectric properties.

Figure 10. Tcvs. molar concentrations(x)of dopants, Li, Be and Mg in ZnO.

242 Advances in Ferroelectrics

In the next section, we shall study the change in electronic distribution, especially in the na‐
ture of d-p hybridization by Li-doping directly by X-ray diffraction, and discuss new elec‐
tronic ferroelectricity in ZnO.

6. X-ray study of electronic density distribution

X-ray diffraction measurements were performed for single crystals of pure ZnO and Zn1-
xLixO at 297 K and 19 K in order to investigate the changes in the crystal structure and the
electronic density distribution by Li-substitution in detail. Single crystal of pure ZnO was
prepared by the hydrothermal method [34]. The content of excess Zn ions of obtained single
crystal was 1.7 ppm and color was light yellowish (Fig. 11). In this hydrothermal method, it
is rather difficult to add a large amount of Li ions into single crystal. In order to dope Li
ions, several c-plate samples (0.16 mm thick) were annealed at an atmosphere of Li ions at
920 K for 24 hours. The light yellowish color of as-grown single crystal became transparent
after this doping as shown in Fig. 12. Li concentration x was measured by chemical analysis
and it is confirmed that x = 0.082~0.086.

Figure 11. Single crystal of as grown ZnO.

Figure 12. Single crystal of pure (left) and Li-doped ZnO (right).

Table 3 shows an experimental data of X-ray diffraction performed at room temperature

(293 K) and low temperature (19 K) by using a He-gas closed-cycle cryostat (Cryogenic
RC-110) mounted on a Huber off-center four-circle diffractometer to reduce the effect of
 Electronic Ferroelectricity in II-VI Semiconductor ZnO 243
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thermal vibration. The space group is confirmed to be P63mc for both pure and Li-doped
crystals. The Lorentz and polarization, thermal diffuse scattering (TDS) (the elastic constants
used in TDS collection are C11=20.96, C33=21.09, C12=12.10, C13=10.51, C44=4.243 [1011dyn/cm2],
absorption (spherical) and extinction (anisotropic, type I) corrections were made. Crystal
structures were refined using a full-matrix least squares program (RADIEL) [35].

ZnO Zn1-xLixO

Temperature 293 K 19 K 293 K 19 K

X-ray Radiation AgKα AgKα MoKα AgKα

(sinθ/λ)max 1.36 1.36 1.00 1.27

Number of Reflections 3157 2533 1296 2377

(|Fo| "/> 3σ |Fo|)

μR 1.91 2.84 7.67 3.96

R(F) (%) 2.61 3.84 3.05 3.62

RW(F) (%) 3.38 4.86 3.90 4.54

S 1.00 1.06 1.09 1.01

Table 3. Experimental data.

Accurate electron densities of single crystals of paraelectricZnO and ferroelectric Li-doped

ZnO at 19 K were analyzed by the maximum-entropy method (MEM) [36]. The MEM analy‐
ses were performed using the MEED (maximum-entropy electron density) program [37].

6.1. Crystal structures of single crystals of ZnO and Li-doped ZnO at 293 K

The final positional parameters and thermal factors at 293 K are given with their estimated
standard deviation in Table 4 [38]. The final discrepancy factors are R(F)=2.61 %, Rw(F)=3.38
% for ZnO, and R(F)=3.05 %, Rw(F)=3.90 % for Zn1-xLixO. The lattice constants a and c of Zn1-
xLixO become smaller than those of pure ZnO by 0.002 ~ 0.003 Å. Lattice distortion in Zn1-

xLixO is only the order of 10 Å along the polar axis, which is consistent with that of ceramic
-3

sample measured by thermal expansion [39]. These changes are regarded as the changes as‐
sociated with ferroelectric phase transition because Li-doped ZnO is ferroelectric phase and
pure ZnO is paraelectric phase. In BaTiO3, the lattice constants change by 0.02 Å. In ZnO,
changes in the lattice constants are smaller than that of BaTiO3 by one order. The thermal
factors U33 of Zn and O atoms in Zn1-xLixO are smaller than U11 by 25-35 %, although those
values in pure ZnO are almost same. This implies that the thermal vibration in Zn1-xLixO is
suppressed along the c-axis. But in ZnO, the effect from bonding electron is also included in
the thermal factors since strong covalence exists. The effects of thermal vibration and bond‐
ing electron cannot be distinguished at 297 K. The Li concentration x, the positional parame‐
ter u and isotropic thermal factor U of Li are refined after all the other parameters are
determined. Two cases are assumed for the Li position: the first is the interstitial position
244 Advances in Ferroelectrics

and the second is host Zn position. The discrepancy factor became larger when Li locates at
interstitial Li position than Zn position. Therefore, present results support that Li substitutes
Zn. The precise refinement shows that Li locates at the off-center position from the Zn posi‐
tion by 0.02 Å in Zn1-xLixO along the c-axis.

ZnO (a=3.2489(1) Å, c=5.2049(3) Å) at 293 K

x y z U 11 U 33 U eq Occupation
Zn 1/3 2/3 0.3815(1) 0.0086(1) 0.0088(1) 0.0087(1) 1.0
O 1/3 2/3 0 0.0085(1) 0.0088(1) 0.0086(1) 1.0
Zn1-xLixO (a=3.2467(3) Å, c=5.2032(1) Å) at 293 K
x y z U 11 U 33 U eq Occupation
Zn 1/3 2/3 0.3804(3) 0.0075(1) 0.0055(1) 0.0068(1) 0.914
Li 1/3 2/3 0.376(36) 0.0036(48) 0.086
O 1/3 2/3 0 0.0088(3) 0.0057(41) 0.0078(3) 0.957

Table 4. Crystal structure of ZnO and Zn1-xLixO at 293 K.(The form of thermal factors are exp[-2π2(U11a*2h2 + U22b*2k2 +
U33c*2l2 + 2U12a*b*hk + 2U23b*c*kl + 2U31c*a*lh)] for anisotropic (Zn and O) and exp(-8π2Ueqsin2θ/λ) for isotropic (Li)
atoms.)

The bond lengths and angles of ZnO4 group are shown in Table 5. The Zn-O bond length
does not change in the basal plane, but becomes short along the c-axis by an amount of 0.007
Å by Li-substitution.

Bond length Bond Angle

Apical Basal Apical Basal

ZnO 1.986(1) Å 1.975(1) Å 108.20(3)o 110.71(3)o

Zn1-xLixO 1.979(1) Å 1.975(1) Å 108.37(4) o

110.55(4)o

Table 5. Bond lengths and angles in ZnO and Zn1-xLixO at 293 K.

The distributions of electronic density around Zn and O atoms at 293 K are obtained by us‐
ing Fourier analysis (Fig. 13). The difference Fourier maps between observed distribution
ρobs and calculated distribution ρcal in the (110) plane are shown in Fig. 14. Since the bonding
electron is not distributed spherically in ZnO, the section of the bonding electron appears in
the difference map. It is seen that there are large negative distributions (blue region) around
Zn atom along the c-axis in Zn1-xLixO. This suggests that the core electrons disappear from
the Zn atom. The broadening of map due to anharmonic thermal vibrations is also appreci‐
ated. The positive electronic density is observed near the O atom. It corresponds to the anti‐
bonding orbital of O 2p-electron.
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Figure 13. The charge density maps of (a) ZnO and (b) Zn1-xLixO at 293 K in the (110) plane obtained by Fourier analysis.

Figure 14. The difference fourier maps of charge densities of (a) ZnO and (b) Zn1-xLixO at 293 K in the (110) plane with
a contour increment of 0.2 e/ Å 3. Bluish cold color means negative charge density and reddish warm region is positive
charge density.
246 Advances in Ferroelectrics

6.2. Crystal structures at 19 K

Crystal structures at low temperature are shown in Table 6 [38]. The final discrepancy fac‐
tors are R(F)=3.84 %, Rw(F)=4.86 % for ZnO, and R(F)=3.62 %, Rw(F)=4.54 % for Zn1-xLixO. Li
ion shifts from the Zn position by 0.08 Å at 19 K, which is four times larger than that at r. t..
The Zn-O bond lengths decrease by an amount of 0.002 Å along both basal and apical axes
in Zn1-xLixO, while their bond angles are almost the same in both crystals (Table 7 and Fig.
15). The Fourier and difference maps of electronic distribution are shown in Figs. 16 and 17.
Comparing with the result of 293 K, bonding electrons are clearly observed around the cen‐
ter of Zn-O bond in both crystals. In Zn1-xLixO, negative distribution is observed around Zn
atom, whose shape corresponds to Zn-3dz2-orbital. It suggests the disappearance of 3d-elec‐
trons from Zn atom in Zn1-xLixO. The positive density near O atoms corresponds to the 2p-
orbital of O atom.

ZnO (a=3.2465(8) Å, c=5.2030(19) Å) at 19 K

x y z U 11 U 33 Occupation

Zn 1/3 2/3 0.3812(1) 0.0033(1) 0.0032(1) 1.0

O 1/3 2/3 0 0.0041(1) 0.0048(2) 1.0

Zn1-xLixO (a=3.2436(5) Å, c=5.1983(30) Å) at 19 K

x y z U 11 U 33 U eq Occupation

Zn 1/3 2/3 0.3811(2) 0.0032(1) 0.0026(1) 0.0030(1) 0.914

Li 1/3 2/3 0.366(12) - - 0.0036(48) 0.086

O 1/3 2/3 0 0.0053(3) 0.0043(3) 0.0050(2) 0.957

Table 6. Crystal structure of ZnO and Zn1-xLixO at 19 K.(The form of thermal factors are exp[-2π2(U11a*2h2 + U22b*2k2 +
U33c*2l2 + 2U12a*b*hk + 2U23b*c*kl + 2U31c*a*lh)] for anisotropic (Zn and O) and exp(-8π2Ueqsin2θ/λ) for isotropic (Li)
atoms.)

0.957 0.957

Apical Basal Apical Basal

ZnO 1.983(2) Å 1.974(1) Å 108.25(4)o 110.66(4)o

Zn1-xLixO 1.981(2) Å 1.972(1) Å 108.27(3)o 110.65(3)o

Table 7. Bond lengths and angles in ZnO and Zn1-xLixO at 19 K.

 Electronic Ferroelectricity in II-VI Semiconductor ZnO 247
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(a) Pure ZnO (b) Li-doped ZnO

Figure 15. Structural Changes of ZnO4 group at 19 K. The shift of Li ion is 0.08 Å from the Zn position.

Figure 16. The charge density maps of (a) ZnO and (b) Zn1-xLixO at 19 K in the (110) plane obtained by Fourier analysis.
248 Advances in Ferroelectrics

Figure 17. The difference maps of charge densities of (a) ZnO and (b) Zn1-xLixO at 19 K in the (110) plane with a con‐
tour increment of 0.2 e/ Å 3. Bluish cold color means negative charge density and reddish warm color region is positive
charge density.

6.3. Bond electron densities at 19 K

The discrepancy factors of MEM analysis for pure ZnO at 19 K are R(F)=1.20 % and
Rw(F)=1.39 % [40]. The electron density map of ZnO in the (110) plane is shown in Fig. 18(b).
The covalent character of Zn-O bonds is clearly observed. Charge densities at the center of
Zn-O bonds are 0.58 e/ Å 3 for the apical bond, and 0.56 e/Å 3 for the basal one. The density of
bonding electron of the apical bond is larger than that of the basal by 3.6 %. The electron
density of O atom distorts toward the Zn atom along the c-axis. The electron density of Zn
atom elongates to the third nearest O atom.

The final discrepancy factors for the ferroelectric Zn1-xLixO at 19 K are R(F)=0.87 % and
Rw(F)=0.85%. The electron density map of Zn1-xLixO in the (110) plane is shown in Fig. 18(c).
The covalent character of Zn-O bonds is also seen in Zn1-xLixO. Charge densities of the Zn-O
at the saddlepoint are 0.46 e/ Å 3 for the apical bond, and 0.49 e/ Å 3 for the basal one. Each
value is smaller than that of pure ZnO. It is considered that this may be due to the decrease
of total charge by Li-substitution. The density of bonding electron of the basal bond is larger
than that of the apical by 6.5 %, on the contrary to the case of ZnO. The electron density of O
atom is distorted anisotropically, similar to the pure ZnO, but the direction is opposite. The
extension of Zn atom toward the third nearest O atom, which is observed in ZnO, was not
detected in Zn1-xLixO.
 Electronic Ferroelectricity in II-VI Semiconductor ZnO 249
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(a)

(b) (c)

Figure 18. The electronic Distribution by MEM method. (a) The (110) plane of ZnO. Shaded atoms are included in the
plane.(b)The MEM charge density map of ZnO at 19 K in the (110) plane. (c) The MEM charge density map of
Zn0.914Li0.086O at 19 K in the (110) plane. Contours are drawn from 0.4 e/ Å 3 at 0.2 e/ Å 3 intervals.

6.4. Difference between Li-doped ZnO and pure ZnO

The difference of the charge densities between two crystals is calculated by subtracting the
MEM charge densities of pure ZnO from those of Zn1-xLixO as in Fig. 19 [40]. The values of
MEM charge densities of pure ZnO are normalized by multiplying 0.930, because the total
charges of two crystals are different. The positive and negative peaks were observed around
the O atom. This is due to the shift of O atom from the host position opposite to the Zn atom
along the c-axis in Zn1-xLixO. Four negative peaks are observed around the Zn atom. These
peaks correspond to the Zn 3d-orbitals and suggest that the 3d-electrons disappear from the
Zn site, compared with wave functions of Zn 3d- and O 2p-orbitals of ZnO obtained by DV-
Xα calculation in Fig. 20. This result is the same as that calculated by the Fourier synthesis
previously. The bonding region around the apical and the basal Zn-O bonds is covered by
positive electron distribution. This implies that the Zn 3d-electrons transfer to the bonding
electrons in Zn1-xLixO.
250 Advances in Ferroelectrics

Figure 19. The difference map between MEM charge densities of Zn1-xLixO and ZnO at 19 K in the (110) plane. Contours are
drawn from -5.0 e/ Å 3 to 5.0 e/ Å 3 at 0.5 e/ Å 3 intervals. Shaded area eith reddish color indicates positive charge.

Figure 20. Wave functions of Zn 3d- and O 2p-orbitals of ZnO obtained by DV-Xα calculation. Red lines indicate the
positive and Blue lines indicate the negative area.
 Electronic Ferroelectricity in II-VI Semiconductor ZnO 251
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In Li-doped ZnO, negative peaks around Zn atom corresponding to 3dz2 orbital were ob‐
served in difference Fourier map, and also in the MEM difference map between the ferro‐
electric phase and the paraelectric phase. These results may be related to the existence of
localized d-holes in Li-doped ZnO. It is considered that 3dz2 electrons transfer to bonding
region and play a role for contribution for the covalence observed from the result of the
MEM analysis. Furthermore, the antibonding orbital of 2p electron is observed in differ‐
ence Fourier map of Li-doped ZnO. It is suggested that the interaction between d-holes
and p-electrons should be closely related to the appearance of the ferroelectricity in Li-
doped ZnO.

7. Discussion

The ferroelectric phase transition accompanies with structural distortions in usual ferro‐
electrics. Portengen, Ostreich and Sham reported the theory of electronic ferroelectricity
[41], which examined possibilities of electronic ferroelectricity, based on the spinless Fali‐
kov-Kimball (FK) model [42] with a k-dependence hybridization in Hartree-Fock approxi‐
mation. The FK model introduces two types of electrons, itinerant d-electrons and
localized f-electrons. The valence transition is driven by on-site Coulomb repulsion be‐
tween the d-electrons and f-electrons. They found that the Coulomb interaction between
itinerant d-electrons and the localized f-electrons give rise to an excitonic<d+f> expectation
value, which breaks the center of symmetry of the crystal and leads to electronic ferroelec‐
tricity in mixed-valent compounds. In this electronic model, the transition involves a
change in the electronic structure rather than the structural one. The estimated spontane‐
ous polarization is of the order of 10 μC/cm2, which is comparable to those in displacive
type ferroelectrics such as BaTiO3.
In the case of Li-doped ZnO, the d-p hybridization should be changed by Li-doping. The d-
holes and itinerant electrons should be closely related to the appearance of Li-doped ZnO. It
should be further detailed studies would be necessary whether this proposed theory is ap‐
plicable for the electronic ferroelectricity found in ZnO or not.
Recently Glinchuk et al propose the mechanism of impurities induced ferroelectricity in
nonperovskite semiconductor matrices due to indirect dipole interaction via free carriers
[43]. They showed that the ferroelectricity in Li-doped ZnO might appear due to indirect
interaction of dipoles, formed by off-center impurities, via free charge carriers, namely, the
Ruderman–Kittel–Kasuya–Yosida (RKKY)-like indirect interaction of impurity dipoles via
free charge carriers. They estimated that the typical semiconducting concentration of the
carriers like 1017 cm−3 is sufficient for the realization of the ferroelectricity. The finite con‐
ductivity does not mean complete destruction of possible ferroelectric order and shows
rather many interesting effects. In this theory, they have succeeded to obtain the sponta‐
neous polarization and the phase diagram of Tcvs. impurity molar ratio (x) as shown in
Fig. 21.
252 Advances in Ferroelectrics

Figure 21. The calculated spontaneous polarization and the phase diagram of Tcvs. impurity molar ratio (x) after Glin‐
chuk et al [36].

Experimental results suggest the existence of localized d-holes and p-electrons in Li-doped
ZnO. We consider that the interaction between d-holes and p-electrons may be related to the
appearance of the ferroelectricity in Li-doped ZnO. However, there are many proposals for
this peculir novel ferroelectricity in ZnO. Scott and Zubko have pointed out the possibility
of a classic electret mechanism for Li-doped ZnO[44]. Tagantsev discussed a Landau theory,
where a crystal on cooling from a state with polar symmetry exhibits a maximum of dielec‐
tric permittivity and D-E hysteresis loops [45]. He proposed that these ferroelectric like phe‐
nomena corresponds to the case for Li-doped ZnO. Furthermore, the multiferroic behavior
has been reported in impurity-doped ZnO [46]. At present, further detailed experiments
should be expected to clarify the nature of Li-doped ZnO.

8. Conclusion

Dielectric properties and crystal structures and electron density distributions studied on
pure ZnO and Zn Li O by the precise X-ray diffraction are reviewed in comparison with fer‐
1-x x

roelectric semiconductors Pb Ge Te and Cd Zn Te. It is considered that the appearance of

1-x x 1-x x

ferroelectricity in ZnO is primarily due to electronic origin. The change in d-p hybridization
caused by Li-substitution is considered to be responsible for this novel ferroelectricity and
dielectric properties. Although the ferroelectric phase transition accompanies with structural
distortions in usual ferroelectrics, the structural changes observed in Zn Li O are the order1-x x

of 10 Å. The clear change of Zn 3d-electron is observed. It suggests Zn 3d-electron of Zn

-3

1-

x
Li O transfers from Zn atom to the bonding. The positive electronic density is observed near
x

the O atom. It corresponds to the antibonding orbital of O 2p-electron. These results suggest
the existence of localized d-holes and p-electrons in Li-doped ZnO. It may be probable that
the interaction between d-holes and p-electrons may be related to the appearance of the fer‐
roelectricity in Li-doped ZnO.
For long time, the importance of electronic contribution has been pointed out in the field of
ferroelectrics, since the simple superposition of electronic polarizability does not hold in
many ferroelectric substances. Many efforts have been done in vain because of complexity of
 Electronic Ferroelectricity in II-VI Semiconductor ZnO 253
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crystal structures of ferroelectrics. As the crystal structure of ZnO is very simple, the elec‐
tronic contribution could be observed rather easily. It is considered that this result is the first
example to discuss the electronic contribution for ferroelectricity.

Author details

Akira Onodera and Masaki Takesada

Department of Physics, Faculty of Science, Hokkaido University, Sapporo, Japan

References

[1] Klingshirn C F, Meyer B K, Waag A, Hoffmann A and Geurts J. Zinc Oxide From
Fundamental Properties Towards Novel Applications. Springer, 2010.
[2] Yao T (ed.). ZnO Its Most Up-to-date Technology and Application, Perspectives (in
japanese). CMC Books, 2007.
[3] Heiland G. Mollwo E and Stockmann F. Solid State Phys 1959; 81: 193.
[4] Campbell C. Surface Acoustic Wave Devices and Their Signal Processing Applica‐
tion. San Diego: Academic Press; 1989.
[5] Hirshwald W. Current Topics Mater Sci 1981; 7, 143.
[6] Tsukazaki A, Ohtomo A, Onuma T, Ohtani M, Makino T, Sumiya M, Ohtani K, Chi‐
chibu S F, Fuke S, Segawa Y, Ohno H, Koinuma H and Kawasaki M. Nature Materi‐
als 2005; 4: 42.
[7] Joseph M, Tabata H and Kawai T. Jpn J Appl Phys 1999; 38: L1205.
[8] Bilz H, Bussmann-Holder A, Jantsch W and Vogel P. Dynamical Properties of IV-VI
[9] Compounds. Berlin: Springer-Verlag; 1983.
[10] Weil R, Nkum R, Muranevich E and Benguigui L. Phys Rev Lett 1989; 62: 2744.
[11] Onodera A, Tamaki N, Kawamura Y, Sawada T and Yamashita H. Jpn. J Appl Phys
1996; 35: 5160.
[12] Abrahams C S and Bernstein L J. Acta Cryst 1969; B25: 1233.
[13] Corso D A, Posternak M, Resta R and Baldereshi A. Phys Rev 1994; B50: 10715.
[14] Zakharov O, Rudio A, Blase X, Cohen L M and Louie G S. Phys Rev1994; B50: 10780.
[15] Massida S, Resta R, Posternak M and Baldereschi A. Phys Rev 1995; B50.
[16] Osikiri M and Aryasetiawan F. J Phys Soc Jpn 2000; 69: 2123.
254 Advances in Ferroelectrics

[17] Minami T, Nanto H and Tanaka S. Jpn J Appl Phys 1984; 23: L280.
[18] Laudise A R, Kolb D E and Caporaso J A. J Am Ceram Soc 1964; 47: 9.
[19] Kolb D E and Laudise A R. J Am Ceram Soc 1966; 49: 302.
[20] Yang CK and Dy S K. Solid State Commun 1993; 88: 491.
[21] Usuda M, Hamada N, Kotani T and Schilfgaarde M. Phys Rev 2001; B66: 075205.
[22] Zhang B S, Wei S -H and Zunger A. Phys Rev 2001; B63: 075205.
[23] Tamaki N, Onodera A, Sawada T and Yamashita H. J Kor Phys 1966; 29: 668.
[24] Onodera A, Tamaki N, Jin K and Yamashita H. Jpn J Appl Phys 1997; 36: 6008.
[25] Islam T Q and Bunker A B. Phys Rev Lett 1987; 59: 2701.
[26] Benguigui L, Weil R, Muranevich E, Chack A and Fredj E. J Appl Phys 1993; 74:513.
[27] Terauchi H, Yoneda Y, Kasatani H, Sakaue K, Koshiba T, Murakami S, Kuroiwa Y,
Noda Y, Sugai S, Nakashima S and Maeda H. Jpn J Appl Phys 1993; 32: 728.
[28] Onodera A, Yoshio K, Satoh H, Yamashita H and Sakagami N. Jpn. J. Phys. Phys.
1998; 37; 5315.
[29] Onodera A, Tamaki N, Satoh H, Yamashita H and Sakai A. Ceramic Transactions
1999; 100; 77.
[30] Onodera A and Satoh H. Frontiers in Science and Technology – Ferroelectrics Vol. 1,
Stefan University Press, 2002; 93.
[31] Islam E, Sakai A and Onodera A. J Phys Soc Jpn 2001; 70: 576.
[32] Kagami D, Takesada M, Onodera A and Satoh H. J Kor Phys 2011; 59: 2532.
[33] Hagino S, Yoshio K, Yamazaki T, Satoh H, Matsuki K and Onodera A. Ferroelectrics
2001; 264: 235.
[34] Onodera A, Yoshio K, Satoh H, Tamaki T, Takama T, Fujita M and Yamashita H. Fer‐
roelectrics 1999; 230: 465.
[35] Sakagami N. J Cryst Growth 1990; 99: 905.
[36] Coppens P, Guru Row N T, Leung P, Stevens D E, Becker J P and Yang W Y. Acta
Crystallogr 1979; A35: 63.
[37] Sakata M and Sato M. Acta Crystallogr 1990; A46: 263.
[38] Kumazawa S, Kubota Y, Tanaka M, Sakata M and Ishibashi Y. J Appl Cryst 1993; 26:
453.
[39] Yoshio K, Onodera A, Satoh H, Sakagami N and Yamashita H. Ferroelectrics 2001;
264; 133.
[40] Onodera A, Tamaki N, Satoh H and Yamashita H. Ferroelectrics 1998; 217: 9.
 Electronic Ferroelectricity in II-VI Semiconductor ZnO 255
http://dx.doi.org/10.5772/52304

[41] Yoshio K, Onodera A, Satoh H, Sakagami N and Yamashita H. Ferroelectrics 2002;

270; 357.

[42] Portengen T, Ostreich Th and Sham J L. Phys Rev 1996; B54: 17452.

[43] Falicov M L and Kimball C J. Phys Rev Lett 1969; 22: 997.

[44] Glinchuk D M, Kirichenko V E, Stephanovich A V and Zaulychny Y B. Appl Phys

2009; 105: 104101.

[45] Scott F J and Zubko P. IEEE Xplore 2005; ISE-12 (12th International Symposium on
Electrets): 113-116.

[46] Tagantsev K A. Appl Phys Let 2008; 93: 202905.

[47] Yang C Y, Zhong F C, Wang H X, He B, Wei Q S, Zeng F and Pan F. Appl Phys 2008;
104: 064102.
 Chapter 12

Doping-Induced Ferroelectric Phase Transition and

Ultraviolet-Illumination Effect in a Quantum
Paraelectric Material Studied by Coherent Phonon
Spectroscopy

Toshiro Kohmoto

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/45744

1. Introduction

There has been significant interest in a quantum paraelectric material strontium titanate
(SrTiO3), and its lattice dynamics and unusual dielectric character have been extensively
studied. In low temperatures, its dielectric constant increases up to about 30 000. The dielec‐
tric constant increases extraordinarily with decreasing temperature while the paraelectric
phase is stabilized by quantum fluctuations without any ferroelectric phase transition even
below the classical Curie temperature Tc=37 K [1]. In SrTiO3, a ferroelectric transition is easi‐
ly induced by a weak perturbation such as an uniaxial stress [2], an isotopic substitution of
oxygen 18 for oxygen 16 [3], and an impurity doping [4,5].

SrTiO3 has a perovskite structure as shown in Fig. 1(a) and is known to undergo a structural
phase transition at Tc=105 K [6]. The cubic (Oh) structure above Tc, where all phonon modes
are Raman forbidden, changes into the tetragonal (D4h) structure below Tc, where Raman-al‐
lowed modes of symmetries A1g and Eg appear [7]. The phase transition is due to the collapse
of the Γ25 mode at the R point of the high-temperature cubic Brillouin zone. Below Tc, the R
point becomes the Γ point of the D4h phase. The phase transition is characterized by the soft‐
ening of phonons at the R point and concomitant doubling of the unit cell.

The distortion consists of an out-of-phase rotation of adjacent oxygen octahedra in the (100)
planes [6]. The order parameter for the phase transition is inferred to be the angle of rotation
of the oxygen octahedra. Only a small rotation of the oxygen octahedra is involved for the
transition. The rotation angle for the oxygen octahedra varies from ~2° of arc near 0 K down

© 2012 Kohmoto; licensee InTech. This is an open access article distributed under the terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
258 Advances in Ferroelectrics

to zero at Tc=105 K; the transition is second order. At liquid nitrogen temperature, the rota‐
tion angle is about 1. 4° and the linear displacement of the oxygen ions about their high-tem‐
perature equilibrium positions is less than 0.003 nm. This oxygen octahedron motion can be
described as a rotation only as a first approximation; the oxygen ions actually remain on the
faces of each cube and therefore increase in separation from the titanium. Because the (100)
planes are equivalent in the cubic phase, the distortion produces domains below Tc in which
the [100], [010], or [001] axis becomes the unique tetragonal c axis.

Figure 1. (a) Perovskite structure in SrTiO3. (b) Doped Ca ions are substituted for the Sr ions in Ca-doped SrTiO3.

According to the measurement of dielectric constants, Sr1−xCaxTiO3 undergoes a ferroelectric

transition above the critical Ca concentration xc=0. 0018, where doped Ca ions are substituted
for the Sr ions [8–11] as shown in Fig. 1(b). The cubic structure above the structural phase-tran‐
sition temperature Tc1 changes in to the tetragonal structure below Tc1 and into the rhombohe‐
dral structure below the ferroelectric transition temperature Tc2. The structural phase transition
at Tc1 is also antiferrodistortive as in pure SrTiO3 at 105 K [8]. As in the case of impurity systems,
Li-doped KTaO3 and Nb-doped KTaO3 [4], off-centered impurity ions are supposed. Their po‐
larized dipole moments show a ferroelectric instability below the ferroelectric transition tem‐
perature [4]. In the case of Ca-dopedSrTiO3, a spontaneous polarization occurs along [110]
directions in the c plane, where the tetragonal (D4h) symmetry is lowered to C2v [8]. With de‐
creasing temperature a ferroelectric ordering process dominates, that is, due to the thermal
growth of the polarization clouds surrounding the off-center Ca2+ dipoles [8]. The system be‐
haves like a super paraelectric as the ferroelectric nano-ordered regions contain disordered
cluster like regions. The investigation by x-ray and neutron diffractions and first-principles cal‐
culations [12] suggests that polar instabilities originating from the off-center displacements of
 Doping-Induced Ferroelectric Phase Transition and Ultraviolet-Illumination Effect in a Quantum Paraelectric... 259
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Ca2+ ions are not likely to directly polarize the host matrix by an electrostatic mechanism. In‐
stead, the possible role of random fields in inducing the presence of disordered polar clusters
was suggested, which is similar to polar nanoregions in relaxor materials.

Recently, a gigantic change in the dielectric constant by an ultraviolet (UV) illumination was
discovered [13,14], and a deeper interest has been taken in SrTiO3 again. The origin of the
giant dielectric constants, however, has not yet been clarified. In Ca-doped SrTiO3, it was re‐
ported that a UV illumination causes a ferroelectric peak shift of the dielectric constant to‐
ward the lower temperature side [11]. In several ferroelectric materials such as BaTiO3 [15],
SbSI [16], and oxygen-isotope-substituted SrTiO3 [17], the Tc reduction under a UV illumina‐
tion has been observed.

The optical information on the dielectric response is usually obtained from the experiments
of Raman scattering or infrared spectroscopy. The usefulness of the investigation of low-fre‐
quency dielectric response by observing coherent phonons have also been demonstrated by
the time-resolved study of the dynamics of phonons [18] and phonon polaritons [19]. At low
frequencies this technique is very sensitive and provides a very good signal-to-noise ratio as
compared to the conventional frequency-domain techniques while at higher frequencies a
better performance will be achieved by using the conventional techniques. Therefore the co‐
herent phonon spectroscopy and the conventional frequency-domain techniques can be con‐
sidered to be complementary methods for the investigation of the dielectric response.

The observed signal of the Raman scattering [20] in SrTiO3 is very weak because the distortion
from cubic structure in the low-temperature phase is very small. The intensity of the first-order
Raman signal is of the same order of magnitude with many second-order Raman signals, and
then a background-free signal of the first-order Raman scattering cannot be observed.

Under a UV illumination, SrTiO3 and Ca-doped SrTiO3 show a broadband luminescence in

the visible region originated from a relaxed excited state [21]. The coherent phonon spectro‐
scopy is not sensitive to the luminescence and a powerful technique to investigate UV-illu‐
mination effects in paraelectric materials as compared to the Raman-scattering measurement
because in Raman-scattering experiments, it is not easy to separate Raman-scattering signals
from the luminescence.

In the present study, ultrafast polarization spectroscopy is used to observe the coherent opti‐
cal phonons in pure and Ca-doped SrTiO3, which are generated by femtosecond optical
pulses through the process of impulsive stimulated Raman scattering [22,23]. Time-depend‐
ent linear birefringence induced by the generated coherent phonons is detected as a change
of the polarization of probe pulses. High detection sensitivity of ~10−5 in polarization change
has been achieved in our detection system. Damped oscillations of coherent phonons in
SrTiO3 were observed below the structural phase-transition temperature (Tc=105 K), and
temperature dependences of the phonon frequency and the relaxation rate are measured
[24]. The mechanism of the phonon relaxation is discussed by using a population decay
model, in which an optical phonon decays into two acoustic phonons due to an harmonic
phonon-phonon coupling.
260 Advances in Ferroelectrics

The doping-induced ferroelectric phase transition in Ca-doped SrTiO3 is investigated by ob‐

serving the birefringence and coherent phonons [25]. In the birefringence measurement, the
structural and the ferroelectric phase-transition temperatures are examined. In the observa‐
tion of coherent phonons, the soft phonon modes related to the structural (Tc1=180 K) and
the ferroelectric (Tc2=28 K) phase transitions are studied, and their frequencies are obtained
from the observed coherent phonon signals. The behavior of the softening toward each
phase-transition temperature and the UV-illumination effect on the ferroelectric transition
are discussed. In addition to the ferroelectric phase transition at Tc2=28 K, another structural
deformation at 25 K is found. A shift of the ferroelectric phase-transition temperature under
the UV illumination and a decrease in the phonon frequencies after the UV illumination are
found. We show the approach in the time domain is very useful for the study of the soft
phonon modes and their UV-illumination effect in dielectric materials.

2. Experiment

The experiments are performed on single crystals of pure SrTiO3 and Ca-doped SrTiO3 with
the Ca concentration of x=0.011. SrTiO3 was obtained commercially (MTI Corporation) and
Ca-doped SrTiO3 was grown by the floating zone method [11]. The thickness of the sample
is 1. 0 and 0.5 mm for the pure and Ca-doped crystals, respectively. In Ca-dopedSrTiO3, the
structural phase-transition (Oh→D4h) temperature, Tc1=180 K, is obtained from the result of
the birefringence measurement in section 3. The ferroelectric phase-transition temperature,
Tc2=28 K, was determined by the measurement of dielectric constants [11]. The value of x
was determined by the empirical relation of Bednorz and Müller [5].

Schematic diagram of the experiment of polarization spectroscopy is shown in Fig. 2. The

change in optical anisotoropy (birefringence) is detected by a polarimeter as the change in
the polarization of the probe light (ellipticity). In the birefringence measurement, the bire‐
fringence generated by the lattice deformation is detected by a continuous-wave (cw) probe
beam with no pump beam. In the coherent phonon spectroscopy, the transient birefringence
due to the coherent phonons generated by a pump pulse is detected by a probe pulse.

Figure 2. Schematic diagram of the experiment of polarization spectroscopy.

 Doping-Induced Ferroelectric Phase Transition and Ultraviolet-Illumination Effect in a Quantum Paraelectric... 261
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2.1. Birefringence measurement

In the birefringence measurement, the linearly polarized probe beam is provided by a
Nd:YAG laser (532 nm, cw) and is perpendicular to the (001) surface of the sample.
The construction of the polarimeter is shown in Fig. 3. The polarimeter [26,27] detects the
rotation of polarization plane of a light beam. A linearly-polarized beam is split by a polar‐
ized beam splitter (PBS) and incident on the two photodiodes (PD) whose photocurrents
are subtracted at a resistor (R). When the polarized beam splitter is mounted at an angle of
45o to the plane of polarization of the light beam, the two photocurrents cancel. If the plane
of polarization rotates, the two currents do not cancel and the voltage appears at the resistor.

Figure 3. Construction of the polarimeter.

In the present experiment, the birefringence generated by the lattice deformation is detected
as the change in polarization of the probe beam using a quarterwave plate and the polarime‐
ter. The birefringence generated in the sample changes the linear polarization before trans‐
mission to an elliptical polarization after transmission. The linearly-polarized probe beam is
considered to be a superposition of two circularly-polarized components which have the op‐
posite polarizations and the same intensities. The generated birefringence destroys the in‐
tensity balance between the two components. The two circularly-polarized beams are
transformed by the quaterwave plate to two linearly-polarized beams whose polarizations
are crossed each other, and the unbalance of circular polarization is transformed to the un‐
balance of linear polarization or the rotation of polarization plane. This rotation is detected
by the polarimeter as the signal of the lattice deformation.

2.2. Observation of coherent phonons

Coherent phonons are observed by ultrafast polarization spectroscopy with the pump-probe
technique. The experimental setup for coherent phonon spectroscopy is shown in Fig. 4. Coher‐
ent phonons are generated by femtosecond optical pulses through the process of impulsive
 5
Running Title
262 Advances in Ferroelectrics
1 In the present experiment, the birefringence generated by the lattice deformation is
2 detected as the change in polarization of the probe beam using a quarterwave plate and the
3 polarimeter. The birefringence generated in the sample changes the linear polarization
4 stimulated
before Raman scattering
transmission [22,23], and
to an elliptical are detected
polarization afterbytransmission.
monitoring the
Thetime-dependent ani‐
linearly-polarized
5 sotropy of refractive index induced by the pump pulse. The pump pulse is
probe beam is considered to be a superposition of two circularly-polarized componentsprovided by a Ti:
6 sapphire regenerative amplifier whose wavelength, pulse energy, and pulse width
which have the opposite polarizations and the same intensities. The generated birefringence at the sam‐
7 destroys the
ple are 790 nm,intensity balance
2 μJ, and 0.2 ps,between the two
respectively. components.
The probe pulse isThe two circularly-polarized
provided by an optical para‐
8 beams are transformed by the quaterwave plate to two linearly-polarized
metric amplifier whose wavelength, pulse energy, and pulse width are 690 nm, 0. beams whose
1 μJ, and 0.2
9 polarizations are crossed each other, and the unbalance of circular polarization
ps, respectively. The repetition rate of the pulses is 1kHz. The linearly polarized pump and is
10 transformed to the unbalance of linear polarization or the rotation of polarization
probe beams are nearly collinear and perpendicular to the (001) surface of the sample, and are plane.
11 This rotation is detected by the polarimeter as the signal of the lattice deformation.
focused on the sample in a temperature-controlled refrigerator. The waist size of the beams at
the sample is about 0.5 mm.
12 2.2. Observation of coherent phonons
13
14
15 1 kHz, 0.2 ps
16 Mode-Locked Ti:Sapphire
17 Ti:Sapphire Regen. Amp.
790 nm
18
19 Optical
20 Parametric
21 Amp.
22 delay
23
24
Computer
25
26
27 690 nm
28 Lock-in Amp.
29
30 probe o
45
31 Polarimeter
32
λ/4 λ/4
33 sample pump
34 polarizer
35
Photoelastic
36 Modulator
37
38 Fig. 4. Experimental setup for coherent phonon spectroscopy.
Figure 4. Experimental setup for coherent phonon spectroscopy.

39 Coherent phonons are observed by ultrafast polarization spectroscopy with the pump-
40 The induced
probe anisotropy
technique. of refractivesetup
The experimental indexfor
is detected
coherentby the polarimeter
phonon spectroscopywithisa shown
quarter-wave
in Fig.
41 4. Coherent phonons are generated by femtosecond optical pulses through theprobe
plate as the polarization change in the probe pulse. The plane of polarization of the pulse
process of
42 is tilted by stimulated
impulsive 45° from that of the scattering
Raman pump pulse. The two
[22,23], anddifferent wavelengths
are detected for the pump
by monitoring and
the time-
43 probe pulses
dependent and pump-cut
anisotropy filters areindex
of refractive used to eliminate
induced by the
the leak
pump of the pump
pulse. Thelight
pumpfrompulse
the in‐
is
44 provided by a Ti:sapphire
put of the polarimeter. The timeregenerative amplifier
evolution of whose
the signal wavelength,
is observed pulsethe
by changing energy,
opticaland
de‐
lay between the pump and probe pulses. The pump pulse is switched on and off shot by shot by
using a photoelastic modulator, a quarter-wave plate, and a polarizer, and the output from the
polarimeter is lock-in detected to improve the signal-to-noise ratio.
 Doping-Induced Ferroelectric Phase Transition and Ultraviolet-Illumination Effect in a Quantum Paraelectric... 263
http://dx.doi.org/10.5772/45744

The source of UV illumination is provided by the second harmonics (380 nm, 3. 3 eV) of the
output from another mode-locked Ti: sapphire laser, whose energy is larger than the optical
band gap of SrTiO3 (3.2 eV). Since the repetition rate of the UV pulses is 80 MHz, this UV
illumination can be considered to be continuous in the present experiment, where the UV-
illumination effect appearing more than one minute after is studied.

3. Birefringence measurement

Figure 5 shows the temperature dependences of the change in birefringence in SrTiO3 and
Ca-doped SrTiO3 between 4.5 and 250 K, where the polarization plane of the probe light is
along the [110]and [100]axes. In SrTiO3, a change in birefringence appears below Tc=105 K,
which is the temperature of the structural phase transition, and is increased as the tempera‐
ture is decreased. In Ca-doped SrTiO3, large changes in birefringence come out at Tc1=180 K,
which is the temperature of the structural phase transition, and at Tc2=28 K, which is the
temperature of the ferroelectric phase transition. The change in birefringence is increased as
the temperature is decreased from Tc1 to Tc2, as well as the case in SrTiO3, and shows a in‐
crease in the gradient for both axes around Tc2. Below Tc2, another kind of lattice distortion is
added, and the peaks of Δn due to the competition between the two kinds of lattice distor‐
tion appear. In both SrTiO3 and Ca-dopedSrTiO3, a cusp on the birefringence curve appears
around Tc=105 K and Tc1=180 K, respectively, because of the fluctuation associated with the
second-order structural phase transition [28].

Figure 5. Temperature dependences of the change in birefringence between 4. 5 and 250 K in SrTiO3 and Ca-doped
SrTiO3. The polarization plane of the probe light for SrTiO3 is along the [110] axis (solid circles). That for Ca-doped
SrTiO3 is along the [110] axis (solid squares) and along the [100] axis (open triangles).
264 Advances in Ferroelectrics

4. Coherent phonon spectroscopy in SrTiO3

4.1. Angular dependence of the coherent phonon signal

Figure 6 shows the transient birefringence in SrTiO3 observed at 6 K for the 0° pumping,
where the polarization direction of the pump pulse is parallel to the [100] axis of the crystal.
Vertical axis is the ellipticity η in electric-field amplitude of the transmitted probe pulse. At
zero delay, a large signal due to the optical Kerr effect, whose width is determined by the
pulse width, appears. After that, damped oscillations of coherent phonons are observed as
shown in Fig. 6(b), where the vertical axis is enlarged by 50 from that of Fig. 6(a). The
change of the polarization for the oscillation amplitude of the coherent phonon signal is
4×10−4 of the electric-field amplitudeof the probe pulse, which corresponds to the change
Δn=7×10−8 of the refractive index. In our detection system, polarization change of ~10−5 in the
electric field amplitude can be detected.

Figure 6. Transient birefringence in SrTiO3 observed at 6 K for the 0° pumping. The vertical axis is the ellipticity η in
electric-field amplitude of the transmitted probe pulse. (a) A large signal due to the optical Kerr effect appears at zero
delay. (b) Damped oscillations of coherent phonons follow after the Kerr signal. The vertical axis of (b) is enlarged by
50 from that of (a).

Angular dependence of the coherent phonon signal in SrTiO3 observed at 6 K is shown in

Fig. 7(a), where the angle between the [100] axis of the crystal and the polarization direction
of the pump pulse is 0°, 15°, and 45°. The angle between the polarization directions of the
pump and probe pulses is fixed to 45°. The 0.7 ps period signal for the 0° pumping disap‐
pears for the 45°pumping, where the 2.3 ps period signal appears. The Fourier transform of
the coherent phonon signals in Fig. 7(a) is shown in Fig. 7(b). Oscillation frequency of the
signal for the 0° pumping is 1.35 THz, and that for the 45° pumping is 0.4 THz. For other
 Doping-Induced Ferroelectric Phase Transition and Ultraviolet-Illumination Effect in a Quantum Paraelectric... 265
http://dx.doi.org/10.5772/45744

pumping angles both frequency components coexist in the coherent phonon signal. From
the oscillation frequencies the 1.35 THz component is considered to correspond to the A1g
mode, and the 0.4 THz component to the Eg mode [7].

Figure 7. (a) Coherent phonon signals in SrTiO3 observed at 6 K for the 0°, 15°, and 45° pumping, where the angle
between the [100] axis of the crystal and the polarization direction of the pump pulse is changed. (b) Fourier trans‐
form of the coherent phonon signals in (a).

In addition to the oscillation signal there exists a dc component. The dc component has a
maximum amplitude for the 0° pumping and minimum amplitude for the 45° pumping.
However, the creation mechanism is not clear at present. In the following we pay attention
to the oscillation component.

4.2. Temperature dependence of the coherent phonon signal

The temperature dependence of the coherent phonon signal in SrTiO3 observed for the 0°
pumping, which corresponds to the A1g mode, is shown in Fig. 8(a). The oscillation period
and the relaxation time of coherent phonons at 10 K are 0.7 and 12 ps. As the temperature is
increased, the oscillation period becomes longer and the relaxation time becomes shorter. At
266 Advances in Ferroelectrics

Tc=105 K, the phase transition point, the oscillation disappears. Above Tc no signal of coher‐
ent phonons is observed. The temperature dependence of the coherent phonon signal in
SrTiO3observed for the 45° pumping, which corresponds to the Eg mode, is shown in Fig.
8(b). The oscillation period and the relaxation time of coherent phonons at 10 K are 2.3 and
45 ps. Similar behavior to that of the A1g mode was observed as the temperature was in‐
creased.

Figure 8. Temperature dependence of the coherent phonon signals in SrTiO3 observed (a) for the 0° pumping which
corresponds to the A1g mode and (b) for the 45° pumping which corresponds to the Eg mode.

4.3. Phonon frequencies

The observed coherent phonon signal S(t) is expressed well by the damped oscillation

S (t ) = Ae-γt sin ωt , (1)

where ω is the oscillation frequency and γ is the relaxation rate. This sine-type function is
expected for phonons induced by impulsive stimulated Raman scattering [22,23]. The tem‐
perature dependence of the oscillation frequency in SrTiO3 obtained from the observed co‐
 Doping-Induced Ferroelectric Phase Transition and Ultraviolet-Illumination Effect in a Quantum Paraelectric... 267
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herent phonon signal below Tc is shown in Fig. 9. The diamonds are the oscillation
frequency for the A1g mode, and the squares are that for the Eg mode. As the temperature is
increased from 6 K, the oscillation frequencies decrease and approach zero at the phase tran‐
sition temperature Tc for both modes. This result is consistent with the temperature depend‐
ence of phonon frequency observed by Raman scattering [7]. The solid curves describe a
temperature dependence of the form ω ∝ (T c - T )n . The experimental results for the temper‐
ature region between 50 K and Tc are explained well by n=0.4 for both modes, while those
below 40 K deviate from that form.

Figure 9. Temperature dependence of the oscillation frequency in SrTiO3 obtained from the coherent phonon signal
below Tc. The diamonds are the oscillation frequency for the A1g mode, and the squares are that for the Eg mode. The
solid curves describe a temperature dependence of the form ω ∝ (T c - T )n , where Tc=105 K and n=0.4 for both modes.

The intensity of the first-order Raman-scattering signal in SrTiO3 is very weak and is of the
same order of magnitude as many second-order Raman-scattering signals because the dis‐
tortion from the cubic structure in the low-temperature phase is very small. Then observa‐
tion of a background-free signal of first-order Raman scattering is not easy, and information
on the relaxation, or the spectral width, is not given in a study of Raman scattering [20]. By
the present method of coherent phonon spectroscopy in the time domain, on the other hand,
background-free damped oscillations can be observed directly, and the oscillation frequency
and the relaxation rate can be obtained accurately.

4.4. Relaxation rates

The temperature dependence of the relaxation rate in SrTiO3 obtained from the observed co‐
herent phonon signal below Tc is shown in Fig. 10. The diamonds in Fig. 10(a) are the relaxa‐
tion rate for the A1g mode and the squares in Fig. 10(b) are that for the Eg mode. The
relaxation rates increase as the temperature is increased.
268 Advances in Ferroelectrics

Figure 10. Temperature dependence of the relaxation rate in SrTiO3 obtained from the coherent phonon signal below
Tc. (a) The diamonds are the relaxation rate for the A1g mode, and (b) the squares are that for the Eg mode. The solid
curves show the theoretical curves including the frequency change obtained from Eq. (2).

In general, relaxation of coherent phonons is determined by population decay (inelastic scat‐

tering) and pure dephasing (elastic scattering). In metals, pure dephasing due to electron-
phonon scattering, which depends on the hot electron density, contributes to the phonon
relaxation [29]. In dielectric crystals, the relaxation process of the coherent phononis consid‐
ered to be dominated by the population decay due to the anharmonic phonon-phonon cou‐
pling [30-32], rather than pure dephasing. According to the anharmonic decay model [30],
the relaxation of optical phonons in the center of the Brillouin zone is considered to occur
through two types of decay process, the down-conversion and up-conversion processes. In a
down-conversion process, the initial ω0 phonon with wave vector k≅ 0 decays into two low‐
er-energy phonons ω i and ω j, with opposite wave vectors k and −k, which belong to the i
branch and the j branch of the phonon. Energy and wave-vector conservation is given by ω
0=ω ik+ω j−k. In an up-conversion process, the initial excitation is scattered by a thermal phonon
(ω ik) into a phonon of higher energy (ω jk), where ω 0+ω ik=ω jk. The down-conversion process
can be realized either for i= j (overtone channel), or for i≠ j (combination channel), depend‐
ing on the phonon band structure of the material, while the up-conversion process contains
only the combination channel and has no overtone channel. The combination channel is less
likely, because three frequencies of phonons and three phonon branches have to be con‐
cerned and stringent limitations are imposed by the energy and wave-vector conservation.
The overtone channel, on the other hand, is more likely because two (an optical and an
acoustic) phonon branches are concerned, and the energy and wave-vector conservation are
necessarily satisfied by two acoustic phonons with the same frequency and opposite wave
vectors, if the frequency maximum of the acoustic branch is higher than half the frequency
of the initial optical phonon.

Here we consider the down-conversion process in which an optical phonon decays into two
acoustic phonons with half the frequency of the optical phonon and with opposite wave vec‐
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tors. Schematic diagram of this down-conversion process is shown in Fig. 11. The tempera‐
ture dependence of the relaxation rate γ of the coherent phonon is given by [30,31]

(
γ = γ0 1 +
2
exp ℏ(ω0 / 2) / k B T -1
) (2)

where ω 0 is the frequency of the optical phonon, and kB is the Boltzmann constant.

Figure 11. Schematic diagram of the down-conversion processe (overtone channel) in the an harmonic decay model
of optical phonons. The initial ω0 optical phonon with wave vector k≅ 0 decays into two ω0 / 2 acoustic phonons, with
opposite wave vectors k and –k.

In ordinary materials the temperature dependence of the phonon frequency is small, and a
theoretical curve with a fixed value of phonon frequency fits the experimental data well. In
SrTiO3, however, the phonon frequencies are changed greatly as the temperature is in‐
creased; thus a frequency change has to be considered. The solid curves in Fig. 10 show the
theoretical curves including the frequency change obtained from Eq. (2) with γ0=8. 0×1010 s−1
for the A1g mode and 1.5×1010 s−1 for the Eg mode, where the observed phonon frequencies in
Fig. 9 are used for each temperature. The broken curves show the theoretical curves in the
case of no frequency change. As is seen in Fig. 10, the solid curves explain well the experi‐
mental data.

Deviation of the experimental data near Tc from the solid curve may be caused by the effect
of the phase transition. However, the relaxation rate just around the phase transition point
cannot be obtained in the present experiment, and the relation between the temperature-de‐
pendent relaxation rate and the structural phase transition is not clear.
270 Advances in Ferroelectrics

5. Coherent phonon spectroscopy in Ca-doped SrTiO3

5.1. Angular dependence of the coherent phonon signal

The angular dependence of the coherent phonon signal in Ca-doped SrTiO observed at 50 K is 3

shown in Fig. 12(a), where the angle between the [100] axis of the crystal and the polarization
plane of the pump pulse is 0°, 25°, and 45°. The angle between the polarization planes of the pump
and probe pulses is fixed to 45°. Vertical axis is the ellipticity in electric field amplitude of the
transmitted probe. At zero delay, a large signal due to the optical Kerr effect, whose width is de‐
termined by the laser-pulse width, appears. After that, damped oscillations of coherent pho‐
nons are observed. For the 0° pumping a 0.5 ps period signal appears while it disappears for the
45° pumping and a 2 ps period signal appears. TheFourier transform of the coherent phonon sig‐
nals in Fig. 12(a) is shown in Fig. 12(b). The oscillation frequency of the signalfor the 0° pumping
is 1. 9 THz and that for the 45° pumping is 0.5 THz. For other pumping angles both frequency com‐
ponents coexist in the coherent phonon signal. These phonon modes are the soft modes related to
the structural phase transition at T =180 K. From the oscillation frequencies the 1.9 THz compo‐
c1

nent corresponds to the A mode, and the 0.5 THz components to the E mode, which are as‐
1g g

signed from the modes of pure SrTiO [7] and from that of Sr Ca TiO (x=0.007) [8].
3 1−x x 3

Figure 12. (a) Coherent phonon signals in Ca-doped SrTiO3 observed at 50 K for the 0°, 25°, and 45° pumping, where
the angle between the [100] axis of the crystal and the polarization direction of the pump pulse is changed. (b) Fourier
transform of the coherent phonon signals in (a).
 Doping-Induced Ferroelectric Phase Transition and Ultraviolet-Illumination Effect in a Quantum Paraelectric... 271
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5.2. Temperature dependence of the coherent phonon signal

The temperature dependence of the coherent phonon signal in Ca-doped SrTiO3 observed
for the 45° pumping, which corresponds to the Eg mode, is shown in Fig. 13. At 6 K some
oscillation components, which have different frequencies, are superposed. As the tempera‐
ture is increased, the number of the oscillation components is decreased, the oscillation peri‐
od becomes longer and the relaxation time becomes shorter. At Tc1=180 K, which is the
structural phase-transition temperature obtained from the birefringence measurement, no
signal of coherent phonons is observed.

Figure 13. Temperature dependence of the coherent phonon signal in Ca-doped SrTiO3 observed for the 45° pumping.

The temperature dependence of the coherent phonon signal in Ca-doped SrTiO observed for 3

the 25° pumping are shown in Figs. 14 and 15. Figure 14(a) shows the coherent phonon signals
below the ferroelectric phase-transition temperature T and Fig. 15(a) shows those above T .
c2 c2

Figure 14(b) shows the Fourier transform of the coherent phonon signals in Fig. 14(a), where the
peaks with arrows 1, 2, and 3 correspond to the ferroelectric phonon modes [8]. Figure 15(b)
shows the Fourier transform of the coherent phonon signals in Fig. 15(a), where modes 1, 2, and
3 disappear but the A and E modes related to the structural phase-transition remain.
1g g
272 Advances in Ferroelectrics

Figure 14. (a) Temperature dependence of the coherent phonon signal in Ca-doped SrTiO3 observed for the 25° pump‐
ing below the ferroelectric phase-transition temperature Tc2. (b) Fourier transform of the coherent phonon signals in (a).

5.3. Phonon frequencies

Each component of the coherent phonon signal is expressed well by damped oscillations in Eq.
(1). The temperature dependence of the oscillation frequencies in Ca-doped SrTiO obtained 3

from the observed coherent phonon signals below T is shown in Fig. 16. The solid circles are
c1

the oscillation frequencies for the A and E modes. The triangles are that for modes 1, 2, and 3
1g g

which are related to the ferroelectric phase transition. As for the A and E modes, as the temper‐
1g g

ature is increased from 6 K, the oscillation frequencies decrease and approach to zero at the
structural phase-transition temperature T for both modes. This result is consistent with the
c1

temperature dependence of phonon frequency observed by Raman scattering [7] and coherent
phonons in section 4.3 for pure SrTiO except for the phase-transition temperature. The broken
3

curves describe a temperature dependence of the form ω ∝ (T c - T )n . The experimental results

for the temperature region between T and T are explained well by n=0.5 for both modes. Be‐
c1 c2

low the ferroelectric phase-transition temperature T , another mode appears at 0.9 THz. It is
c2
 Doping-Induced Ferroelectric Phase Transition and Ultraviolet-Illumination Effect in a Quantum Paraelectric... 273
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considered that the doubly degenerate E mode is split into two components under the tetrago‐
g

nal-to-rhombohedrallattice distortion.

Figure 15. (a) Temperature dependence of the coherent phonon signal in Ca-doped SrTiO observed for the 25°
3

pumping above the ferroelectric phase-transition temperature T . (b) Fourier transform of the coherent phonon sig‐
c2

nals in (a).

The temperature dependence of the phonon frequencies, which are related to the ferroelec‐
tric phase transition, obtained from the observed coherent phonon signals below T is shown c2

in Fig. 17, where only the frequencies of the reproducible peaks in the Fourier spectrum are
plotted. While the lowest peaks at 6 and 16 K in Fig. 14, for example, may be the third mode
observed in the Raman experiment [8], the frequencies of the peaks with poor reproducibili‐
ty are not plotted in Figs. 16 and 17. Under dark illumination, two phonon modes 1 and 2
are softened toward about 25 K and degenerate into mode 3, which seems to be softened to‐
ward the ferroelectric phase-transition temperature T =28 K. The lift of degeneracy for mode
c2

3 below T suggests that another structural deformation occurs at 25 K. In the Raman-scat‐

c2

tering experiment [8], three modes deriving from the TO mode has been observed. The
1

three modes do not all split off at the same temperature; the highest-energy component
splits off at the ferroelectric transition temperature while the other two split off at the tem‐
perature about 3 K lower. These two temperatures may correspond to the two temperatures,
28 and 25 K, observed in our experiment, and the temperature differences are nearly equal
to each other. The existence of the second structural deformation at 25 K is consistent with
the Raman-scattering data.
274 Advances in Ferroelectrics

Figure 16. Temperature dependence of the phonon frequencies in Ca-doped SrTiO3 obtained from the coherent pho‐
non signals below T . The solid circles are the oscillation frequencies for the A and E modes. The broken curves de‐
c1 1g g

scribe a temperature dependence of the form ω ∝ (T c - T )n , where T =180 K and n=0.5 for both modes. The triangles
c

are that for modes 1, 2, and 3 related to the ferroelectric phase transition.

Figure 17. Temperature dependence of the phonon frequencies (a) under dark (1, 2, 3) and under UV (1’,2’,3’) illumi‐
nation below T , which correspond the phonon modes related to the ferroelectric phase transition, and (b)under dark
c2

(1, 2, 3) and after UV(1’’,2’’,3’’) illumination, where the intensity of the UV illumination is 7 mW/mm .
2
 Doping-Induced Ferroelectric Phase Transition and Ultraviolet-Illumination Effect in a Quantum Paraelectric... 275
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5.4. UV-illumination effect

In order to examine the UV-illumination effect, two types of measurements, under the UV
illumination and after the UV illumination, are carried out. The temperature dependence of
the phonon frequencies under the UV illumination is shown in Fig. 17(a), where the intensi‐
ty of the UV illumination is 7 mW/mm2. As is seen in Fig. 17(a), the temperature, toward
which the two modes 1 and 2 are softened and degenerate into mode 3, shifts to the lower
temperature side. The temperature shift due to the UV-illumination effect is ~3 K.
Doped Ca ions behave as permanent dipoles and ferroelectric clusters are formed around Ca
dipoles with high polarizability of the host crystal. The ferroelectric transition is caused by
the ordering of randomly distributed Ca dipoles. The UV-illumination-induced T reduction c2

is related to the screening of the internal macroscopic field by UV-excited carriers. Under the
UV-illumination non equilibrium carriers appear, which are captured by traps and screen
the polarization field. The ordering is prevented by the photo excited carriers. Thus, the
screening effect due to the UV-excited carriers weakens the Coulomb interaction between
dipoles, and the transition temperature is decreased.
The theoretical T reduction under the UV illumination ∆ T is given by [11]
c2 c2

∆ T c2
T c2(0)
(
= 1 - 1 + λa +
γ
4π
)
λ2a 2 exp (-λa), (3)

where T (0) is the transition temperature before the UV illumination, λ is the inverse of the
c2

screening length, a is the mean separation between the dipoles, and γ is the number of the
nearest-neighbor dipoles. The expression of λ is presented by λ = ne 2 / εε0k B T , where n is
the carrier concentration which depends on the UV-illumination intensity and ε is the rela‐
tive dielectric constant. In the present case, the domain is large enough and the dipole-di‐
pole interaction is expressed as a simple Coulomb interaction. The UV-illumination-
intensity dependence of the T reduction for Sr Ca TiO (x=0. 011) was analyzed by using Eq.
c2 1−x x 3

(3). Assuming that the carrier concentration is proportional to the UV-illumination intensity,
the fitting result reproduced well the experimental result obtained in the measurement of
dielectric constants [11]. Here we estimate the inverse λ of the screening length at the UV-
illumination intensity of 7 mW/mm . As a result of the measurement of dielectric constant
2

[11], the carrier concentration is n=2. 5× 10 cm at 3 mW/mm . From this value we can esti‐
17 −3 2

mate the carrier concentration to be n=5. 8× 10 cm at 7 mW/mm . The value of the inverse
17 −3 2

of the screening length is obtained as

ne 2 8πnaB E1s
λ= = = 1.1 × 107 cm-1, (4)
εε0k B T εk B T

where a and E are Bohr radius and the energy of the hydrogen atom in the 1s ground state,
B 1s

respectively, and we use the dielectric constant ε =4 in the visible region. Substituting the
value of λ into Eq. (3), the shift of the transition temperature can be estimated to be ∆ T ~8 K. c2

This estimation is not inconsistent with the observed values of the temperature shift in the
276 Advances in Ferroelectrics

experiment of coherent phonons, in which the value of the observed transition temperature
shift is ~3 K.

The temperature dependence of the phonon frequencies after the UV illumination is shown
in Fig. 17(b), where theUV illumination of 7 mW/mm is on before the coherent phonon
2

measurement but is off during the measurement. In this case, on the other hand, the shift of
the softening temperature for modes 1 and 2 is not clear. The phonon frequencies for modes
1 and 2 are decreased while the coherent phonon signal for mode 3 is not observed. The re‐
laxation time of the UV-illumination induced carriers is on the order of milliseconds below
30 K for SrTiO [21]. As is seen in Fig. 17(b), however, it is suggested that the UV-illumina‐
3

tion effect, frequency decrease for modes 1 and 2 and disappearance of mode-3 signal, re‐
mains for at least several minutes, even if the UV illumination is switched off, although the
T shifting effect disappears immediately.
c2

6. Summary

We observed coherent phonons in pure and Ca-doped SrTiO using ultrafast polarization
3

spectroscopy to study the ultrafast dynamics of soft phonon modes and their UV-illumina‐
tion effect. Coherent phonons are generated by linearly polarized pump pulses. The time-
dependent linear birefringence induced by the generated coherent phonons is detected asa
change of the polarization of the probe pulses. A high detection sensitivity of ~10 in polari‐
−5

zation change, which corresponds to the change ∆ n=2× 10 of the refractive index for a 1
−9

mm sample, has been achieved in our detection system.

In SrTiO , damped oscillations of coherent phonons for the A and E modes, which contrib‐
3 1g g

ute to the structural phase transition at 105 K, were observed. The temperature dependences
of the frequency and the relaxation rate of the observed coherent phonons were measured.
Softening of the phonon frequencies was observed. The phonon relaxation is explained well
by a decay model of a frequency-changing phonon, in which the optical phonon decays into
two acoustic phonons due to the anharmonic phonon-phonon coupling.

We observed the temperature dependences of the birefringence and the coherent phonon
signal to investigate the doping-induced ferroelectric phase transition in Ca-dopedSrTiO 3

with the Ca concentration of x=0.011. In the birefringence measurement, it was confirmed

that the structural phase-transition temperature is T =180 K. Coherent phonons were ob‐
c1

served by using ultrafast polarization spectroscopy. The damped oscillations of coherent

phonons for the A and E modes, which contribute to the structural phase transition at
1g g

T =180 K, and for the modes 1, 2, and3, which contribute to the ferroelectric phase transition
c1

at T =28 K, were observed. The phonon frequencies were obtained from the observed signals
c2

of coherent phonons, and their softening toward each phase-transition temperature was ob‐
served. Another structural deformation at 25 K was found in addition to the ferroelectric
phase transition at T . It was found that the UV illumination causes the shift of the ferroelec‐
c2

tric phase-transition temperature toward the lower temperature side, and the temperature
 Doping-Induced Ferroelectric Phase Transition and Ultraviolet-Illumination Effect in a Quantum Paraelectric... 277
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shift is ~3 K. The decrease in the phonon frequencies after the UV illumination suggests the
UV-illumination effect remains even if the UV illumination is switched off.
It was shown that the coherent phonon spectroscopy in the time domain is a very useful ap‐
proach to study the soft phonon modes and their UV-illumination effect in dielectric materi‐
als.

Acknowledgement

We would like to thank Dr. Y. Koyama for experimental help and Dr. Y. Yamada and Prof.
K. Tanaka for providing us the samples of Ca-doped SrTiO3.

Author details

Toshiro Kohmoto

Graduate School of Science, Kobe University, Japan

References

[1] K. A. Müller and H. Burkard, Phys. Rev. B 19, 3593 (1979).

[2] H. Uwe and T. Sakudo, Phys. Rev. B 13, 271 (1976).
[3] M. Itoh, R. Wang, Y. Inaguma, T. Yamaguchi, Y.-J. Shan, and T.Nakamura, Phys.
Rev. Lett. 82, 3540 (1999).
[4] B. E. Vugmeister and M. P. Glinchuk, Rev. Mod. Phys. 62, 993 (1990).
[5] J. G. Bednorz and K. A. Müller, Phys. Rev. Lett. 52, 2289 (1984).
[6] J. F. Scott, Rev. Mod. Phys. 46, 83 (1974), and references therein.
[7] P. A. Fleury, J. F. Scott, and J. M. Worlock, Phys. Rev. Lett. 21,16 (1968).
[8] U. Bianchi, W. Kleemann, and J. G. Bednorz, J. Phys.: Condens. Matter 6, 1229 (1994).
[9] U. Bianchi, J. Dec, W. Kleemann, and J. G. Bednorz, Phys. Rev. B 51, 8737 (1995).
[10] Bürgel, W. Kleemann, and U. Bianchi, Phys. Rev. B 53, 5222 (1995).
[11] Y. Yamada and K. Tanaka, J. Phys. Soc. Jpn. 77, 5 (2008).
[12] G. Geneste and J.-M. Kiat, Phys. Rev. B 77, 174101 (2008).
[13] M. Takesada, T. Yagi, M. Itoh, and S. Koshihara, J. Phys. Soc. Jpn. 72, 37 (2003).
278 Advances in Ferroelectrics

[14] T. Hasegawa, S. Mouri, Y. Yamada, and K. Tanaka, J. Phys. Soc. Jpn. 72, 41 (2003).

[15] G. Godefroy, P. Jullien, and L. Cai, Ferroelectrics 13, 309 (1976).

[16] S. Ueda, I. Tatsuzaki, and Y. Shindo, Phys. Rev. Lett. 18, 453 (1967).

[17] Y. Yamada and K. Tanaka, J. Lumin. 112, 259 (2005).

[18] T. P. Dougherty, G. P. Wiederrecht, K. A. Nelson, M. H. Garrett,H. P. Jensen, and C.

Warde, Science 258, 770 (1992).

[19] H. J. Bakker, S. Hunsche, and H. Kurz, Rev. Mod. Phys. 70, 523 (1998).

[20] W. G. Nilsen and J. G. Skinner, J. Chem. Phys. 48, 2240 (1968).

[21] T. Hasegawa, M. Shirai, and K. Tanaka, J. Lumin. 87-89, 1217 (2000).

[22] Y.-X. Yan, E. B. Gamble, Jr., and K. A. Nelson, J. Chem. Phys.83, 5391 (1985).

[23] G. A. Garrett, T. F. Albrecht, J. F. Whitaker, and R. Merlin, Phys. Rev. Lett. 77, 3661
(1996).

[24] T. Kohmoto, K. Tada, T. Moriyasu, and Y. Fukuda,Phys. Rev. B 74, 064303 (2006).

[25] Y. Koyama, T. Moriyasu, H. Okamura, Y. Yamada, K. Tanaka, and T. Kohmoto, Phys.

Rev. B 81, 024104 (2010).

[26] T. Kohmoto, Y. Fukuda, M. Kunitomo, and K. Isoda, Phys. Rev. B 62, 579 (2000).

[27] R. V. Jones, Proc. R. Soc. London, Ser. A 349, 423 (1976).

[28] E. Courtens, Phys. Rev. Lett. 29, 1380 (1972).

[29] K. Watanabe, N. Takagi, and Y. Matsumoto, Phys. Rev. Lett. 92,057401 (2004).

[30] F. Vallée, Phys. Rev. B 49, 2460 (1994).

[31] M. Hase, K. Mizoguchi, H. Harima, S. I. Nakashima, and K. Sakai, Phys. Rev. B 58,
5448 (1998).

[32] M. Hase, K. Ishioka, J. Demsar, K. Ushida, and M. Kitajima, Phys. Rev. B 71, 184301
(2005).
 Chapter 13

Raman Scattering Study on the Phase Transition

Dynamics of Ferroelectric Oxides

Hiroki Taniguchi, Hiroki Moriwake,

Toshirou Yagi and Mitsuru Itoh

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52059

1. Introduction

Ferroelectric phase transitions are conventionally divided into two types: an order-disorder
and a displacive-type.[1] In the former one, which is frequently seen in hydrogen-bond-type
ferroelectrics such as KH2PO4 (KDP), local dipole moments μs are randomly distributed be‐
tween opposite directions in the paraelectric phase, leading to zero macroscopic net polariza‐
tion P (= Σμ). A spontaneous polarization in the ferroelectric phase is then driven by their
ordering through the ferroelectric phase transition. In the later type, in contrast, there are no
dipole moments in the paraelectric phase. The spontaneous polarization in the ferroelectric
phase stems from relative polar displacement between cationic and anionic sublattices. It is in‐
duced by freezing of a so-called ferroelectric “soft mode”, which is known as a strongly anhar‐
monic optical phonon mode at Γ-point in the Brillouin zone (BZ). The displacive-type
transition is often found in the ferroelectric oxides as represented by perovskite-type com‐
pounds such as PbTiO3. Since the ferroelectric oxides have been widely applied for the elec‐
tronic devices, such as actuators, sensors, and memories, due to their chemical stability, the
large spontaneous polarization, and the relatively high transition temperature, a better under‐
standing of the soft mode behavior would be important from viewpoints of both application
and fundamental sciences. Spectroscopic techniques employing light scattering, infrared ab‐
sorption, and neutron scattering have been generally utilized for investigating the dynamics
of the soft mode. Among them, Raman scattering has an advantage especially in a low-fre‐
quency region, which is significant to resolve the critical dynamics of the soft mode near the
transition temperature. In the present review, we will discuss the soft mode behavior at the
ferroelectric phase transition by referring the Raman scattering studies on CdTiO3 and 18O-
substituted SrTiO3. Furthermore, a microscopic origin of the soft mode is figured out from a
viewpoint of local chemical bonds with the help of first-principles calculations.

© 2012 Taniguchi et al.; licensee InTech. This is an open access article distributed under the terms of the
Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
280 Advances in Ferroelectrics

2. Ferroelectric soft mode in the classical scheme

Since a concept of the soft mode was proposed, many theoretical and experimental studies
have been conducted to clarify its dynamics.[2-4] In this section, we discuss the soft mode
behavior in the classical scheme.

2.1. Theoretical background of the ferroelectric soft mode in the classical scheme

The potential of the soft mode is approximately described by accounting only a biquadratic
phonon-phonon interaction as follows:

1 1
U0 = M ( s,0)wbare
2
( s,0)Q 2 ( s,0) + åå J ( s,0; l , k )Q 2 ( s,0)Q 2 (l , k ) (1)
2 l k 2

where M(s,0), ωbare(s,0), Q(s,0) in the first term are effective mass, bare frequency, and dis‐
placement of the soft mode at the Γ-point. The J(s,0;λ,k) in the second term denotes an inter‐
action between the soft mode at the Γ-point and the optical phonon mode λ at the wave
vector k, where the summation runs over all blanches and BZ. The equation can be trans‐
formed by a pseudo-harmonic approximation as

1 1
U0 » M ( s,0)wbare
2
( s,0)Q 2 ( s,0) + åå J ( s,0; l , k )Q 2 ( s,0) Q 2 (l , k )
2 l k 2

1 é 2 J ( s,0; l , k ) 2 ù
= M ( s,0) êwbare ( s,0) + åå Q (l , k ) ú Q 2 ( s,0) (2)
2 ë l k M ( s ,0) û
1
º M ( s,0)ws Q ( s,0)
2 2

where the inside of the brackets is redefined by the soft mode frequency ωs. In the classical
regime, the mean square displacement <Q2(λ,k)> is proportional to kBT, where kB is a Boltz‐
mann constant. The soft mode frequency is thus expressed as

J ( s,0; l , k ) kBT
ws2 º w 2 ( s,0) = wbare
2
( s,0) + åå (3)
l k M ( s,0) M (l , k )w 2 (l , k )

Since ωs is ideally zero at Tc of the second-order phase transition,

J ( s,0; l , k ) kBTc
ws2 = wbare
2
( s,0) + åå =0 (4)
l k M ( s,0) M (l , k )w 2 (l , k )

leading to
 Raman Scattering Study on the Phase Transition Dynamics of Ferroelectric Oxides 281
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J ( s,0; l , k ) kBTc
wbare
2
( s,0) = -åå (5)
l k M ( s,0) M (l , k )w 2 (l , k )

We thus obtain

J ( s,0; l , k ) kBT J ( s,0; l , k ) kBTc

ws2 = åå - åå (6)
l k M ( s,0) M (l , k )w 2 (l , k ) l k M ( s,0) M (l , k )w 2 (l , k )

Defining C as

12
é J ( s,0; l , k ) kB ù
C º ê åå ú (7)
ë l k M ( s,0) M (l , k )w (l , k ) û
2

it finally comes to Cochran’s law

ws = C (T - Tc )1 2 (8)

where

-1
é J ( s,0; l , k ) kB ù
Tc º -wbare
2
( s,0) ê åå ú (9)
ë l k M ( s,0) M (l , k )w (l , k ) û
2

As seen in the above equation, the soft mode decreases its frequency with approaching Tc,
and finally freezes to induce the ferroelectric phase transition. In the second-order phase
transition, in particular, the displacement of the soft mode Q(s,0) corresponds to the polar
displacement in the ferroelectric phase. It should be noted that the bare frequency ωbare(s,0)
of the soft mode is assumed to be imaginary at zero-Kelvin. The softening of the soft mode
connects to the divergent increase of the dielectric constant through Lyddane-Sachs-Teller
(LST) relation,

1
e¢ µ (10)
ws2

2.2. Experimental observation of the ferroelectric soft mode in the classical scheme

The experimental observation of the typical soft mode behavior in the perovskite-type ferro‐
electric oxide, CdTiO3, is presented in this section.
282 Advances in Ferroelectrics

CdTiO3 possesses an orthorhombic Pnma structure at room temperature due to (a+b-b-)-type

octahedral rotations in the Glazer's notation from the prototypical Cubic Pm-3m structure.
The CdTiO3 undergoes ferroelectric phase transition into the orthorhombic Pna21 phase
around 85 K.[5-7]

The confocal micro-Raman scattering is the one of useful techniques to investigate the soft
mode dynamics in the displacive-type ferroelectric phase transition due to the following rea‐
son; In general, the complicated domain structure forms across the ferroelectric phase transi‐
tion, where the principle axis of the crystal orients to various directions, which are allowed
by the symmetry relation between the paraelectric and the ferroelectric phases. The size of
the individual domain generally ranges over several nanometers to microns. When the do‐
mains are smaller than the radiated area of the incident laser, the observed Raman spectrum
is composed of signals from differently oriented domains, leading to difficulty in the precise
spectral analyses. With application of the confocal micro-Raman scattering, on the other
hand, we can selectively observe the spectrum from the single domain region, because its
spatial resolution reaches sub-microns not only for lateral but also depth directions.[8] Note
that the Raman scattering can observe the soft mode only in the non-centrosymmetric phase
due to the selection rule, therefore the critical dynamics of the soft mode is in principle in‐
vestigated in the ferroelectric phase below Tc.

Figure 1. Raman spectra of CdTiO3 at room temperature observed with several scattering geometries. See text for
configuration notations, for instance Y(X,X)-Y.

Flux-grown colorless single crystals of CdTiO3 with a rectangular solid shape were used for
this study. The two samples have dimensions of approximately 0.3×0.2×0.1 mm3 and
 Raman Scattering Study on the Phase Transition Dynamics of Ferroelectric Oxides 283
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0.2×0.1×0.1 mm3. Since the present samples were twinned, we carefully determined the di‐
rections of the axes in the observed area by checking the angular dependence of the Raman
spectra with the confocal micro-Raman system, whose spatial resolution is around 1 μm
(Fig. 1). Here we use laboratory coordinates X, Y, and Z, corresponding respectively to the
crystallographic axes of [100], [010], and [001] in the paraelectric phase, to denote the Raman
scattering geometries. For example, XZ(Y,Y)-Z-X means that the incident laser polarized
parallel to the [010] direction penetrates the sample along the [101] direction, and the [010]-
polarized scattered light is collected with the backscattering geometry. The scattered light
was analyzed by a Jovin-Yvon triple monochromator T64000 with the subtractive dispersion
mode, and was finally observed by a liquid-N2-cooled CCD camera. The frequency resolu‐
tion of the present experiment was better than 1 cm-1 The temperature of the sample was
controlled by an Oxford microstat with a temperature stability of ±0.01 K.

Figure 2 shows the temperature dependence of the Raman spectrum of CdTiO3, which is ob‐
served in Y(ZX,ZX)-Y scattering geometry with several temperatures from 85.0 K to 40.0 K.
In the vicinity of Tc, in particular, spectra were observed with the temperature intervals of
0.5 K. As shown in the figures, the soft mode is seen at around 60 cm-1 at 40 K. It gradually
softens toward zero-frxuency as approaching Tc ~ 85 K. The spectral profile of the soft mode
is analyzed by a damped-harmonic-oscillator (DHO) model;

Bw02Gw
I (w ) = (11)
(w - w 2 ) 2 + G 2w 2
2
0

where B, ω0, and Γ denote amplitude, harmonic frequency, and a damping constant of the
soft mode, respectively. The soft mode frequency ωs is defined here as

Figure 2. Temperature Dependence of the Raman spectrum of CdTiO3 observed in the Y(ZX,ZX)-Y scattering geome‐
try, and from 40K to 85 K on heating.

ws2 = w02 - G 2 (12)

284 Advances in Ferroelectrics

The temperature dependence of the soft mode frequency and the damping constant, which
are determined by the analyses, are plotted by solid circles and open squares in Fig. 3. Syn‐
chronizing with the softening of the soft mode, the damping constant is increased as ap‐
proaching Tc.

Figure 3. Temperature Dependencies of (a) the soft mode frequency and (b) the damping constant of CdTiO3. The
solid line in (a) is calculated by Cochran’s law (see text).

Figure 4. a) Phonon dispersion in CdTiO3 obtained by the first-principles calculations. (b) The displacement pattern of
the soft mode, and configurations of three O-Cd-O bonds along (1) [-101], (2) [101], and (3) [010] directions.
 Raman Scattering Study on the Phase Transition Dynamics of Ferroelectric Oxides 285
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The temperature dependence of the soft mode frequency obeys the Cochran’s low (Eq. 1.8)
with C = 8.5 and Tc = 85 K as expressed by the solid curve in the figure, indicating the typical
displacive-type ferroelectric phase transition on CdTiO3.
The displacement pattern of the soft mode is obtained by first principle calculations. The cal‐
culations were conducted with a pseudopotential method based on a density functional per‐
turbation theory with norm-conserving pseudopotentials, which was implemented in the
CASTEP code.[9] Figure 4a presents phonon dispersion curves of CdTiO3 in the paraelectric
Pnma phase, which was obtained by the first-principle calculations. As seen in the figure, the
soft mode, which is indicated by an imaginary frequency, is observed at Γ-point in Brillouin
zone. According to the calculation, a displacement pattern of the Γ-point soft mode is com‐
posed of relative displacement of Ti with respective to the octahedra and an asymmetric
stretching of O-Cd-O bond. It has been previously proposed that the hybridization between
O-2p and empty Ti-3d orbitals triggers the non-centrosymmetric displacement of Ti thor‐
ough a second-order Jahn-Teller (SOJT) effect to induce the ferroelectricity as exemplified by
BaTiO3.[10] The SOJT effect, however, does not provide clear understanding on the role of
A-site ion. In the case of CdTiO3, in particular, the ferroelectricity disappears when the Cd is
replaced by Ca, though the CaTiO3 is an isomorph of CdTiO3. Therefore, the ferroelectricity
in CdTiO3 can not be explained only by the B-O orbital hybridization. Here, we focus on the
asymmetric stretching of O-Cd-O to elucidate the mechanism of ferroelectricity in CdTiO3.
The asymmetric stretching in the Γ-point soft mode is schematically illustrated by arrows in
the right panel in Fig. 4b, where large and small spheres denote Cd and O ions, respectively.
Ti and O ions that do not participate in the O-Cd-O bonds are omitted for simplicity. In a
prototypical Pm-3m structure of the perovskite-type oxide, an A-site ion is surrounded by
neighboring twelve O ions. In the CdTiO3 of paraelectric Pnma structure, however, the num‐
ber of closest oxygen ions for Cd ion is reduced to four due to the octahedral rotations.
(Note that the octahedral rotations in the Pnma structure are different from each other ac‐
cording to the direction; the rotation is in-phase for a [010] direction whereas those for [101]
and [-101] are anti-phase.) As a result, CdTiO3 has three different O-Cd-O bonds along
[-101], [101], and [010] directions, whose equilibrium structures are respectively denoted by
(1), (2), and (3) in the Fig. 2(b). The result of first-principles calculations indicates that the
soft mode displacement is inherently dominated by the asymmetric stretching of the O-Cd-
O bond along the [010] direction denoted by (3). By comparing three equilibrium structures
for O-Cd-O bonds presented in the right-hand side of Fig. 4b, it is found that the O-Cd-O
bond along [010] direction is symmetric with the Cd-O bond lengths of 2.186 Å in the para‐
electric Pnma phase, in contrast the other two are composed of non-equivalent bonds having
2.326 and 2.165 Å. Therefore, there is a remaining degree of freedom for further O-Cd-O off-
center ordering due to the covalent bonding along the [010] direction. This remaining degree
of freedom would be the origin of the ferroelectric soft mode.

3. A role of covalency in the ferroelectric soft mode

As indicated above, the covalency of the A-site ion plays an important role in the ferroelec‐
tricity in addition to that of B-site ion. The A-site substitution with an isovalent ion is in‐
286 Advances in Ferroelectrics

structive for the better understanding on the mechanism of the ferroelectricity in the
perovskite-type oxides. This section is thus devoted to the effect of the isovalent Ca-substitu‐
tion on the ferroelectricity of CdTiO3. [11, 12]

Figure 5. a) Dielectric constants of CCT-x. (b) Ca concentration dependence of the ferroelectric phase transition tem‐
perature Tc. Solid curve denotes Curie–Weiss fit of data points for CCT-0, 0.01, and 0.03.

Ceramics form of Ca-doped CdTiO3, Cd1-xCaxTiO3 (CCT-x) with x = 0, 0.01, 0.03, 0.05, and
0.07, were fabricated by conventional solid state reactions from stoichiometric mixtures of
CdO (3N), CaCO3 (4N), and TiO2 (3N). The mixtures were calcined during 24 h in air at 975
~ 1175ºC. Then the reground powders were pressed at 4 ton/cm2, and sintered at 1200 ~
1230ºC. Dielectric measurements were performed by a LCZ meter.

Temperature dependencies of the dielectric constants in CCT-x are presented in Fig. 5a. As
seen in the figure, the dielectric constant of CCT-0 divergently increases and culminates at
the phase transition temperature Tc ~ 85 K. The Tc decreases with Ca doping, and the peak
transforms into a low-temperature plateau at x = 0.05, indicating a quantum paraelectric
state as discussed later. The Ca concentration dependence of Tc, which is estimated from the
dielectric peaks, is shown in Fig. 5b. The fit curve with conventional Curie-Weiss law (a red
line in the figure) indicates that the ferroelectricity in the CCT-x system is suppressed with a
value of x larger than xc = 0.047.

The temperature dependence of the soft mode frequency is presented in Fig. 6 as a func‐
tion of x. The soft modes in CCT-x increase in frequency and intensity with distance from
Tc on cooling, exhibiting typical behavior of the soft-mode-driven phase transition. Ac‐
cording to the Lyddane–Sachs–Teller relationship (Eq. 1.10), the squared soft mode fre‐
quency ωs2 and the dielectric constant ε' are inversely proportional as mentioned in the
preceding section. Therefore, if the dielectric properties of the CCT-x system are governed
by the lattice dynamics, the soft mode frequency at the lowest temperature should de‐
 Raman Scattering Study on the Phase Transition Dynamics of Ferroelectric Oxides 287
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crease with increasing x because the dielectric constant near 0 K increases with x (see Fig.
5a). The Raman spectra at 4 K presented in the bottom panels in Fig. 6 show that the soft
mode softens as x increases, indicating a displacive-type phase transition of the CCT-x
system. This result suggests that the phase transition of CCT-x can be discussed in terms
of lattice dynamics. Note that, the soft mode become observable at low temperature in
CCT-0.05 and -0.07, although it does not undergo the ferroelectric phase transition within
a finite temperature range. This is a typical characteristic of precursory softening of the
soft mode in the quantum paraelectric state.[13, 14]

Figure 6. Contour plots for the temperature dependence of soft mode spectra in CCT-x (upper panels). Bottom panels
show the low-frequency spectra observed at ~ 4 K.

Figure 7 presents the partial electronic density of states (p-DOS) for CdTiO3 (left) and CaT‐
iO3 (right) obtained by the first-principles calculations, where the p-orbital of oxygen, the s-
orbital of Cd and Ca, and the total DOS are denoted by oppositely hatched and blank areas,
respectively. As shown in the figure, the s-orbital of Cd ion has strong hybridization with
the p-orbital of oxygen. In marked contrast, the s-orbital of Ca has little hybridization, indi‐
cating larger A-O covalency in CdTiO3 than CaTiO3. This characteristic substantially agrees
with the difference in electronegativity of Cd and Ca ions, where those in Cd and Ca are 1.7
and 1.0, respectively. A calculated charge density distributions around the O-Cd(Ca)-O
bonds along the [010] direction are indicated in Fig. 8. As shown in the panels, larger charge
density is observed between Cd and O ions in CdTiO3, confirming its strong covalency. In
contrast, Ca-O bond is nearly ionic. If the Cd(Ca) bonding is ionic, Cd(Ca) ion in the O-
Cd(Ca)-O bond tends to locate a centric position. Therefore, Ca-substitution suppresses the
freezing of the asymmetric stretching vibration with the off-centering of Cd(Ca) by decreas‐
ing the covalency. Since the asymmetric stretching of the O-Cd-O bond along [010] direction
is suggested to be the origin of the soft mode, Ca-substitution results in the suppression of
the softening of the soft mode. The present result confirms that the ferroelectric instability of
CCT-x stems from A-site covalency.
288 Advances in Ferroelectrics

Figure 7. Partial electron density of states (p-DOS) for CdTiO3 (left) and CaTiO3 (right). Blue, red, and black curves rep‐
resent p orbital of oxygen ions, s orbital of Cd and Ca ions, and total DOS.

Figure 8. Cross sections of charge density around 4-coordinated Cd (left) and Ca (right) ions obtained by first principle
calculations. Note that the upper and lower cross sections include O–Cd(Ca)–O bonds, which are involved in O–
Cd(Ca)–O chains along the b and a direction, respectively.

4. Ferroelectric Soft Mode in the Quantum Scheme

It has been known that the quantum fluctuation plays a non-negligible role in the phase
transition dynamics when the Tc goes down near 0 K, where the transition is suppressed
though the dielectric permittivity reaches to several tens thousand. This effect is known as
"quantum paraelectricity", which was first proposed as an origin of the giant dielectric pla‐
teau of SrTiO3 at the low-temperature.[15] Twenty years later, it has been discovered that an
isotope substitution with 18O induces the ferroelectricity of SrTiO3, attracting considerable
attention of researchers.[16] In this section, the dynamics of quantum para/ferroelectric is
discussed from a view point of the soft mode.

4.1. Theoretical background of the ferroelectric soft mode in the quantum scheme

In the classical case as mentioned before, the soft mode frequency can be described as Eq.
1.3. At the low-temperature, where the influence of the quantum fluctuation can not be ig‐
 Raman Scattering Study on the Phase Transition Dynamics of Ferroelectric Oxides 289
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nored, the approximation <Q2(λ, k)> ~ kBT is not appropriate. Therefore, Eq. 1.3 should be
modified with quantum statistic treatment as

J ( s,0; l , k ) h hw (l , k )
ws2 = wbare
2
( s,0) + åå coth (13)
l k M ( s,0) 2 M (l , k )w (l , k ) 2kBT

At the sufficiently low-temperature, where only the Γ-point soft mode that is the optical
phonon with lowest energy can be thermally excited, any other optical phonons are not ef‐
fective in the second term except for λ = s at k = 0. The soft mode frequency can thus be ex‐
pressed as

J ( s,0; s,0) h hws

ws2 = wbare
2
( s,0) + coth (14)
2 M 2 ( s,0) ws 2kBT

As in the classical case,

J ( s,0; s,0) h hws

ws2 = wbare
2
( s,0) + coth =0 (15)
2 M 2 ( s,0) ws 2kBTc

gives

J ( s,0; s,0) h hws

wbare
2
( s,0) = - coth (16)
2 M 2 ( s,0) ws 2kBTc

We thus obtain the soft mode frequency at the low-temperature,

12
æT T ö
ws = C ¢ ç 1 coth 1 - Tc¢ ÷ (17)
è 2 2T ø

with

12
é J ( s,0; s,0) kB ù hws T T
C¢ º ê 2 ú
, T1 º , Tc¢ º 1 coth 1 (18)
ë M 2
( s ,0) ws û k B 2 2Tc

In this treatment, the temperature dependence of the squared soft mode frequency, which is
inversely proportional to the dielectric permittivity, in no longer linear with respect to tem‐
perature, but saturated with the constant value near 0 K. The qualitative behavior of the soft
290 Advances in Ferroelectrics

mode in the quantum para/ferroelectrics is schematically illustrated as a function of T1 with

the fixed T'c in Fig. 9.

Figure 9. The schematic illustration describing the variation of the temperature dependence of the soft mode fre‐
quency as a function of T1. See text for the detail.

The classical limit is also presented for comparison. Note that the value of T1 is varied with
constant intervals. As presented in the figure, the phase transition is completely suppressed
when T1 is sufficiently large, whereas it recovers as decreasing T1. Interestingly, the T1 de‐
pendence of the transition temperature becomes extremely sensitive when the transition
temperature is close to 0K, suggesting that the quantum paraelectric-ferroelectric transition
can be induced by subtle perturbation such as the isotope substitutions. [17]

Figure 10. Temperature dependencies of the squared frequencies of the soft mode in STO18-x with various x. Solid lines
in the figures denote temperature dependencies calculated by Eq. 3.7 with optimized control parameters (see text).

4.2. Experimental observation of the ferroelectric soft mode in the quantum scheme

The isotopically induced phase transition of the quantum paraelectric SrTiO3 is a good ex‐
ample for the quantum paraelectric-ferroelectric phase transition driven by the soft mode.
 Raman Scattering Study on the Phase Transition Dynamics of Ferroelectric Oxides 291
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Here we show the Raman scattering study on the soft mode in SrTi(16O1-x18Ox)3 (STO18-100x)
as functions of temperature and the isotope substitution rate x. The experiments were per‐
formed with the Raman scattering geometries of X(YY)-X, where X, Y, and Z are denoted by
the cubic coordination of SrTiO3.[13,14,18]
Figure 10 presents the temperature dependence of the squared soft mode frequency in
STO18-100x for 0.23, 0.32, 0.50 0.66, and 0.96, observed in the X(YY)-X scattering geometry,
respectively. In x = 0.50, 0.66, and 0.96, the soft mode frequency is shown only for the ferro‐
electric phase. As indicated in the figure, the softening of the soft mode in STO18-23 satu‐
rates at the low-temperature region near 0 K, showing excellent agreement with the theory.
Since the square of the soft mode frequency is inversely proportional to the dielectric per‐
mittivity as indicated by the LST-relation as mentioned before, it is clear that the dielectric
plateau in SrTiO3 stems from the soft mode dynamics. Note that the soft mode is nominally
Raman inactive in the centrosymmetric structure as for the paraelectric phase of SrTiO3 due
to the selection rule. In the present case, however, the centrosymmetry is locally broken in
the low-temperature region of STO18-100x (x < xc ~ 0.32), leading to the observation of the
soft mode even in the macroscopic centrosymmetry. The local non-centrosymmetric regions
grow with 18O-substitution to activate the soft mode spectrum even in the paraelectric phase
as indicated in Fig. 11. A mechanism of such defect-induced Raman process and an expected
spectral profile are discussed in detail in Ref. [13] and [14]. The date points for STO18-x (x <
xc) in Fig. 10 are obtained by the spectral fitting with the defect-induced Raman scattering
model.

Figure 11. Temperature dependencies of the Raman spectra in STO18-x (x = 0 [STO16: the pure SrTiO3], 0.23, and
0.32).

With the isotope substitution, softening of the soft mode is enhanced and the phase transi‐
tion takes place above the critical concentration xc as manifested by the hardening of the soft
mode on cooling in the low temperature region. The transition temperature elevates as in‐
creasing x. The temperature dependencies of the soft modes in all samples except for that in
292 Advances in Ferroelectrics

STO18-32 were examined by the generalized quantum Curie-Weiss law, which was pro‐
posed in Ref. 19, where the power of Eq. 3.5 is modified by γ/2;

g 2
æT T ö
ws = C ¢ ç 1 coth 1 - Tc¢ ÷ (19)
è2 2T ø

The γ is the one of critical exponents, which characterizes the critical behavior of the sus‐
ceptibility. As seen in the figure, the plots are well reproduced by the fitting with the sys‐
tematic variations of T1 and γ as indicated in Fig. 12.

Figure 12. a) The x dependence of T1obtained by the fitting. The dashed line is a guide for the eye. (b) The x depend‐
ence of critical exponent γ. In STO18-23, -50, -66, -96, γ is determined by the fitting of the observed soft mode fre‐
quency with Eq. 3.7. In STO18-32, we directly determined γ = 2 from the linear temperature dependence of the soft
mode frequency with T, as seen in the inset. The solid lines are eye guides.

In STO18-32, the strongly rounded soft mode behavior keeps us from fitting with Eq. 3.7.
However, we can determine γ = 2 for STO18-32 from the obvious linear temperature de‐
pendence of the soft mode frequency, as seen in the inset of the panel (b). It should be noted
here that γ = 2 corresponds to the theoretical value for the quantum ferroelectric phase tran‐
sition [20–22], and is caused by the quantum mechanical noncommutativity between kinetic
and potential energy. These results show experimentally that the quantum phase transition
of STO18-x is an ideal soft mode-type transition driven by direct control of the quantum
fluctuation with the 18O-substitution. An origin of the strongly rounded softening was sug‐
gested in our previous study to be the nanoscopic phase coexistence between ferroelectric
and paraelectric region. (See Ref. 18 for the detail)

5. Summary

In the present review, we overviewed the soft mode behavior in both classical and quantum
schemes through Raman scattering experiment in the CdTiO3 and the 18O-substituted
SrTiO3. The analyses show excellent agreement qualitatively between the fundamental theo‐
ry and experimental observations. The systematic studies with Raman scattering experi‐
 Raman Scattering Study on the Phase Transition Dynamics of Ferroelectric Oxides 293
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ments and the first-principles calculations on Ca-substituted CdTiO3 clarified that the
covalency between constituent cation and oxygen plays an essential role in the origin of the
soft mode. We hope the present review serves better understanding on the mechanism of
displacive-type ferroelectric phase transition.

Author details

Hiroki Taniguchi1*, Hiroki Moriwake2, Toshirou Yagi3 and Mitsuru Itoh1

*Address all correspondence to:

1 Materials and Science Laboratory, Tokyo Institute of Technology, Yokohama, Japan

2 Nanostructures Research Laboratory, Japan Fine Ceramics Center, Nagoya, Japan

3 Research Institute for Electronic Science, Hokkaido University, Sapporo, Japan

References

[1] Line, M. E., & Glass, A. M. (1997). Principles and Applications of Ferroelectrics and
Related Materials,. Claredon, Oxford,.

[2] Cochran, W. (1960). Crystal stability and the theory of ferroelectricity. Adv. Phys., 9,
387.

[3] Cochran, W. (1961). Crystal stability and the theory of ferroelectricity part II. Piezo‐
electric crystals. Adv. Phys., 10, 401 EOF-420 EOF.

[4] Scott, J. F. (1974). Soft-mode spectroscopy: Experimental studies of structural phase

transitions. Rev. Mod. Phys. ., 46, 83 EOF-128 EOF.

[5] Shan, Y. J., Mori, H., Imoto, H., & Itoh, M. (2002). Ferroelectric Phase Transition in
Perovskite Oxide CdTiO3. Ferroelectrics, 381 EOF-386 EOF.

[6] Shan, Y. J., Mori, H., Tezuka, K., Imoto, H., & Itoh, M. (2003). Ferroelectric Phase
Transition in CdTiO3 Single Crystal. Ferroelectrics, 107 EOF-112 EOF.

[7] Moriwake, H., Kuwabara, A., Fisher, C. A. J., Taniguchi, H., Itoh, M., & Tanaka, I.
(2011). First-principles calculations of lattice dynamics in CdTiO3 and CaTiO3: Phase
stability and ferroelectricity. Phys. Rev. B, 84, 104.

[8] Taniguchi, H., Shan, Y. J., Mori, H., & Itoh, M. (2007). Critical soft-mode dynamics
and unusual anticrossing in CdTiO3 studied by Raman scattering. Phys. Rev. B, 76,
212103.
294 Advances in Ferroelectrics

[9] Clark, S. J., Segall, M. D., Pickard, C. J., Hasnip, P. J., Probert, M. I. J., Refson, K., &
Payne, M. C. (2005). First principles methods using CASTEP. Z. Kristallogr, 220, 567.

[10] Bersuker, I. B. (1995). Recent development of the vibronic theory of ferroelectricity:.

Ferroelectrics, 164, 75.

[11] Taniguchi, H., Soon, H. P., Shimizu, T., Moriwake, H., Shan, Y. J., & Itoh, M. (2011).
Mechanism for suppression of ferroelectricity in Cd1−xCaxTiO3. Phys. Rev. B, 84,
174106.

[12] Taniguchi, H., Soon, H. P., Moriwake, H., Shan, Y. J., & Itoh, M. (2012). Effect of Ca-
Substitution on CdTiO3 Studied by Raman Scattering and First Principles Calcula‐
tions. Ferroelectrics, 268 EOF-273 EOF.

[13] Taniguchi, H., Takesada, M., Itoh, M., & Yagi, T. (2004). Effect of oxygen isotope ex‐
change on ferroelectric microregion in SrTiO3 studied by Raman scattering. J. Phys.
Soc. Jpn., 73, 3262 EOF-3265 EOF.

[14] Taniguchi, H., Takesada, M., Itoh, M., & Yagi, T. (2005). Isotope effect on the soft-
mode dynamics of SrTiO3 studied by Raman scattering. Phys. Rev. B, 72, 064111.

[15] Müller, K. A., Burkard, H., & Sr Ti, O. (1979). An intrinsic quantum paraelectric be‐
low 4 K. Phys. Rev. B, 19, 3593.

[16] Itoh, M., Wang, R., Inaguma, Y., Yamaguchi, Y., Shan, Y. J., & Nakamura, T. (1999).
Ferroelectricity Induced by Oxygen Isotope Exchange in Strontium Titanate Perov‐
skite. Phys. Rev. Lett., 82, 3540 EOF-3543 EOF.

[17] Tokunaga, M., & Aikawa, Y. (2010). Isotope-Induced Ferroelectric Phase Transition
in Strontium Titanate Only by a Decrease in Zero-Point Vibration Frequency. J. Phys.
Soc. Jpn., 79, 024707.

[18] Taniguchi, H., Itoh, M., & Yagi, T. (2007). Ideal Soft Mode-Type Quantum Phase
Transition and Phase Coexistence at Quantum Critical Point in 18O-Exchanged
SrTiO3. Phys. Rev. Lett., 99, 017602 EOF.

[19] Dec, J., & Kleemann, W. (1998). From barrett to generalized quantum curie-weiss
law. Solid State Commun., 106, 695 EOF.

[20] Vojta, M. (2003). Quantum phase transitions. Rep. Prog. Phys., 66, 2069.

[21] Sondhi, S. L., Girvin, S. M., Carini, J. P., & Shahar, D. (1997). Continuous quantum
phase transitions. Rev. Mod. Phys., 69, 315 EOF-333 EOF.

[22] Schneider, T., & Stoll, E. F. (1976). Quantum effects in an n-component vector model
for structural phase transitions. Phys. Rev. B, 13, 1123 EOF-1130 EOF.
 Chapter 14

Electromechanical Coupling Multiaxial Experimental

and Micro-Constitutive Model Study of
Pb(Mg1/3Nb2/3)O3- 0.32PbTiO3 Ferroelectric Single
Crystal

Wan Qiang, Chen Changqing and Shen Yapeng

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52540

1. Introduction

Compared to polycrystalline ferroelectric ceramics such as Pb(Zr1/2Ti1/2)-O3 (PZT), domain en‐

gineered relaxor ferroelectric single crystals Pb(Zn1/3Nb2/3)O3-xPbTiO3 (PZN-xPT) and
Pb(Mg1/3Nb2/3)O3-xPbTiO3 (PMN-xPT) show greatly enhanced electromechanical properties:
the piezoelectric coefficient d33 and electrically induced strain of <001> oriented single crystals
direction can respectively reach 2500pC/N and 1.7%, or even greater [1],[2]. PZN-xPT and
PMN-xPT with outstanding properties are usually near the morphotropic phase boundary
(MPB), separating rhombohedra (R) and tetragonal (T) phases [1], [4], [5]. For example, the
MPB is located within a range of x=0.275-0.33 for PMN-xPT [6], [7]. Recent investigations have
also shown that the MPB of PMN-xPT and PZN-xPT is actually in a multi-phase state at room
temperature [8], [9]. e.g., the coexistence of rhombohedra (R) and monoclinic (M) phases at
x=0.33 or rhombohedra and tetragonal phases at x=0.32. Other phases can also exist near MPB
under stress and/or electric field loading. Experiment studies [10], [11], [12] and first-princi‐
ples calculations [4], [13]reveal that two different homogeneous polarization rotation path‐
ways are present between rhombohedra and tetragonal phases under an electric field. It is
found that three kinds of intermediate monoclinic phases MA, MB and MC are associated with
the two pathways [9], [10]. Orthorhombic phase has also been observed between the rhombo‐
hedra and tetragonal phases when PMN-PT is loaded with strong electric field along the <110>
direction [9],[14]. Although the mechanism underlying the high performance of these crystals
is not completely clear, the existence of the intermediate phases and the associated phase tran‐
sitions are believed to be one of the main reasons [1], [3], [4], [8], [10].

© 2012 Qiang et al.; licensee InTech. This is an open access article distributed under the terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
296 Advances in Ferroelectrics

Note that PZN-PT and PMN-PT single crystals usually experience electric and/or mechani‐
cal loading during their in-service life. It has been shown that externally applied loading has
significant effect on the properties of these crystals [1], [5]-[28]. A number of studies have
focused on the loading induced behavior of <001> and <110> oriented anisotropic PZN-xPT
and PMN-xPT crystals [1], [5], [9], [15]-[19]. It is has been shown loading in the form of elec‐
tric field [1]-[21], and stress[21]-[26], can lead to polarization switching and phase transi‐
tions, which changes the crystal phase and domain structure of these single crystals, and
hence dramatically alter their electromechanical properties. A mature level understanding
of their responses to electrical, mechanical and temperature loading condition is thus essen‐
tial to fulfill the applications of these crystals.

Rhombohedral phase of PZN-xPT(0<x<0.1) and PMN-xPT(0<x<0.35) exhibit excellent electro‐

mechanical properties along {001} and {110} orientations compared to the {111}(cubic cell ref‐
erence) spontaneous polarization direction. A number of studies have focused on the
loading induced behavior of {001}, {011} and {111} oriented PZN-xPT and PMN-xPT single
crystals. It has been shown that loadings in the form of electric field and stress can lead to
polarization rotation and phase transition, which change the crystal phase and domain
structure of these single crystals, and hence dramatically alter their electromechanical prop‐
erties. When an electric field is applied along the {001} direction of PZN-PT, polarization ro‐
tation occurs from {111} towards {001} via either MA or MB, depending the composition (e.g.,
the rotation is R-MA-T for PMN-4.5PT). For {110}-oriented PMN-PT, polarization rotates
from {111} to {110} via MB when electric field is along {110} and ends up with an orthorhom‐
bic phase when the electric field exceeds a critical value. These single crystals can be polar‐
ized into a single domain state with {111} oriented electric field. Most available studies on
the effect of bias stress on the crystal behavior focus only on uni-polar electric field loading.
However, it has been shown that the uni-polar and bi-polar responses of these crystals can
be very different.

A number of studies have focused on experimental, but the constitutive model of ferroelec‐
tric single is absent. Huber [29] and Bhattacharya[30], [31] et.al established a model based on
the micromechanical method, but the simulation is not well compare to experimental result.

At present, a mature model to explain the stress-strain behavior of ferroelectric single is ab‐
sent all along. In this study, electric field induced “butterfly” curves and polarization loops
for a set of compressive bias stress of {001}, {011} and {111} poled PMN-0.32PT single crystals
will be explored by systematical experiment study. The effects of the compressive bias stress
on the material properties along these three crystallographic directions of PMN-0.32PT sin‐
gle crystals will be quantified. The underlying mechanisms for the observed feature will be
explained in terms of phase transformation or domain switching,depending on the crystallo‐
graphic direction.The stress-strain curves along <001> crystallographic direction of ferroelec‐
tric single crystals BaTiO3 will be calculated in the first principle method to validate
polarization rotation model. Finally, Based on the experimental phase transformation mech‐
anism of ferroelectric single crystal, a constitutive model of ferroelectric single crystal is pro‐
posed based on micromechanical method. This constitutive model is facility and high
computational efficiency.
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2. Experimental methodology

At the test room temperature, PMN-0.32PT single crystals used in this study are of mor‐
photropic composition, and in the rhombohedral phase, very close to MPB. The pseudo-
cubic {001}, {011} and {111} directions of these crystals are determined by x-ray
diffraction (XRD). Pellet-like specimens of dimensions 5 × 5 × 3mm3 are then cut from
these crystals, with the normal of the 5 × 5mm2 major specimen surfaces along the pseu‐
do-cubic {001}, {011} or {111} direction. All specimens are electroded with silver on the
5 × 5mm major surfaces and poled along the {001}, {011} and {111} orientations (i.e., the
specimen thickness direction) under a field of 1.5kV/mm. Note that there are eight possi‐
ble dipole orientations along the body diagonal directions of unpoled PMN-0.32PT sin‐
gle crystals (i.e., the <111> direction). When an electric poling field is applied to the
crystals along the {001} direction, a multi-domain structure can be produced, comprising
four degenerate states. For {011} direction poled single crystals, the number of degener‐
ate states is two. The single crystals can be poled into a single domain state when they
are poled along the {111} direction. The states of {001}, {011} and {111} poled
PMN-0.32PT single crystals are sketched in Fig. 1, where solid arrows refer to the do‐
main states induced by poling (also labeled as type 1 in Figs. 1b and 1c), dotted arrows
represent possible domains switched from type 1 domains upon loading or unloading,
and vice versa (also labeled as type 2, ).

s

[111] E3
s [011] s type 1
[001]
E3 E3
R type 1 type 2
54.70 35.50 710

O
T type 2

(a) (b) (c)

Figure 1. (a) Multidomain rhombohedral crystal obtained by poling along the {001} orientation. The solid line arrows
show possible directions of the polarization vector in a fully {001} poled rhombohedral crystal, the dashed line arrows
show possible directions of the polarization vector in orthorhombic and tetragonal phases crystal. (b) Two domain
rhombohedral crystal obtained by {011} poling. The solid line arrows indicate type 1 domains in a fully {011} poled
crystal and dashed line arrows indicate possible type 2 domains under compressive stress. (c) Monodomain rhombo‐
hedral crystal poled along the {111} orientation. The solid and dashed line arrows have similar means to (b). The hol‐
low arrows in Fig. a ~ Fig. c show the electric field and stress loading. The small rhombohedral distortion is neglected
and all numbers and notations refer to a quasi-cubic unit cell.
298 Advances in Ferroelectrics

Since the focus of this study is to explore the effect of bias stress on the electromechani‐
cal properties of PMN-0.32PT single crystals along different crystallographic directions,
experimental setup is adapted from Ref. [31] (Fig.2) to allow simultaneously imposing
uniaxial stress and electric field to the specimen along the thickness direction. Mechani‐
cal load is applied by a servo-hydraulic materials test system (MTS) and electric field is
applied to the specimen using a high voltage power amplifier. Once the specimen is
placed in the fixture, a compressive bias stress with magnitude of at least 0.4MPa is
maintained throughout the test to ensure electrical contact. Stress controlled loading in‐
stead of displacement controlled loading is adopted during the test, so that the speci‐
men is not clamped but is free to move longitudinally when electric field E3 and
mechanical stress σ33 loading are applied, where subscript 3 refers to the thickness direc‐
tion of the samples, corresponding to the {001}, {011} and {111} direction of {001}, {011}
and {111} oriented PMN-0.32PT single crystals, respectively. During test, polarization P3
(or electric displacement) is measured using a modified Sawyer-Tower bridge, and the
deformation (i.e., the strain) is monitored by two pairs of strain gauges (in total four
strain gauges used) mounted on the four 5 × 3mm2 surfaces: one pair placed on two op‐
posite 5 × 3mm2 surfaces is applied to measure the longitudinal normal strain ε33 along
the {001}, {011} and {111} direction and another pair to measure the transverse normal
strain ε11 in the direction perpendicular to the {001}, {011} and {111} direction respective‐
ly. Output of the strain gauges during deformation is recorded by a computer through a
multiple-channel analog-to-digital (AD) converter.

The first set of tests is performed for electric field loading of triangular wave form of
magnitude 0.5kV/mm and frequency 0.02Hz, free of stress loading. The low frequency is
chosen to mimic quasistatic electric loading, which is of particular interest in this study
[32]. Unless stated otherwise, this loading frequency for the electric field is used
throughout the following test. The second set of tests consists of mechanical loading
upon short circuited samples. The samples are compressed to –40MPa and unloaded to
–0.4MPa at loading and unloading rate of 5MPa/min, followed by an electric field which
is sufficiently large to remove the residual stress and strain to re-polarize the samples.
In the third set of tests, triangular wave form electric field is applied to the samples
which are simultaneously subject to co-axial constant compressive stress preload. The
magnitude of the preload is varied from test to test and is in the range between 0 and
-40MPa. Note that there is a time-dependent effect of the depolarization and strain re‐
sponses under constant compressive stress. To minimize this effect, each electric field
loading starts after a holding time of 150 seconds for a new stress preloading. It is
found that three cycles of electric field loading and unloading are sufficient to produce
stabilized response for each constant prestress, and the results for the last cycle are re‐
ported in the following.
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Force

Steel Steel
ball
High
voltage
Strain
Ethoxyline
gauges
Brass
Oil Oil
Brass bath

Ethoxyline
Ground

Figure 2. The sketch of experimental set

3. Experimental results and discussion

3.1. Crystallographic dependence of electric behavior and piezoelectric properties

The measured electric field induced polarization hysteresis loops and butterfly curves for
{001}, {011} and {111} oriented poled PMN-0.32PT single crystals without stress loading are
shown in Figs. 3a and 3b. The remnant polarizations Pr (defined as the polarization value at
zero electric field), the coercive electric fields Ec (defined as the electric field value at zero
polarization) and the piezoelectric coefficients d33 (defined as d33=Δε33 / ΔE3 where ΔE3 is
limited between –0.05 and +0.05 kV/mm, namely the slops of the ε33 − E3curves as the electric
field passes through zero) depend strongly on the crystallographic orientation. From Figs.
3a and 3b, one can calculate that Pr , Pr and Pr are 0.247, 0.324 and 0.395C/m2,
001 011 111
Ec , Ec and Ec are 0.255, 0.298 and 0.216kV/mm, and d33 , d33 and d33
001 011 111 001 011 111
are 1828, 1049 and 200pC/N, respectively. It is noticed that there are eight possible polariza‐
300 Advances in Ferroelectrics

tion orientations along the pseudo-cubic {111} for un-poled rhombohedral PMN-0.32PT sin‐
gle crystals. Upon poling, the dipoles switch as close as possible to the applied electric field
direction: For {001} poled crystals, there are four equivalent polar vectors along the {111} ori‐
entation, with an inclined angle of -54.7º from the poling field (Fig. 1a); For {011} poled crys‐
tals, there are two equivalent polar vectors along the {111} direction (labeled as type 1 in Fig.
1b); For {111} poled crystals, there is one polar vector along {111} (type 1 in Fig. 1c). Accord‐
ing to the domain configurations in Fig. 1, the remnant polarizations Pr and Pr are
001 011

approximately related to Pr
111
by Pr
001
= Pr
111
/ 3 and Pr
011
= 2Pr
111
/ 3, respective‐

ly. By taking the measured value for Pr (0.395C/m ), Pr 2

and Pr are predicted to
111 001 011
be 0.228 and 0.322C/m2, respectively, which are very close to the measured ones ( Pr
001
=0.227C/m2 and Pr =0.324C/m2). Therefore, the measured results are consistent with the
011
domain configurations shown in Fig. 1.

It is also seen from Figs. 3a and 3b that the coercive field is lowest for the {111} oriented crys‐
tals, and becomes successively higher for {001} and {110} orientations. This is same to Ref.25
except for {110} orientation. This trend of coercive field is due to two reasons: One is due to
reorientation driving force being proportional to the component of electric field aligned with
the rhombohedral direction; The other one is due to the domain switching process. In {111}-
oriented PMN-0.32PT single crystals, there are two types of domains (shown as type 1 and
type 2 in Fig.1c). When the electric field is decreased from 0.5kV/mm to –0.05kV/mm, the
strain first decreases linearly (see Fig.3b). When the electric field is decreased further, the
type 1 domain switches to type 2 domains, leading to abrupt displacement change. When
the electric field exceeds the coercive field –0.216kV/mm, the type 2 domains switch back to
type 1 domain, recovering the deformation. In type 2 domain state, three equivalent polar
vectors with an angle of 71º from the {111} direction can coexist and are separated by do‐
main walls across which the normal components of electric displacement and displacement
jump are zero. Ideally, this type of domain walls has no associated local stress or electric
field. So the existing of type 2 domain state and the largest component of electric field along
polarization direction induces the lowest coercive field in {111} orientation poled crystal. In
the {011} orientation crystals, there are also two types of domains (i.e., type 1 and type 2 do‐
main in Fig. 1b), the domain switching process is similar to {111}-poled crystals. In the type 2
domain state, however, the four possible polar vectors are perpendicular to the applied elec‐
tric field (Fig. 1b). It is thus difficult to switch type 2 domain to type 1 domain only by ap‐
plying electric field. Both the type 2 domain state and the smallest component of E
contribute to the largest coercive field in {011} oriented crystals. In {001} oriented crystals,
there will be no associated local stress or electric field, similar to type 2 domain state of {111}
poled crystals. This feature again renders domain switching easy. On the other hand, the do‐
main structure of {001} poled crystals is stable [4] and the component of electric field is
smaller, giving the coercive field higher than that of {111} poled crystals but lower than that
of {011} oriented crystals (see, Figs. 3a and 3b).
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Figure 3. Electric field induced polarization and strain responses for {001}, {011} and {111}-oriented crystals of
PMN-0.32PT: (a) P3 − E3 curves and (b) ε33 − E3 curves. (c) Relationship between rhombohedral (solid lines) and cubic
(dashed lines) coordinate systems. Subscripts r and c denote directions with respect to the rhombohedral and cubic
coordinate systems, respectively. (d) Orientational dependence of piezoelectric coefficient d * of PMN-0.32PT in the
33
polar plane.

Some researchers attribute the high piezoelectric coefficients along {001} and {011} oriented
ferroelectric single crystals to the engineered domain state [4, 11]. It has also reported that,
however, the piezoelectric coefficient along the {001} direction of single crystals with mono-
domain structure is comparable to that of crystals with multi-domain structure [17], imply‐
ing the origins of the high piezoelectric constants of PMN-0.32PT single crystals may not be
due to the engineered domain state. Instead, it could be due to the effect of crystal lattice
properties. To further explore this issue, we follow Ref. [17] to calculate the piezoelectric co‐
efficients d * along an arbitrary direction in a mono-domain crystal. For a direction defined
ij
302 Advances in Ferroelectrics

by the Euler angles (φ, θ, ψ ) (see Fig. 3c), d * is related to dij (measured along the principal
ij
crystallographic axes) by,

d* 33 (f ,q ) = d33 cos 3 q + (d15 + d31 )cosq sin 2 q - d22 cos f sin 3 q (cos 2 f - 3sin 2 f ) (1)

With d33=200pC/N taken from our measured value and d15=4100, d31=–90 and d22=1340pC/N,
d* (0, θ) for PMN-0.32PT single crystals can be calculated and is shown in Fig. 3d. Note
33 111
that in the case of ϕ = 0 θ =-35.5º and -54.7º correspond to {011} and {001} direction, respec‐
tively. d * =1471pC/N and d * =2311pC/N can be inferred from Figs. 3d, which are
33 011 33 001
not far away from our measured values (d =1049 pC/N and d =1828 pC/N). The
33 011 33 001
small discrepancy between the predictions and measurements is believed to be due to the
fact that the predictions are based on ideal mono-domain single crystals while the material
parameters used in Eq. (1) are actually from less ideal mono-domain crystals (in fact, they
are more or less multi-domain crystals). Nevertheless, we can conclude that the dominant
contribution to the large {001} and {011} piezoelectric response should be the crystal aniso‐
tropy other than engineered domain state.

3.2. Crystallographic dependence of stress induced strain and polarization responses

Figure 4 shows the measured σ33 − ε33 and σ33 − P3 curves for {001}, {011} and {111} oriented
short circuited samples. The results indicate obvious crystallographic anisotropy in stress in‐
ducing responses. From domain switching viewpoint, there should be no significant defor‐
mation in the thickness dimension of {001} poled crystal samples under stress loading,
except for the elastic strain. However the longitudinal strain of {001} is contractive with a
maximum magnitude of 0.3% under –40MPa. The contractive strain of {001} oriented crys‐
tals is about twice as much as those of {011} (about –0.18%) and {111} (about –0.17%) orient‐
ed crystals under a loading of –40MPa (Fig. 4a). This abnormal behavior of {001}-oriented
crystals lies in that the mechanism underlying the stress induced response of {001}-oriented
crystals is the R to O and T phase transition (see, Fig. 1a) rather than domain switching for
{011} and {111} oriented crystals: the lattice distortion due to phase transition induces large
deformation in the thickness dimension of {001} poled crystals. In {011} and {111}- poled
crystals, on the contrary, the type 2 multi-domain state induced by compressive stress is the
stable and preferred state (Figs. 1b and 1c), and can form more easily by domain switching
than phase transformation. Therefore, the stress induced strain and polarization curves in
{011} and {111} orientation crystals are similar to those of ferroelectric polycrystals of which
domain switching is also the dominant deformation mechanism (Figs. 4a and 4b). During
the unloading of {001} oriented crystals (corresponding to the returning to R phase of the
unstable O phase), the σ33 − ε33 and σ33 − P3 curves show obvious nonlinear behavior. Note
that the remnant strain and polarization at the end of unloading are attributed to the stable
T phase which does not switches back to the R phase. For {011} and {111}-oriented crystals,
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however, there is only domain switching (i.e., switching between type 1 and type 2 do‐
mains) and no phase transformation occurs. During unloading, the σ33 − ε33 curves and
σ33 − P3 curves of {011} and {111} show linear response since almost no domain switches back
(Figs. 4a and 4b).

0 0
-5 -5
-10 -10

s33 (MPa)
s33 (MPa)

-15 -15
-20 -20
-25 [001] -25 [001]
-30 [011] -30 [011]
-35 [111] -35 [111]
-40 -40
-3.5 -3 -2.5 -2 -1.5 -1 -0.5 0 -0.25 -0.2 -0.15 -0.1 -0.05 0
e33(microstrain) D3(C/m )
2

Figure 4. Compressive loading and unloading stress cycles induced polarization and strain responses for {001}, {011}
and {111}-oriented crystals of PMN-0.32PT: (a) σ33 − ε33 curves and (b) σ33 − P3 curves.

The stress cycles of {001} poled crystals can be explained by the polarization vector rota‐
tion mechanism sketched in Fig. 5 as follows. In general two most possible mechanisms
responsible for the observed features of {001} poled crystals in Figs.4 are domain switch‐
ing and polarization rotation associated phase transformation. Recall that the PMN-0.32PT
single crystals considered here are in the R phase close to MPB (although in reality there
could also be M or T phase in these crystals near MPB [8], [9] the R phase is nevertheless
the dominant phase). It is noted that that, upon application of a field along the <001> po‐
ling axis of R phase domain engineered PMN-0.32PT single crystals, only four of the eight
polarization orientations are possible, i.e., <111>, <1̄11>, <11̄1>, and <1̄1̄1>. Since the <001>
components of these four polar vectors are completely equivalent, each domain wall can‐
not move under an external electric field along the <001> direction owing to the equiva‐
lent domain wall energies [32]. In other words, no ferroelectric domain switching is
possible. Equally, no ferroelastic domain switching is expected when a compressive stress
is applied along the <001> axis. (For PMN-PT systems with orthorhombic 4O <001> do‐
main engineered structure [33], 60º switching from <011> to <110> would be driven by an
applied stress. But, this is not what we are considering). Such facts partly rationalize our
hypothesis that the underlying mechanism associated with the observed behavior of the R-
phased PMN-0.32PT single crystals considered in this paper is phase transformation. Nev‐
ertheless, it should be emphasized that since no in situ diffraction observation is
conducted to properly identify the stress induced phase transformation in PMN-0.32PT
single crystals, discussions in this paper on phase transition are solely inferred from the
measured stress induced strain and polarization curves.
304 Advances in Ferroelectrics

s 33 s 33
R
R
MA MA R

MC T MC
T T
O O O

(a ) (b) (c)

R
R

T MC T
O O

( e) (d )

Figure 5. Schematic drawing of the polarization rotation from R to T and O phases due to <001> direction compres‐
sion: (a) the initial state, (b) polarization starts to rotate from R to O and T via two pathways MA and MC, (c) R phase
completely transformed, (d) O phase starts to switch back to R phase upon unloading, (e) O phase completely switch‐
ed back to R phase. The states (a) to (e) correspond to the stress levels marked in Figs. 2(a) and 2(b). At the initial poled
state (a), PMN-0.32PT possesses four equivalent <111>-oriented polarizations vector close to <001> direction though
only one polarization rotation processes is shown here.

Fig. 5 illustrates the polarization rotation mechanism of PMN-0.32PT single crystals under
stress loading and unloading cycle. The polarization vector states shown in Figs. 5(a)-5(e)
correspond to the stress levels marked on the curves in Figs. 4 for the -40MPa stress cycle. In
the initial poled state, PMN-0.32PT single crystals possess four equivalent <111> polariza‐
tions, with only one shown in Fig. 5a for the sake of clarity. Upon loading, polarization vec‐
tor starts to rotate from R to O and T phases through intermediate phases MA and MC, when
the compressive stress exceeds about 15MPa in magnitude (Fig. 5(b)). This gives a mixture
of R and T phases and remarkable augment in the polarization and strain change around σ33
=-20MPa (Figs. 4). When the presence of an electric field along <110> direction, polarization
rotation only occurs from R to O under compression along <001> direction. In the absence of
electric field along <110>, however, almost all the polarization vectors may switch to T and
O phases when the compression exceed 30MPa in magnitude (Fig. 5(c)). When the magni‐
tude of the compressive loading is further increased, there is no more polarization rotation
and the PMN-0.32PT single crystal shows linear response in Figs. 4. It is noted that O phase
is usually unstable (its free energy balance between R and T phases depends on the electric
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and mechanical loading history [9], [14]). Upon unloading, the O phase switches back to R
phase when the compression lower than -10MPa (Figs. 4, and 5(d)). On the other hand T
phase is a stable phase. It will not switch back to R phase upon unloading, leading to rem‐
nant strain of about -0.07% for and remnant polarization of about -0.13C/m2 at the end of the
-40MPa stress cycle (Figs. 4(a) and 4(b), Fig. 5(e)). After the stress cycle, a unipolar electric
field of 0.5kV/mm in magnitude is applied to re-pole the single crystal to its initial state, i.e.,
the polarization vector completely switches back. As a result, the remnant strain and polari‐
zation diminish to zero at the end of the re-polarization process (Figs. 5(a) and 5(e)).

3.3. Crystallographic dependence of electric field induced behavior at constant bias

compressive stress

The ε33 − E3 “butterfly” curves and P3 − E3 hysteresis loops of {001}, {011} and {111} poled
crystals under different constant compressive bias stresses are shown in Fig. 6. Depend‐
ence of the electric coercive Ec , remnant polarization Pr , dielectric permittivity χ33, piezo‐
electric coefficient d33 and aggregate strain Δε for {001}, {011} and {111} oriented crystals
on the compressive bias stress is summarized in Fig. 7. The aggregate strain Δε is defined
as the difference between the maximum and minimum strain for a complete responsive
butterfly curves. Similar to d33, χ33 are calculated by ΔP3 / ΔE3 where ΔP3 is the polariza‐
tion difference between –0.05 and +0.05kV/mm. The calculated χ33 within such a small
field range is almost equal to the slope of P3 − E3 hysteresis loops when the electric field
passes through zero. The calculated χ33 includes both the reversible (intrinsic dielectric
property) and irreversible (extrinsic domain switching and phase transformation related
property) contributions of the material, which is generally higher than the permittivity
measured by a dynamic method [32].

The influence of the preloaded compressive stress on the aggregate strain Δε , remnant po‐
larization Pr and piezoelectric coefficient d33 seems to be similar for {001}, {011} and {111}
oriented crystals: The remnant polarization Pr decreases with increasing the magnitude of
the compressive prestress; The aggregate strain Δε and piezoelectric coefficient d33 first in‐
crease and then decrease with the magnitude of the prestress increasing. As suggested earli‐
er, however, the underlying mechanisms for the electromechanical behavior of {001} {011},
and {111} oriented crystals are different. The change of the dielectric permittivity χ33 {001}
oriented crystals under compressive stress is similar to that of χ33 induced by temperature:
near the phase transformation temperature there is a peak in the χ33 curves, As is shown in
Fig. 7c, there is a small peak near –6MPa and a big peak near –20MPa in χ33 curves for {001}
oriented crystals. This may be due to R-M (near –6MPa) and M-R and M-O phase transfor‐
mation (near –20MPa). On the other hand, there is no obvious peak in χ33 curves for {011}
and {111}-oriented crystals (Fig.7c). The change of χ33 curves induced by compressive stress
and the aforementioned stress induced strain and polarization responses are consistent with
the hypothesis that there is phase transformation for {001}-orientated crystals under com‐
pressive stress.
306 Advances in Ferroelectrics

As suggested by Fu et al. [7], for {001} oriented crystal origins of large aggregate strain and
high piezoelectric coefficient at a moderate compressive bias stress (i.e., around -20MPa for
the single crystals considered here) may be attributed to the stress induced intermediate
states between rhombohedral and tetragonal phases. Under a bias stress of about -20MPa,
PMN-0.32PT single crystals, after a phase transformation, are in a state of monoclinic phase
which has a larger c / a (c and a are lattice parameters) and a smaller polarization component
along the field direction than those of rhombohedral phase [20], implying electric field in‐
duced greater aggregate strain and piezoelectric coefficient (Figs. 7d and 7e). With the mag‐
nitude of the compressive bias stress increased further (i.e., σ33=-30 and -40MPa), the {001}
oriented single crystals are in the state of a mixture of orthorhombic and tetragonal phases.
Although O and T phases also have large c to a ratio, the presence of a large compression
has an opposite effect (i.e., preventing larger deformation induced by electric field) and re‐
sults in small aggregate strain (Fig.7e).
*
As is noted, the polarization rotation introduced by compression gives rise to θ in d33 (ϕ, θ)
in the range between -54.7º and -90º (the angle between loading and polarization direction of
*
T or O phase) under -20MPa, and results in larger d33 in accordance with Eq. (1) (see in Fig.
7d). When the magnitude of the compressive bias stress increases further, θ approaches 90º
*
and d33 becomes smaller. Meanwhile, the remnant polarization Pr and coercive field Ec de‐
crease monotonically with the applied compressive bias stress because of the decreased
component polarization along the {001} direction under compression (Fig.7b).

Under zero stress, the initial state of {011}-oriented crystals is of multi-domain with two
equivalent polarization directions (Fig.1b). For {111}-oriented crystals, the initial state is of
mono-domain with polarization direction in the {111} direction (Fig.1c). When the applied
electric field decreases from 0.5kV/mm to – Ec , the strain and polarization decrease linearly.
Upon approaching –Ec , domain state switches to four polar domain state for {011} oriented
crystals (type 2 in Fig. 1b) and three polar domain state for {111} oriented crystals (type 2 in
Fig. 1c), giving the jumps in strain and polarization responses. When electric field exceeds –
Ec , domain complete second switching, from four polar domain state to two polar domain
state for {011} oriented crystals and from three polar domain state to mono-domain state for
{111} oriented crystals. When the electric field reaches -0.5kV/mm, the strain and polariza‐
tion change linearly again (Fig. 7).

Note that compressive stress can induce domain switching in {011} and {111}-orientated
crystals. When compressive stress is superimposed on the samples, the shapes of ε33 − E3 and
P3 − E3 curves are different from those under the zero stress state (Fig.6c-f). Due to compres‐
sion inducing depolarization, the remnant polarization decreases in {011} and {111} oriented
crystals (Fig. 7b). A low compressive stress (e.g., -5MPa for {011}, -7MPa for {111} ) can lead
to type 1 to type 2 domain switching. As a result, more domains take part in switching dur‐
ing the electric field loading cycle and larger aggregate strainΔε than under zero compres‐
sive stress is observed. This partly explains the observed features in Fig. 7e.
 Electromechanical Coupling Multiaxial Experimental and Micro-Constitutive Model Study of... 307
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(a) 0.5 (b) 0.3 -0.4

-0.4 -6
0 M Pa 0.2 -14
33 (microstrain)

-20
-0.5 -6 0.1 -30

P3 (C/m )
2
-14 -40
-1
-20 0 M Pa
-1.5
-2 -30 -0.1
-2.5 -40 -0.2 [001]
-3 [001]
-0.3
-0.6 -0.4 -0.2 0 0.2 0.4 0.6 -0.6 -0.4 -0.2 0 0.2 0.4 0.6
E3(kV/mm) E3(kV/mm)

(c) 1 (d) 0.4 -0.4

-0.4 0.3 -6
0.5 -14
33 (microstrain)

0.2 -20
-6
P3 (C/m 2 )

0 -30
0.1 -40
-14
-0.5 0 M Pa
-20 -0.1
-1
-30 -0.2
-1.5 [011]
[011] MPa -0.3
-2 -0.4
-0.6 -0.4 -0.2 0 0.2 0.4 0.6 -0.6 -0.4 -0.2 0 0.2 0.4 0.6
E3(kV/mm) E3 (kV/mm)

(e) 0.5 (f) 0.4

[111]
0 -0.4
33 (microstrain)

-6 0.2
P3 (C/m )
2

-0.5 M Pa
-14 0 -40
-1 -30
-20 -0.2 -20
-1.5 -14
-30 -6 [111]
-40 -0.4 -0.4
-2 M Pa
-0.6 -0.4 -0.2 0 0.2 0.4 0.6 -0.6 -0.4 -0.2 0 0.2 0.4 0.6
E3(kV/mm) E3 (kV/mm)

Figure.6 Electric field induced  33  E3 and P3  E3 curves at different compressive bias stresses: (a) and
(b) for6.{001}-oriented;
Figure (c) and
Electric field induced ε −(d) for {011}-oriented,
E and (e) andcompressive
P − E curves at different (f) for {111}-oriented.
bias stresses: (a) and (b) for {001}-
33 3 3 3
oriented; (c) and (d) for {011}-oriented, (e) and (f) for {111}-oriented.
308 Advances in Ferroelectrics

0.3 0.4
(a) (b)
0.35
0.25 0.3
Ec(kV/mm)

Pr(C/mm )
2
0.2 [001] 0.25
0.2
[011] [001]
0.15 0.15
[111] [011]
0.1
0.1
0.05 [111]
0.05 0
0 5 10 15 20 25 30 35 40 0 5 10 15 20 25 30 35 40
-s33 (MPa) -s33 (MPa)
(d) 5000 [001]
4000 [011]
[111]
d 33(pC/N)

3000

2000

1000

0
0 5 10 15 20 25 30 35 40
-s33(MPa)

(e) 2

1.5
De33(microstrain )

1
[001]
[011]
0.5
[111]
0
0 5 10 15 20 25 30 35 40
-s33(MPa)

Figure 7. Effect of compressive bias stress on (a) the coercive field Ec , (b) remnant polarization Pr , (c) piezoelectric con‐
stant d33, (d) relative dielectric constant X33/X0, and (e) and aggregate strainΔε33.
 [001]

33(m
[011]
0.5
[111]
Electromechanical Coupling Multiaxial Experimental and Micro-Constitutive Model Study of... 309
0 http://dx.doi.org/10.5772/52540
0 5 10 15 20 25 30 35 40
-33(MPa)
4. The first principle calculation of stress-strain
Figure.7 Effect of compressive bias stress on (a) the coercive field Ec , (b) remnant polarization Pr , (c
4.1. Calculation methodology
piezoelectric constant d 33 , (d) relative dielectric constant 33/0, and (e) and aggregate strain  33 .
PMN-PT and BaTiO3 have the similar ABO3 structure, so they have the similar ferroelectric
properties.
4 The There is only
first principle Ti4+ particle
calculation ofinstress-strain
B site of BaTiO3, however, there is not only Ti4+ but
4.1also minim Mn methodology
Calculation 4+
and Ni particle in B site of PMN-PT. So the single cell of BaTiO3 is conven‐
2+

ient in calculation
PMN-PT and BaTiO and3 ithave
keepsthethe similar
similar ferroelectric to PMN-PT.
ABO3 structure, so they have the similar ferroelectric
4+
properties. There
In this paper,
is only
we calculate
Ti particle in B site of BaTiO
a single cell of BaTiO3, the single cell
3 , however, there is not only Ti4+ but also
should be the smallest peri‐
4+ 2+
minim
odic Mn and Ni
reduplicate particle
cell, it includes inone
B site
Ti4+ of PMN-PT.
particle, three So
O2- the singleand
particles cellone
of Ba
BaTiO
2+ 3 is convenient in
particle
calculation and it keeps the similar ferroelectric to PMN-PT.
(Fig.8). It is suggested that the initialized state of BaTiO3 ferroelectric single crystal is R
phase after {001} oriented polarization. Refer to literature [34], the crystal lattice constant of
In this paper, we calculate a single cell of BaTiO3, the single cell should be the smallest periodic
R phase BaTiO
reduplicate cell,3 itferroelectric
includes onesingle
Ticrystal
4+ is 4.001
particle, A, the
three O2-coordinate
particlesofand
particle
one Bain single
2+ cell
particle(Fig.8). It i
is shown in table 1.The loading along {001} direction is carried out through application in‐
suggested that the initialized state of BaTiO3 ferroelectric single crystal is R phase after {001}
creasing strain by degrees. Stress and other parameters under each strain level is calculated
oriented polarization. Refer to literatureError! Reference source not found., the crystal lattice
by VASP. Calculation under each strain level include two steps. Firstly, the particle coordi‐
nate of of
constant single cell under
R phase BaTiOeach3 ferroelectric
strain level is calcluated by first
single crystal is principle
4.001 Amolecular dynamic of particle in
, the coordinate
method. Secondly, Stress and other parameters are obtained through
single cell is shown in table 1.The loading along {001} direction is carried relaxation that is based out through
on the first result. Each increment of strain in this paper is 0.5%, untill 4%.
application increasing strain by degrees. Stress and other parameters under each strain level i
calculated by VASP. Calculation under each strain level include two steps. Firstly, the particle
coordinate of single cell under each strain level is calcluated by first principle molecula
dynamic method. Secondly, Stress and other parameters are obtained through relaxation that i
based on the first result. Each increment of strain in this paper is 0.5%, untill 4%.

O32- 
Ti 4
[001] PR
O 22-
c/2

O12-
[100] b/2
a/2
[010] Ba 2
Figure.8 The cell calculation model of BaTiO3 in R phase

Figure 8. The cell calculation model of BaTiO3 in R phase

14
310 Advances in Ferroelectrics

4.2. Discussion

In order to validate that the method a mentioned in this paper is correct, we calculate the
elasticity constant C33 of T phase BaTiO3 using the method mentioned before. Fig.9 shows
that the C33 is 180GPa, which is approach to the experimental value 189± 8Gpa reported in
refer[34]. This means that the method used in this paper is trusty.

0
-0.5
-1
s33(GPa)

-1.5
-2
-2.5
-3
-3.5 BaTiO3
-4
-2 -1.5 -1 -0.5 0
e33(%)

Figure 9. The stress-train curve of BaTiO3 ferrorlctric single crystal obtained by the method amentioned in this paper,
the {001} oriented BaTiO3 ferroelectric single crystal is in T phase.

Stress-strain curve of {001} orientated R phase BaTiO3 calculated in first principle method is
shown in Fig.10(a). Fig.10(a) shows that the result has simlar nonlinear behavior to the ex‐
perimental result of PMN-0.32PT during the loading that sketched in Fig.4(a), namely, there
is obvious “a,b,c” steps during loading. We know that the nonlinear behavior of
PMN-0.32PT shown in Fig.4(a)should be polarization rotation (R→M→O and R→M→T).
The R→M→O is corresponding to the processing of polarization vector PR switching to PO ,
which is shown in Fig.10(b). table 2 is calculated coordinate of particle in BaTiO3, the coordi‐
nate is correspond to point A in fig.10(a). Table 3 is coordinate of particle in O phase BaTiO3
ferroelectric single crystal from refer [35]. Data in table 2 are equal to those in table 3, which
indicates that “A” point in fig.10(a) should be O phase. With increasing strain, the coordi‐
nates of particle are unchangeable after “A”, this indicates BaTiO3 ferroelectric single crystal
is stable in O phase after “A”. From the first principle calculation, we testify that the
PMN-0.32PT ferroelectric single crystal undergoes polarization rotation(R→M→O), this
prove the polarization rotation model is reasonable.
 Electromechanical Coupling Multiaxial Experimental and Micro-Constitutive Model Study of... 311
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0
a
-2 A

s33 (GPa)
-4 b
-6

-8
c BaTiO 3
-10
-4 -3.5 -3 -2.5 -2 -1.5 -1 -0.5 0
e33 (%)
(a)
2-
O 3

[001] PO Ti 4+

c O 22-

b
O12-
[100] a PR

[010] Ba 2+
(b)

Figure 10. (a)The stress-strain curve of {001} oriented BaTiO3 ferroelectric single crystal calculated in first principle cal‐
culation, the scatter point is calculation value and the broken line fit the scatter point.(b) The sketch map of polariza‐
tion rotation during the calculation. The “a,b,c” letter in (a) is correspond to the “a,b,c” letter in (b), the letter indicates
different polarization states during loading.

5. The viscoplastic model of ferroelection single

5.1. The viscoplastic model

From the experimental analysis, it is known that the <001>-oriented PMN-0.32PT single
crystal undergo the R→M→T and R→M→O phase transformation under the compression.
In order to establish a compact model and keep the essence of experiment, R→O phase
312 Advances in Ferroelectrics

transformation of PMN-0.32PT is considered in this study. Polarization rotation cause bulk

deformation and shear deformation associated with the slip planes. It is assumed that the
corresponding deformation associated with the slip planes is shear dominated, a feature
similar to that of the multi-slip system of the crystal plasticity. This similarity renders possi‐
ble to use crystal plasticity models to describe the transformation deformation of
PMN-0.32PT single crystal.

The poled ferroelectric single is four domain state, the polarization vector is along <111>, <1̄
11>, <1 1̄1> and <1̄1̄1> respectively. In this study, it is assumed that the polarization vector of
R phase can switch to the polarization vector of O phase, such as <111> vector switches to
<001>, the vector also can switch back from O phase to R phase. The polarization rotation
has an analogy to crystal plasticity slip, so we suggest there is eight slip systems in
PMN-0.32PT ferroelectric single crystal. According to the crystalgraphic theory, we suggest
ferroelectric single crystal has possible 8 variants; transformation of variants can be charac‐
terized by the habit planes illustrated in Fig.11. where n denotes the unit normal to the habit
plane and s refers to the direction of transformation.

In general, a criterion (i.e., the phase transformation criterion) exists for the phase transfor‐
mation of ferroelectric single crystal, and the material is assumed to undergo phase transfor‐
mation when at least one of the 8 variants satisfies the phase transformation criterion. This is
detailed as follows. Upon loading, the condition to produce R→O polarization rotation on a
specified habit plane is that the driving force G of that plane reaches the critical value G0O.
The driving force is composed of the chemical driving force Gchem and mechanical driving
force Gmech[36]

G = Gchem + Gmech = G0O (2)

A similar condition holds for reverse transformation from O→R polarization rotation with a
critical value G0A

G = Gchem + Gmech = G0 A (3)

In Eqs. (2) and (3), the mechanical driving force can be expressed by

r
Gmech = t ag * + Ea P * (4)

Where τ a and E a are the resolved stress on the “a” transformation system, and γ * and P *
denote the associated transformation strain and transformation polarization. Following the
crystal theory of plasticity, the resolved stress τ a of the variant “a” is related to the stress
tensor σij and the Schmid factor aija by
 Electromechanical Coupling Multiaxial Experimental and Micro-Constitutive Model Study of... 313
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3
ta = å a ijas ij (5)
i , j =1

where the Schmid factor is defined as follow

1
a ija = ( mianaj + maj nia ) (6)
2

with mi and ni being the unit normal to the habit plane and shear direction to the variant
“a”, respectively. The resolved stress E a of the variant “a” is related to the electrical field
tensor Ei

3
Ea = å Ei si (7)
i =1

The chemical driving force in Eqs. (2) and (3) is assumed to be a linear function of the tem‐
perature

Gchem = b (T - T0 ) (8)

where T and T 0 denote the temperature in the single crystal and the equilibrium tempera‐
ture respectively, and β is the stress-temperature coefficient. Note that the equilibrium tem‐
perature T 0 is defined as the average of the starting temperature of O phase transformation
and that of R phase transformation, that is

1
T0 = (Os + Ts ) (9)
2

When applying the rate independent crystal theory based model, Eqs. (2) and (3), to simu‐
late the behavior of ferroelectric single crystals, one of the most computationally consuming
tasks is to determine the set of instantaneously active transformation systems among the 8
possible variants at crystal level. This determination is usually achieved by an iterative pro‐
cedure and must be carried out at each loading step, requiring extensive computation. Note
that in the crystal theory of plasticity, a similar problem exists whilst in a rate dependent
viscoplastic version of crystal theory of plasticity, determination of the set of active transfor‐
mation systems is not necessary. As a result, computation effort can be reduced significant‐
ly. Following this idea, a viscoplastic version of Eqs. (21) and (32) are proposed and
employed in this study. In the viscoplastic crystal model for PMN-0.32PT ferroelectric single
314 Advances in Ferroelectrics

crystals all transformation systems are assumed to be instantaneously active of varying ex‐
tent, which is governed by a rate dependent viscoplastic law. In this paper, the phase trans‐
formation of variant “a” is assumed to comply with the following power law of
viscoplasticity,

1
-1 1/ k
Ga m Ga c
f& a = f&0 (10)
G0 G0 c0

where ḟ a is phase fraction transformation rate of variant “a”, ḟ 0 is reference phase fraction
transformation rate, G a is the driving force of variant “a”, G0 is the critical driving force, ex‐
ponents k and m are material parameters dictating the rate effect, c depends upon the phase
fraction, c0 the reference value at initial state.

The phase fraction of variant “a” is calculated as,

x a = f a / f0 (11)

Summation over all possible variants provides the phase fraction for the whole ferroelectric
single crystal, that is

8
x = åx a (12)
a =1

The incremental form of Eq. (12) can be written as

dx a = df a / f0 (13)

The transformation strain tensor εijtr , which is associated with d f a, can be obtained as

8
de ijtr = å a ijag * df a (14)
r =1

where αij is Schmid factor. d εijtr is increment of phase train. γ * is the maximal strain transfor‐
mation during loading. d f a is increment of phase fraction.

Elastic strain and electrical field induced strain during loading can expressed as
 Electromechanical Coupling Multiaxial Experimental and Micro-Constitutive Model Study of... 315
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de ije = Cijkl ds ij de ijE = dkij dEk (15)

Increment of the total strain d εij can then expressed as the sum of an elastic component dεije ,
a electrical field induced component d εijE and a transformation induced component dεijtr ,

de ij = de ije + de ijE + de ijtr (16)

5.2. Numerical results

To validate the model, the corresponding calculation result is compared to experimental

stress-strain curve. The material parameters used in this study are as follow [37, 38]. Materi‐
al parameters of R phase are C11R = 9.2GPa, C12R = 10.3GPa, C44R = 6.9GPa. γ * = 0.0033,
G0R = 0.5073MJ/m3, β = 0.004MPa/K, 1 / m = 11, 1 / k = 1.0. T = 403, T 0 = 298K. Material parame‐
O O O
ters of O phase are C11 = 38GPa, C12 = 40GPaC44 = 28GPa. G0O = 0.276MJ/m3 β = 0.039MPa/K,
1 / m = 11.5, 1 / k = 1.1. Fig.12 shows the model predicted and experimental measured re‐
sponse. Result in fig.8 shows that stress-strain response of PMN-0.32PT can be predicted by
the developed constitutive model, with quantitative agreement.

Figure 11. The comparison between ferroelectric phase transformation and plastic slip of single crystal, n is direction
normal to slip surface, s is direction along phase transformation.
316 Advances in Ferroelectrics

0
-10
-20
s33(MPa)

-30
-40
Experiment
-50
Model
-60
-3.5 -3 -2.5 -2 -1.5 -1 -0.5 0
-3
e33(10 )

Figure 12. The comparison between experimental and simulation stress-strain curve along <001> direction of ferro‐
electric single crystal.

100 010 001

Ba 2+
0 0 0
O1 2- 0.5133 0.5133 0.0192
O2 2- 0.5133 0.0192 0.5133
O3 2- 0.0192 0.5133 0.5133
Ti4+ 0.489 0.489 0.489

Table 1. The coordinate of particle in R phase BaTiO3 ferroelectric single crystal cell [34]

100 010 001

Ba 2+
0 0 0
O1 2- 0.514 0.514 0.01
O2 2- 0.514 0.016 0.521
O3 2- 0.016 0.521 0.499
Ti4+ 0.4846 0.4846 0.499

Table 2. The calculated coordinate that is correspond to point A in fig.6(a)

 Electromechanical Coupling Multiaxial Experimental and Micro-Constitutive Model Study of... 317
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100 010 001

Ba 2+
0 0 0
O1 2- 0.5144 0.5144 0
O2 2- 0.5 0.0162 0.523
O3 2- 0.0162 0.523 0.5
Ti4+ 0.4857 0.4857 0.5

Table 3. The coordinate of particle in O phase BaTiO3 ferroelectric single crystal cell from refer.

6. Conclusion and discussion

In this paper, Stress induced strain and polarization, and electric field induced “butter‐
fly” curves and polarization loops for a set of compressive bias stress for {001}, {011}
and {111} poled PMN-0.32PT single crystals are experimentally explored. Obtained re‐
sults indicate that high piezoelectric responses of PMN-0.32PT single crystals are con‐
trolled by the anisotropy of the crystals and the multi-domain structure (i.e., engineered
domain structure) has a relatively minor effect. Analysis shows that in all three direc‐
tions the electric field induced aggregate strain Δε and piezoelectric constant d33 in‐
crease with increasing the magnitude of the compressive bias stress. However, when the
magnitude of the compressive bias stress is further increased the electric field induce
Δε and d33 decrease. As a result, an optimized compressive bias stress exists for the
purpose of enhancing the electromechanical properties of {001} and {111} oriented
PMN-0.32PT single crystals. These results have apparent importance in the design of ac‐
tuators and sensors using PMN-0.32PT single crystals. It is found that the observed
stress induced strain and polarization in {001}-oriented PMN-0.32PT can be described by
a polarization rotation mechanism, i.e., polarization rotates from rhombohedral (R) to
orthohombic (O) and tetragonal (T) phases through the intermediate Monoclinic (M)
phase during loading, and O to R transition during unloading. However, domain
switching is believed to be the main mechanism dictating the electromechanical behav‐
ior of {011} and {111} oriented PMN-0.32PT single crystals. polarization rotation model
is developed to explain the observed behaviors of PMN-0.32PT. The stress-strain curve
along <001> crystallographic direction of ferroelectric single crystal BaTiO3 is calculated
with the first principle method. Obtained results show that the R→M→O polarization
rotation (phase transformation) takes place in rhombohedral BaTiO3 ferroelectric single
crystals under compression, which is consistent with the polarization rotation model.
Based on the polarization rotation model, a constitutive model of PMN-0.32PT is pro‐
posed based on micromechanical model. It is shown that the developed model can
faithfully capture the key characteristic of the observed constitutive behavior of <001>
oriented PMN-0.32PT.
318 Advances in Ferroelectrics

Acknowledgments

The authors are grateful for the financial supported by the Natural Science Foundation of
China (No. 10425210,10802081) and the Ministry of Education of China.

Author details

Wan Qiang1, Chen Changqing2 and Shen Yapeng2

1 Institute of Structural Mechanics, China Academy of Engineering Physics, Mianyang, Si‐

chuan, China

2 Key Laboratory, School of Astronautics and Aeronautics, Xi’an Jiaotong University, Xi’an,
China

References

[1] Park S. Shrout TR. Ultrahigh strain and piezoelectric behavior in relaxor based ferro‐
electric single crystals. Journal of Applied Physics 1997:82,1804-1812.
[2] Service RF. Shape-changing Crystals Get Shifter. Science 1997:275,1878-1880.
[3] Liu SF. Park S. Shrout TR. Cross LE. Electric field dependence of piezoelectric prop‐
erties for rhombohedral 0.955Pb(Zn1/3Nb2/3)O3– 0.045PbTiO3 single crystals Journal of
Applied Physics 1999:85,2810-2815.
[4] Fu H. Cohen RE. Polarization Rotation Mechanism for Ultrahigh Electromechanical
Response in Single-crystal Pizeoelectrics. Nature(London) 2000:403,281-283.
[5] Choi SW. Shrout TR. Jang SJ. Bhalla AS. Morphotropic phase boundary in
Pb(Mg1/3Nb2/3)O3-PbTiO3 system. Mater. Lett. 1989:8(6-7),253–255
[6] Luo HS. Xu GS. et. Compositional Homogeneity and Electrical Properties of Lead
Magnesium Niobate Titanate Single Crystals Grown by a Modified Bridgman Tech‐
nique. Jpn. J. Appl. Phys. 2000:39,5581-5585.
[7] Sreemoolanadhan H. Dielectric ceramics in the BaO-Ln2O3-5TiO2 composition. Fer‐
roelectrics. 1996:189,43-46.
[8] Xu GS. Luo HS. Xu HQ. Third ferroelectric phase in PMNT single crystals near the
morphotropic phase boundary composition. Phys. Rev. B, 2001:64(2),020102-020105.
[9] Viehland D. Li JF. Amin A. Electromechanical and elastic isotropy in the (011) plane
of 0.7Pb(Mg1/3Nb2/3)O3-0.3PbTiO3 crystals: Inhomogeneous shearing of polarization.
Journal of Applied Physics 2002:92,3985-3990.
 Electromechanical Coupling Multiaxial Experimental and Micro-Constitutive Model Study of... 319
http://dx.doi.org/10.5772/52540

[10] Noheda B. Zhong Z. Cox DE. Shirane G. Park SE. Electric-field-induced phase transi‐
tions in rhombohedral Pb(Zn1/3Nb2/3)1-xTixO3. Physics Review B.
2002:65,224101-224104.

[11] Ye ZG. Noheda B. Dong M. et al. Monoclinic phase in the relaxor-based piezoelectric/
ferroelectric Pb(Mg1/3Nb2/3)O3-PbTiO3 system. Physics Review B
2001:64,184114-184117.

[12] Ge WW. Luo CT. Zhang QH. Devreugd CP. et al. Ultrahigh electromechanical re‐
sponse in (1−x)(Na0.5Bi0.5)TiO3-xBaTiO3 single-crystals via polarization extension.
Journal of Applied Physics 2012:111, 093508-093511.

[13] Xing ZP. Xu K. Dai G. Li JF. Viehland D. Giant magnetoelectric torque effect and
multicoupling in two phases ferromagnetic/piezoelectric system. Journal of Applied
Physics 2011:110,104510-104514

[14] Tu CS. Tsai CL. Schmidt VH. Luo HS. Dielectric, hypersonic, and domain anomalies
of Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystals. Journal of Applied Physics 2001:89(12),
7908-7916.

[15] Farokhipoor S. Noheda B. Conduction through 71° Domain Walls in BiFeO3 Thin
Films. Physics Review Letter 2011:107,127601-127605.

[16] Topolov VY. Cao H. Viehland D. Correlation between non-180° domain structures in
(1−x)PbA1/3Nb2/3O3−xPbTiO3 single crystals (A = Mg or Zn) under an applied (001)
electric field. Journal of Applied Physics 2007:102,024103-024106

[17] Christelle J. Li JF. Viehland D. Investigation of polarization switching in (001)c,

(110)c, and (111)c oriented Pb(Zn1/3Nb2/3)O3–4.5%PbTiO3 crystals. Journal of Applied
Physics 2004:95,5671-5675.

[18] Cao H. Li JF. Viehland D. Electric-field-induced orthorhombic to monoclinic MB

phase transition in [111] electric field cooled Pb(Mg1/3Nb2/3O3)–30%PbTiO3 crystals.
Journal of Applied Physics 2006:100,084102-084106

[19] Chen KP. Zhang XW. Luo HS. Electric-field-induced phase transition in <001>-orient‐
ed Pb(Mg1/3Nb2/3)O3-PbTiO3 single crystals. Journal of Physics: Condensed Matter
2002:14 (29),571-576.

[20] Tu CS. Tsai CL. Chen LF. Luo HS. Dielectric properties of relaxor ferroelectric
Pb(Mg1/3Nb2/3)O3-xPbTiO3 single crystals. Ferroelectrics 2001:261(1-4),831-836.

[21] Catalan G. Janssens A. Rispens G. Polar Domains in Lead Titanate Films under Ten‐
sile Strain. Physics Review Letter 2006:96,127602-127606.

[22] Viehland D. Powers J. Ewart L. Ferroelastic switching and elastic nonlinearity in

<001>-oriented Pb(Mg1/3Nb2/3)O3–PbTiO3 and Pb(Zn1/3Nb2/3)O3–PbTiO3 crystals. Jour‐
nal of Applied Physics. 2000:88,4907-4912
320 Advances in Ferroelectrics

[23] Viehland D. Li JF. Investigations of electrostrictive Pb(Zn1/3Nb2/3)O3–PbTiO3 ceramics

under high-power drive conditions: Importance of compositional fluctuations on re‐
sidual hysteresis. Journal of Applied Physics 2001:89,1826-1829.

[24] Viehland D. Powers J. Effect of uniaxial stress on the electromechanical properties of

0.7Pb(Mg1/3Nb2/3)O3–0.3PbTiO3 crystals and ceramics. Journal of Applied Physics
2001:89,1820-1824.

[25] Viehland D. Ewart L. Powers J. et al. Stress dependence of the electromechanical

properties of <001> -oriented Pb(Mg1/3Nb2/3)O3–PbTiO3 crystals: Performance advan‐
tages and limitations. Journal of Applied Physics 2001:90,2479-2484

[26] Viehland D. Li JF. Anhysteretic field-induced rhombhohedral to orthorhombic trans‐

formation in <110> -oriented 0.7Pb(Mg1/3Nb2/3)O3–0.3PbTiO3 crystals. Journal of Ap‐
plied Physics 2002:92,7690-7696

[27] Noheda B. Cox DE. Shirane G. Park SE. Polarization Rotation via a Monoclinic Phase
in the Piezoelectric 92% PbZn1/3Nb2/3O3-8% PbTiO3. Physics Review Letter
2001:86,3891-3895.

[28] Shang JK. Tan X. Indentation-induced domain switching in PMN-PT piezoelectric

crystal. Acta Materialia 2001:49,2993-2999.

[29] Sani A. Noheda B. Kornev IA. High-pressure phases in highly piezoelectric

PbZr0.52Ti0.48O3. Physics Review B 2004:69,020105-020108.

[30] Burcsu E. Ravichandran G. Bhattacharya K. Large strain electrostrictive actuation in

barium titanate. Applied Physics Letter 2000:77,1698-1670.

[31] Shu YC. Bhattacharya K. Domain patterns and macroscopic behaviour of ferroelectric
materials. Philosophical Magazine Part B 2001:81(12),2021-2054.

[32] Yu HF. Zeng HR. Wang HX. Li GR. et al. Domain structures in tetragonal
Pb(Mg1/3Nb2/3)O3-PbTiO3 single crystals studied by piezoresponse force microscopy.
Solid State Communications 2005:133,311-314.

[33] Ye ZG. Bing Y. Gao J. Bokov AA. Development of ferroelectric order in relaxor (1-
x)Pb(Mg1/3Nb2/3)O3–xPbTiO3(0<~x<~0.15). Physics Review B. 2003:67,104104-104107.

[34] Ghosez P. Gonze X. Michenaud JP. First-principles characterization of the four phas‐
es of barium titanate. Ferroelectrics 1999:220,1-15.

[35] Shuo D. Yong Z. Long LY. Elastic and Piezoelectric Properties of Ce:BaTiO3 Single
Crystals.Chinese Physics Letter 2005:22(7),1790-1792.

[36] Feng ZY. Tan OK. Zhu WG. et al. Aging-induced giant recoverable electrostrain in
Fe-doped 0.62Pb(Mg1/3Nb2/3)O3-0.38PbTiO3 single crystals. Applied Physics Letters
2008:92, 142910-142914.
 Electromechanical Coupling Multiaxial Experimental and Micro-Constitutive Model Study of... 321
http://dx.doi.org/10.5772/52540

[37] Weaver PM. Cain MG. Stewart M. Room temperature synthesis and one-dimensional
self-assembly of interlaced Ni nanodiscs under magnetic field. J. Phys. D: Appl. Phys.
2010:43,275002-275006.

[38] Desheng F. Takahiro A. Hiroki T. Ferroelectricity and electromechanical coupling in

(1− x)AgNbO3-xNaNbO3 solid solutions. Applied Physics Letter
2011:99,012904-012907.
 Chapter 15

'Universal' Synthesis of PZT (1-X)/X Submicrometric

Structures Using Highly Stable Colloidal Dispersions:
A Bottom-Up Approach

A. Suárez-Gómez, J.M. Saniger-Blesa and

F. Calderón-Piñar

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/51996

1. Introduction

The synthesis of nanostructured ferroelectric materials has been a subject of increasing interest
for more than a decade due to their possible applications as nonvolatile/dynamic random ac‐
cess memories (NVRAMs/DRAMs), tunnel effect capacitors for high frequency microwave ap‐
plications, infrared detectors, micro-electromechanical systems (MEMs) and electro-optical
modulators among others. These materials, when fully integrated into appropriately designed
micro-systems, are promising candidates for robotics sensing and for future medical proce‐
dures requiring an in situ, real time and nondestructive monitoring with very high sensitivity.

As a logical consequence, the quest for nanostructured ferroelectric materials has also led to
modify the synthesis routes usually considered for obtaining conventional bulk materials and
thin films. One of those routes, the sol–gel method, overcomes the inherent limitations of the
conventional powders-based synthesis routes when dealing with molecular homogeneity
and, therefore, it has been extensively studied and applied in different scenarios in order to
obtain not only thin films, nanotubes or nanorods, but also submicron grains due to the dis‐
tinctive dielectric and ferro/piezoelectric features that are associated with size related effects
when average grain size is well below 1 μm [1]-[5]and because of the potential use of these
materials in a plethora of nanodevices [6].

One of the backbones of the ferroelectrics industry is the Lead zirconate titanate [PZT:
Pb(Zr1−xTix)O3] ceramic system, a well-known ABO3 perovskite with a wide range of industri‐
al applications since the early 1950s of the 20th century. Its dielectric and electromechanical
properties have made possible to develop and implement a myriad of devices such as under‐

© 2012 Suárez-Gómez et al.; licensee InTech. This is an open access article distributed under the terms of the
Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
324 Advances in Ferroelectrics

water sonar systems, sensors, actuators, accelerometers, ultrasonic equipment, imaging devi‐
ces, microphones and multiple active and passive damping systems for the car industry.
The sol–gel synthesis of PZT ceramics has evolved a lot since it was first reported in the
mid-1980s of the last century [7]-[9]; thermal treatments, precursors, additives, diluents and
stabilizers have been incorporated and/or modified in order to achieve less hydrolysable,
more stable, compounds to suit a specific need. In the case of the synthesis of thin films,
nanotubes or nanorods, sol–gel routes have been used in many different ways: from the
well-known spin-coating method to the electrophoretic deposition on a given substrate [10]
or the insertion on nanoporous templates [11]. Submicron and nanosized PZT particles are
also important in the fabrication of highly dense bulk ceramics which, even nowadays, com‐
prise almost the entirety of the electroceramics market. In this particular case, several works
have been published in which PZT powders are synthesized first via sol–gel and then put to
sinter for densification [12]-[15]. In this procedure, sintering temperatures tend to lower and
densification attains notably high values mostly due to a higher Gibb’s free energy per unit
surface area while some material properties strongly dependent on grain size are also en‐
hanced [16].
Accordingly, in this chapter we will be devoted to analyze the feasibility of a 'customized' syn‐
thesis of PbZr1-xTixO3 [PZT (1-x)/x] nano/submicrometric structures by using a sol-gel based
colloidal dispersion as a precursor solution. This study will be done on the basis of a 'bottom-
up' approach as it will take into account (i) Synthesis route, (ii) Properties of colloidal disper‐
sions and (iii) Final crystallization. We will try to thoroughly illustrate every synthesis step
while paying special attention to the physicochemical depiction of some phenomena that not
always are sufficiently described or explained. It has to be pointed out that most of the main
procedures, discussions and results contained herein could be easily extrapolated to a wide
range of materials, not exclusively PZT-based ones.

2. Sol-gel based synthesis route

The complexity of the intermediate reactions, one of the few handicaps of the sol–gel meth‐
od, makes almost mandatory a step by step study of the synthesis method. The chemical re‐
activity of precursors is a well-known key feature determining the nature of the
intermediate organic ligands and the control of the hydrolysis rate in the final sol–gel. Sever‐
al studies have been made for particular synthesis routes both theoretical and experimental
and many possible reaction pathways have been proposed and dissected. Particularly, the -
chemistry of metal alkoxides has been intensively studied by Sanchez et al. [17] and Sayer
and coworker [18]. It is our purpose here to analyze the different reaction steps and inter‐
mediates involved in the PZT (1-x)/x sol–gel synthesis using propoxides as starting metal
alkoxides.

2.1. Synthesis
The followed sol-gel route was the acetic acid, acetylacetone and 2-methoxyethanol pro‐
poxy-based sol-gel method as illustrated in Figure 1. Starting reagents for the sol-gel PZT (1-
 ‘Universal’ Synthesis of PZT (1-X)/X Submicrometric Structures Using Highly Stable Colloidal Dispersions... 325
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x)/x solutions were: (1) lead(II) acetate trihydrate (Pb(OAc)2∙3H2O, Mallinckrodt Baker, Inc.,
99.8% pure), (2) glacial acetic acid (HOAc, Mallinckrodt Baker, Inc., 99.7% pure), (3) acetyla‐
cetone (AcacH, Sigma-Aldrich Co., 99% pure), (4) 2-methoxyethanol (2-MOE, Mallinckrodt
Baker, Inc., 100% pure), (5) zirconium(IV) propoxide (Zr(OPr)4, Sigma-Aldrich Co., 70 wt.%
in 1-propanol), and (6) titanium(IV) propoxide (Ti(OiPr)4, Sigma-Aldrich Co., 97% pure).

First, lead acetate was dissolved in acetic acid with a 1:3 molar ratio while stirred and re‐
fluxed at 115 °C during 3 h for dehydration and homogeneity purposes. After this step, a
thick transparent solution was obtained which will be referred hereafter as solution A. On a
separate process, stoichiometric amounts of zirconium and titanium propoxides were mixed
with acetylacetone on a 1:2 molar ratio in order to avoid fast hydrolysis of reactants. This
mixture was stirred and refluxed at 90 °C during 4 h forming a clear yellow solution refer‐
red hereafter as solution B. When this solution cooled down, the precipitation of several nee‐
dle shaped crystals was verified. In order to keep stoichiometry unaffected, we then
repeated the solution B procedure to isolate and characterize some of those crystals by sin‐
gle crystal XRD.

Figure 1. Flow chart depicting the basic experimental procedure followed in order to obtain a 0.4M PZT (1-x)/x sol–
gel based precursor.

Solutions A and B were then mixed together as appropriate amounts of solvent (2-MOE)
were slowly added for complete dilution of the precipitated crystals and for controlling the
PZT concentration on the final solution. Afterwards, a light yellow solution was obtained af‐
ter stirring for 24 h at room temperature.

It must be stated here that we devoted our work to several Zr:Ti molar ratios that are com‐
monly used in practical applications: (i) PZT 25/75, (ii) PZT 53/47, (iii) PZT 60/40, (iv) PZT
80/20 and (v) PZT 95/05. Besides, we also tried to cover a relatively wide concentration range
for every PZT (1-x)/x sol-gel precursor under study: from 0.05 M to 0.4 M. Due to these facts,
we will only focus on the discussion of representative samples instead of discussing irrele‐
vant data of samples that showed no significant discrepancies between each other. As de‐
picted in Figure 1, this section will analyze the synthesis of a 0.4 M PZT 53/47 precursor
solution.
326 Advances in Ferroelectrics

2.2. Experimental techniques

Every reactant and intermediate product was analyzed using FT-IR and Raman spectroscop‐
ies. As was described earlier, single crystal XRD was also carried out for the solution B acic‐
ular precipitates.

2.2.1. Raman spectroscopy

Raman characterization was made on an Almega XR Dispersive Raman spectrometer equip‐

ped with an Olympus microscope (BX51). An Olympus 10x objective (N.A. = 0.25) was used
both for focusing the laser on the sample, with a spot size ∼ 5 μm, and collecting the scat‐
tered light in a 180° backscattering configuration. The scattered light was detected by a CCD
detector, thermoelectrically cooled to -50 °C. The spectrometer used a grating (675 lines/mm)
to resolve the scattered radiation and a notch filter to block the Rayleigh light. The pinhole
of the monochromator was set at 25μm. The Raman spectra were accumulated over 25 s
with a resolution of ∼ 4 cm-1 in the 100-2000 cm-1 interval. The excitation source was a 532
nm radiation from a Nd:YVO4 laser (frequency-doubled) and the incident power at the sam‐
ple was of ∼ 8 mW.

2.2.2. FT-IR spectroscopy

FT-IR analysis was carried out on a Thermo Nicolet Nexus 670 FT-IR in transmission mode
with a resolution of ∼ 4 cm-1 in the 400-2000 cm-1 interval. The excitation source was a Heli‐
um-Neon laser light incident on a KBr compact target containing ∼ 0.5 % in weight of the
sample of interest.

2.2.3. Single crystal XRD

Single crystal XRD experiments were carried out for selected specimens. A Bruker SMART
APEX CCD-based X-ray three circle diffractometer was employed for crystal screening, unit
cell determination and data collection. A Van Guard 40x microscope was used to identify
suitable samples and the goniometer was controlled using the SMART software suite. The
X-ray radiation employed was generated from a Mo sealed X-ray tube (Kα= 0.70173 Å with
a potential of 50 kV and a current of 30 mA) and filtered with a graphite monochromator in
the parallel mode (175 mm collimator with 0.5mm pinholes).

2.3. Solution A

Figure 2 shows, from bottom to top, the IR and Raman spectra of starting acetic acid and
lead acetate as well as the final product, solution A, after stirring and refluxing. There are
several features in common between these spectra due to the organic nature of ligands. Basi‐
cally, bands corresponding to the CH2 and CH3 groups in the 1300-1400 cm-1 interval as well
as in the low frequency range [19].

The glacial acetic acid spectra reveal several representative peaks found at 619 cm-1 (RA:
Raman active), 889-893 cm-1 (RA, IRA: Infrared active), 1294 cm-1 (IRA), 1410 cm-1 (IRA), 1668
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cm-1 (RA), 1716 cm-1 (IRA) and 1757 cm-1 (IRA) for this molecule. Those peaks correspond,
respectively, to the τ(C-C=O), ν(C-C), δS(CH3), δA(CH3), ν(C=O), ν(C=O)dimer and ν(C=O)mono‐
mer vibrations [20],[21]. The clear splitting detected for the C=O dimeric and monomeric
stretch vibrations somewhat evidences the presence of some small amounts of water in the
acidic medium that, for the purpose of our study, will not be taken into consideration.

Figure 2. Infrared and Raman spectra of the reactants involved in solution A formation.

On the other hand, the lead(II) acetate trihydrate spectra also feature some representative
peaks located at 216 cm-1 (RA), 615-617 cm-1 (RA, IRA), 665 cm-1 (IRA), 934-935 cm-1 (RA,
IRA), 1342-1346 cm-1 (RA, IRA), 1417-1420 cm-1 (RA, IRA) and 1541-1543 cm-1 (RA, IRA) re‐
lated to the ν(Pb-O), ρ(COO), δS(COO), νS(C-C), δS(CH3), νS(C-O) and νA(C=O) vibrational
modes, respectively [20],[22]. It is well known that the acetate ligands can complex a metal
ion in three different ways (monodentate, bidentate chelating and bridged) and that, un‐
fortunately, none of these can be uniquely identified by symmetry considerations. Tradition‐
ally, the various types of bonding have been identified by the magnitude of the difference
between symmetric νS(C-O) and asymmetric νA(C=O) vibrations. In our case, this difference
is 122 cm-1 indicating a bidentate chelating coordination for the acetate-metal complex that
has been widely accepted for lead(II) acetate even though the Δν criterion has led sometimes
to incorrect conclusions [20],[22].
Solution A vibrational spectra shown in Figure 2 evidences the expected dilution of lead(II)
acetate in acetic acid: there are no new vibrational modes and a strong band overlapping is
seen. There is some band shift due to the overlapping and is worth to notice the weakening
328 Advances in Ferroelectrics

of the lead acetate Raman active Pb-O band at 216 cm-1 when in solution. Unfortunately, a
noticeable fluorescence in the Raman spectrum could not be avoided and this fact made
very difficult to carry on an appropriate analysis with useful data.

Nevertheless, and according to our results, the formation of Solution A could be fairly de‐
scribed by the following equation:

(
Pb OAc ) × 3 H 2 O( S ) + 3 HOAc( Aq ) ¾¾¾
® Pb(
T ~ 115° C 2+ +
( ) -

) + 3a H 3 O( Aq ) + 2 + 3a OAc( Aq ) +
(1)
2 t ~ 3 hrs . Aq

(
+3 1 - a HOAc( Aq ) )

Where α is the HOAc dissociation degree under our experimental conditions and where we
have also assumed, on the simplest approach, neglectable losses due to evaporation of H2O
and HOAc during the whole process.

2.4. Solution B

FT-IR spectra for Solution B precursors, Figure 3, showed some features like the ones dis‐
cussed above. A Raman spectra based analysis for these compounds could not be completed
due to the strong fluorescence exhibited by the zirconium and titanium alkoxides at our
fixed operating laser wavelength.

The titanium propoxide IR spectrum exhibit sharp bands at 1377-1464 cm-1 corresponding,
respectively, to the stretching and bending vibrations of the aliphatic CH3 groups. A distinc‐
tive single peak at 1011 cm-1 corresponds to the propoxy- Ti-O-C vibration and a similar be‐
havior is found for zirconium propoxide with Zr-O-C vibrations located at 1142 cm-1[18].

The acetylacetone vibrational spectrum shows the main features attributed to the most prob‐
able staggered conformation of this compound. This conformation has some typical weak IR
active vibrations in the low frequency range, as it is shown. Modes at 509, 554 and 640 cm-1
correspond to the in plane ring deformation (Δ ring), out of plane ring deformation (Γ ring)
and Δ ring + ρ(CH3) modes, respectively [23].

As described above, when reaction took place, some crystals precipitated short after solution
B reached room temperature; IR spectra of these single crystals are also shown in Figure 3.
Unlike solution A, a reaction is now verified by the shifting and/or reinforcement of bands
associated to reactants vibrations. A discussion of several mechanisms for this kind of reac‐
tion has been reviewed by several authors taking into account, primarily, the mixing condi‐
tions, the reactivity of metal alkoxides and the Acac/Alkoxides molar ratio [17],[18],[24].

2.4.1. Single crystal XRD characterization

At this stage, a suitable colorless parallelepiped 0.356 mm × 0.162 mm × 0.066 mm was chos‐
en from a representative sample of crystals of the same habit. After the determination of a
suitable cell, it was refined by nonlinear least squares and Brava is lattice procedures. The
unit cell was then verified by examination of the (h k l) overlays on several frames of data,
 ‘Universal’ Synthesis of PZT (1-X)/X Submicrometric Structures Using Highly Stable Colloidal Dispersions... 329
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including zone photographs, and no super cell or erroneous reflections were observed. A
search performed on the Cambridge Structural Database and updates using the program
Conquest afforded 77 coincidences within 1% of the longest length of a monoclinic C-cen‐
tered cell whose lattice parameters and reported structure are shown in Figure 4(a). Two en‐
tries, those with ACACZR and ZZZADD CCD reference code, in addition, revealed
chemical coincidences (both in composition and stoichiometry) for the compound tetra‐
kis(acetylacetonate-O,O’)-zirconium(IV) or Zr(Acac)4.

Figure 3. Infrared spectra of the reactants involved in solution B formation. The IR spectra for the resultant precipitat‐
ed single crystals are also shown.

According to these data, the Zr(Acac)4 structure was simulated using the Accelrys Materials
Studio 3D visualizer environment [25]as shown in Figure 4(b). In this case, the acetylacetone
reaction with the Zr propoxide results in the formation of an oxo cluster where the metallic
atom changes its coordination number from 4 to 8 which is the highest possible value for
zirconium. Metallic cations are now bonded to the acetylacetonate chelating ligand giving
rise to a less hydrolysable organic complex.

In the case of the titanium propoxide reaction, and taking into account our experimental
conditions, it is not a bad assumption to consider the formation of a fully chelated organo‐
metallic complex, just as it was described for zirconium. Given the maximum coordination
number of 6 for titanium, a Ti(Acac)2(OPr)2 compound will be the most likely to expect as is
also confirmed by earlier reports that consider the multiple chelation routes for titanium
330 Advances in Ferroelectrics

propoxide [18],[20]. Figure 4(c) shows a very simple Materials Studio 3D modeling for the
most probable configuration of Ti(Acac)2(OPr)2 as determined by the Forcite package [25] on
a single step relaxation and energy minimization routine.

Accordingly, bands located at 1280, 1370-1440 and 1530-1595 cm-1 in the crystals spectrum,
shown in Figure 3, can be assigned to the ν(C-CH3:Acac), δ(CH3:Acac) and ν(C-C) + ν(C-
O:Acac) vibrational modes, respectively [26].

Figure 4. Fully chelated metal-acetylacetonate complexes. (a) Zr(Acac)4 as reported by single crystal XRD charateriza‐
tion, (b) Zr(Acac)4 structure simulated by Materials Studio (MS) according to its crystallographic data and (c)
Ti(Acac)2(OPr)2 simulated by MS according to its most probable configuration.

2.4.2. Chemical reaction

As seen before, solution B can be thought as the resulting chelated metal complexes mixed
with residual isopropanol. In this case, an appropriate chemical equation for the reaction
could be:

(
0.53Zr O Pr
i
)(
4 Aq )
+ 0.47Ti O Pr ( i
)(
4 Aq )
+ 2 AcacH ( Aq ) ¾¾¾
T ~ 90° C
t ~ 4 hrs .
® 2 HO i Pr( Aq ) + yZr ( Acac )4 ( S ) +
(2)
+ ( 1 - 2 y ) Ti ( Acac ) 2 O Pr ( i
)( 2 Aq )
+ ( 0.53 - y ) Zr O Pr ( i
)(
4 Aq )
(
+ ( 2 y - 0.53 ) Ti O Pr
i
)(
4 Aq )

where we have assumed that all the acetylacetone reacts with the alkoxides thus forming the
chelated organometallic complexes. As we see, there is still a fraction of nonchelated reac‐
tants due to the insufficient amount of acetylacetone needed for that purpose. Let us find
now the exact amount of acetylacetone required for obtaining fully chelated organometallic
complexes without any further byproducts. We could rewrite equation [2] as:

(
0.53Zr O Pr
i
)(
4 Aq )
+ 0.47Ti O Pr( i
)(4 Aq )
+ (2 + D ) AcacH ( Aq ) ¾¾¾
T ~ 90° C
t ~ 4 hrs .
®(2 + D ) HO i Pr( Aq ) +
(3)
+0.53Zr ( Acac ) 4
(S) (
+ 0.47Ti ( Acac ) 2 O Pr
i
)(
2 Aq )
 ‘Universal’ Synthesis of PZT (1-X)/X Submicrometric Structures Using Highly Stable Colloidal Dispersions... 331
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Now, it is obvious that Δ = 1.06 implying an alkoxides: acacH molar ratio of 1:3.06 for full che‐
lation of metallic centers. Equation [3] can now be written for any given Zr:Ti ratio (1-x)/x:

( i
(1 - x )Zr O Pr )(
4 Aq )
(
+ xTi O Pr
i
)(
4 Aq )
+ 2(2 - x ) AcacH ( Aq ) ¾¾¾
T ~ 90° C
t ~ 4 hrs .
® 2(2 - x ) HO i Pr( Aq ) +
(4)
+(1 - x )Zr ( Acac ) 4
(S) (
+ xTi ( Acac ) 2 O Pr
i
)(
2 Aq )

This equation represents an extension for the initially proposed sol-gel based route in order
to obtain fully chelated and no hydrolysable precursor solutions for PZT based ferroelectric
materials. It allows us to synthesize PZT at any Zr:Ti ratio while maximizing solution stabili‐
ty and offering a noticeable repetitiveness for both small and large scale manufacturing and
processing.

On the following section we will analyze some features of different sol-gel based PZT (1-x)/x
precursors when synthesized using the universal 1:2(2-x) alkoxides: acacH molar ratio al‐
ready discussed above.

3. Some properties of the PZT precursors

In the final step of the synthesis, when mixing Solutions A and B with 2-methoxyethanol,
the dissolved lead acetate complex can react with 2-MOE forming a very stable acetate–me‐
thoxyethoxy lead complex [27] that, along with the chelated metal complexes already
formed, may lead to turn this final solution into a hydrophobic sol, poorly hydrolysable
and, therefore, very stable.

Stability issues tend to be crucial when using sol-gel based precursors in research, small
scale applications and industry. Therefore, it is very important to keep control over some
parameters that affects the solution stability and, most of all, the average particles size. Par‐
ticularly, particles size can be an indicator of some undesirable processes that could be tak‐
ing place in the sol: aggregation, flocculation and sedimentation; aggregation, even though
is a reversible process, is a good indicator of instability since the other two processes, which
are not reversible, generally follows after some time.

In this respect, the aging time dependences of some physical parameters directly related to
the stability of colloidal dispersions must be explored and discussed. Two of the most im‐
portant parameters that should be taken into account are pH and the average particles size.
The first one is determinant for fixing the thickness of the ionic layers surrounding any giv‐
en charged colloidal particle (Stern layers) while affecting, at the same time, the Zeta poten‐
tial, the electrophoretic mobility and the aggregation mechanisms as well as the apparent
hydrodynamic particle size. As a consequence, the average particles size is the final result of
the conjugate action of all the physicochemical variables hardly mentioned before. It is also
the definitive experimental variable on which any post processing technique should be
332 Advances in Ferroelectrics

based on as it explicitly defines the size range of the so called “building blocks” for bottom-
up studies or applications.
Currently, there are no known extensive reports in the literature directly concerned to the
study of the time dependence of the average particles size or pH in a PZT precursor sol. It
must be noted that, in the case of magnetic nanoparticles, some studies have been carried
out [28]-[30]and all of them stress the strong correlation between the size of the colloidal
particle and the final properties of the conceived structure, whether it will be nano- or not.

3.1. pH
For this study, we synthesized PZT (1-x)/x precursor solutions by using the same route de‐
scribed in 2.1 with the only difference being the propoxides: acacH molar ratio. In this case,
and for the rest of our text, that ratio will be 1:2(2-x) for full chelation of the metal alkoxides.
As it was stated earlier, we will avoid again showing and discussing irrelevant data of sam‐
ples that showed no significant discrepancies between each other and, because of this, this
section will analyze the pH vs. Concentration vs. aging time behaviors of several PZT 53/47
precursor solutions with concentrations ranging from 0.05 M to 0.37 M in a time interval of
up to 4 months of stocking.
As can be seen in Figure 5, the acidity/basicity of the solutions clearly shows a tendency
with both sols concentration and aging time. Figure 5(a) shows the measured pH vs concen‐
tration for the studied sols at several aging steps and, as expected, the more concentrated
sample implies the more acidic medium which is consistent with the chemical reaction pro‐
posed for sols synthesis.
Figure 5(b), on the other hand, shows the measured pH vs. time behavior. As a general ten‐
dency, sols pH dependency with aging time can be divided in three stages which are high‐
lighted in the graph: (i) pH increases notably in the first days after which (ii) it decreases to
values somehow close to the initial ones. In this moment, (iii) pH starts to rise again but
with a slower time gradient than on stage (i). In our opinion, for the understanding of the
pH vs. aging time behavior, we have to take into account the coexistence of different com‐
petitive processes right after sols were prepared. In this way, a qualitative description could
be done as follows [31]: (i) Remnant unreacted acetic acid evaporates during the first days
implying a decrement on the acidity of sols. At this point, (ii) particles are less positively
charged and are able to aggregate via condensation reactions followed by the formation of
small portions of alcohol (1-propanol) and thus implying a more acidic environment as seen
in Figure 5. The number of polyanions per aggregate chain must be limited, however, by the
high chemical stability of the chelated metal complexes and that is why the aggregation
process does not imply polymerization and/or gelation as it has been reported for more hy‐
drophilic sols. Shortly after condensation rate vanishes, (iii) it is possible for the residual al‐
cohols to evaporate as solutions age thus allowing pH to rise slowly, as seen in Figure 5 for
the more aged solutions.
At this scenario, however, hydrolysis is not expected due to (a) the complete chelation of the
metal complexes, (b) to the short lengths of the already formed polymeric chains and, there‐
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fore, (c) to the small amount of alcohol that could be formed afterwards. After 4 months of
aging, no noticeable changes in pH values were detected. Moreover, the stability of these
solutions could be eye inspected by verifying neither the absence of sedimentation nor pre‐
cipitation of single particles or aggregates after almost 1 year of stocking.

Figure 5. a) pH vs. concentration dependencies for the PZT 53/47 samples understudy measured at different time in‐
tervals. Semi-log fittings to guide the eye are also drawn. (b) Aging effects on pH for the same samples. Three distinc‐
tive stages were detected and are highlighted in the graph.

3.2. Mean particle size

3.2.1. Experimental technique

Particles size measurements were carried out by means of the dynamic light scattering
(DLS) technique in a Zetasizer Nano ZS90 manufactured by Malvern Instruments Ltd.
equipped with a HeNe laser source. Approximately 1.5 ml of as synthesized sols were stor‐
ed in polystyrene cells (DTS0012 cells) provided by the same manufacturer and then size
distributions curves were recorded from the very first day until 125 days after synthesis. For
this purpose, several solvent parameters were needed for further processing of dispersed
light intensity, namely viscosity (η2-MOE ~ 1.5410 cP), dielectric constant (ε2-MOE ~ 16.9) and re‐
fraction index (n2-MOE ~ 1.33) [32]. After each measurement, a nonlinear least squares fitting
(NLLSF) was made to the experimental data according to a log-normal distribution function:

b1 1 é 1 æ ö
x
2
ù
fln ( x , b i ) = b 0 + exp ê - ln ç ÷ ú (5)
p b2 x êë 2b2
2
è b3 ø úû

Where βI are fitting parameters. It must be stressed that this fitting was carried out only for
size intervals where unimodal distribution curves were measured.
334 Advances in Ferroelectrics

3.2.2. Concentration dependence

Figure 6 shows the results obtained for particles size distribution for two concentrations un‐
der study (a PZT 53/47 precursor) after different time lapses that are also shown in the figure.
According to what is shown, an appropriate discussion relaying on the acidity/particles size
dependence cannot be easily established: oscillations in the pH values, see Figure 5, during
aging are not followed by oscillations in the mean particles size values. Even though this
feature is not fully understood, it may be due to the short lengths of the oligomeric chains
present in the solution and to the weak sensitivity of the completely chelated metal com‐
plexes to the ionic strength of the solvent medium. Another possible explanation could be
given in terms of the irreversibility associated to the formation of these chains when the sol‐
vent medium is not acidic enough to break the corresponding bonds and/or coordinations.
As can be seen, as prepared sols featured multimodal distributions with some small percent
of particles that could even have sizes higher than 1μm. As solutions are aged, these distri‐
butions tend to be unimodal featuring a mean particles size well below 10 nm. We consider
that this is a remarkable result of this work as it shows that there is no rule of thumb closely
related to the need of using fresh, as prepared solutions for synthesizing several kinds of
nanodimensional systems by means of electrophoretic deposition(EPD) or simple template
immersion, [33]-[36]. Moreover, in this case we could have chosen solutions aged for 20 days
or more for bulk, thin films or nanostructures synthesis due to the better homogeneity re‐
garding particles size distribution in both cases under study.

Figure 6. Particles size distribution functions for the analysed PZT 53/47 precursor solutions and for several aging
times in the whole measurement range. Log-normal fittings for the more populated size intervals are also depicted.

This behavior could be explained, in principle, on the basis of the chemical reaction which
was described for obtaining what we called solution B, see Section 2.4. As we stated, by the
end of this step we observed the crystallization of the compound Zr(Acac)4. Such crystalliza‐
tion does not occur after mixing solutions A and B in the presence of 2-MOE which can be
attributed (I) to the higher acidity of the final A+B+2-MOE solution, (II) to the solubility of
 ‘Universal’ Synthesis of PZT (1-X)/X Submicrometric Structures Using Highly Stable Colloidal Dispersions... 335
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Zr(Acac)4 in 2-MOE, (III) to a dilution process while mixing A+ B, or (IV) to a combined ef‐
fect of all of the above. Must be noted that the less acidic solution (C = 0.20M) possesses, at
the same time, the less unimodal distribution function which is an expected result in con‐
cordance to the relationship between ionic strength and particles size.
Thus, it seems plausible to assume solution B as a dispersion containing the Ti(Acac)2(OPr)2
compound at molecular level and submicrometric aggregates of Zr(Acac)4 that do not pre‐
cipitate; these are redissolved afterwards when mixed with the acetate rich solution A and 2-
MOE. After stirring the resultant sol for one day, the size of some percentage of the
Zr(Acac)4 aggregates still ranges between 100 and 1000 nm; after 20 days, however, size is
well below 10 nm. From these results, and somehow confirming our previous discussion,
we can also see that the less concentrated solution features a considerable amount of parti‐
cles with sizes well above 50nm even after 100 days of stocking. For this reason, we will fo‐
cus our attention from now on in precursor solutions with 0.35 M aged during the first 30-35
days, a time period that, according to our results, seems to be critical in the colloidal stability
of as synthesized sols.

3.2.3. Aging time dependence

As it was said before, all samples under study featured a noticeable stabilization when aged
for about 1 month. Figure 7 shows this aging behavior for two PZT (1-x)/x precursor solu‐
tions concentrated at 0.35 M. In all cases, it could be observed a similar time evolution as the
one described earlier for Figure 6.

Figure 7. Aging behavior, as depicted by the time evolution of particles size distribution curves, for two PZT (1-x)/x
precursor solutions concentrated at 0.35 M: (a) PZT 25/75 and (b) PZT 60/40.

On the other hand, Figure 8 shows the whole dataset of the measured mean particles size for
the synthesized solutions. Fitting curves shown here were determined by considering a time
dependence given by <d>= C1t1/(1 -λ)+ C2 that, according to the classical Smoluchowski theory
in the van Dongen–Ernst approximation, describes appropriately a nongelling system of dis‐
336 Advances in Ferroelectrics

persed clusters. Moreover, in the same approximation, the small values of λ(λ<<1) are usual‐
ly associated with a Brownian diffusion limited aggregation process vastly dominated by
collisions between larger clusters with smaller ones [31].

Another view of the aging process could be illustrated by means of the dimensionless nor‐
malized distribution curves, not shown here. In that representation, the broadening of the
distribution curves with aging is an indicator of very likely aggregation processes and some‐
how will help to complete the kinetic analysis that we have been through in this section.

In a way of summarizing our results, it could be said that, just after synthesis, several popu‐
lations of particles were detected until homogenized a few days later; then particles tend to
grow very slowly with time according to an almost linear law (corresponding to that de‐
scribing a nongelling system) and aggregation is expected. Moreover, these cases fit very
well in the Brownian diffusion limited aggregation type where smaller clusters stick to big‐
ger ones when they collide. The slow but evident increase in the mean cluster size, as well as
the noticeable broadening in the distribution peaks, must warn us about an undesirable and
irreversible precipitation process for, hypothetically, t → ∞.

The high stability shown by our samples even after 4months of stocking and the small val‐
ues for mean particles size (well below 10 nm) are good indicators that the complete chela‐
tion of the organometallic compounds plays a key role in keeping short, and poorly reactive,
oligomeric chains. An aggregation process dominated exclusively by Brownian motion is
highly desirable when solution stability needs to be maximized.

Figure 8. Mean particles size vs. aging time dependence for the systems under study. Fitting curves obeying a t1/(1 -
λ)
scaling law are depicted.
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Our samples were also characterized by the High Resolution Transmission Electron Micro‐
scopy (HR-TEM) technique. A few drops of the synthesized sols were deposited on copper
grids, evaporated afterwards and put under a JEOL JEM2200 microscope with Omega filter
and a spherical aberration corrector; some of the obtained images are shown in Figure 9 for
a PZT 95/05 precursor solution. As expected, particles are likely to coalesce as the solvent
evaporated prior to characterization, see Figure 9(a) and (b), and some of those nanoparti‐
cles are shown in higher magnification images in Figure 9(c) and (d). Most of the features
regarding particle size that were discussed earlier were corroborated by means of this tech‐
nique for all the precursor solutions.

At this point, and considering what has been discussed until now, it must be highlighted
that a rigorous control of the chelation rate, pH and aging time could give us a chance to
“tune” the average nanoparticles size and/or the colloidal stability as desired. By looking
back at Figure 5 through Figure 8 one may feel free to choose to explore several “working
points” according to our research or technological needs for every (1-x)/x Zr:Ti ratio in the
PZT system.

Figure 9. HR-TEMimages at different magnifications for a PZT 95/05 precursor solution, with C = 0.35 M and aged for
2 months.
338 Advances in Ferroelectrics

This, in fact, is a powerful tool provided by the physicochemical phenomena and mecha‐
nisms previously discussed and, generally speaking, could be extended to other material
systems of technological interest at a moderate cost.

4. Crystallization route

The final A + B + 2-MOE solutions were dried at 100°C for several days and, after that, they
were thermally treated in order to analyze the phase evolution from the amorphous PZT
sol-gel network to the expected final Perovskite structure. Due to fundamental similarities
among the different samples we will be discussing only the case where Zr:Ti ratio is 53/47,
concentrated at 0.35 M and aged for 2 months.

4.1. Experimental techniques

Crystallization was monitored by means of FT-IR and Raman vibrational spectroscopies, see
Sections 2.2.1 and 2.2.2, and by X-Ray Diffraction (XRD) and Scanning Electron Microscopy
(SEM) techniques after treating the samples for 12 hours at certain temperatures that were
previously chosen. For the sake of clarity, we decided to divide the crystallization study in
two temperature intervals: (i) 100 ≤ T ≤ 510°C and (ii) 550 ≤ T ≤ 900°C. At this point, it is im‐
portant to say that, for powders heated at 850°C and 900°C, the treatment was carried out for
just 2 hours due to the high volatility of lead for 850°C and beyond.

Scanning Electron Microscopy (SEM) was carried out on fine ground powders in a Leica
Cambridge Stereoscan 440 microscope and the X-Ray powder diffraction patterns were re‐
corded over a 20-60° 2θ range on a Bruker D8 Advance diffractometer with filtered CuKα
radiation. In this technique, the identified phases were indexed by comparing the resulting
diffraction patterns with those of similar compositions reported in the International Union
of Crystallography (IUCr) JCPDS-ICDD database.

4.2. 100 ≤ T ≤ 510 °C

In this temperature range the material goes through very noticeable phase transformations;
the initial amorphous powder starts to show some crystallinity for about 500°C, right after
the combustion of the remaining organic species. Figure 10 shows these first crystallization
stages as recorded by the Raman (a) and FT-IR (b) vibrational spectroscopies. The vibration‐
al modes associated to the remnant organic compounds coexisting after heat treating at 100
°C are also highlighted in this graph, Figure 10(b), and it must be noticed that they corre‐
spond, basically, to the lead acetate and to the completely chelated organometallic com‐
plexes. More explicitly, numbered modes in Figure 2(b) have been assigned to:
(1)Pb(OAc)2:ρ(COO), (2)Pb(OAc)2:δS(COO), (3)Pb(OAc)2:νS(C-C), (4)Ti(OPr)2(Acac)2:Ti-Acac,
(5)Zr(Acac)4:Zr-Acac,(6)Pb(OAc)2:δS(CH3), (7)Ti(OPr)2(Acac)2/Zr(Acac)4:δ(CH3:Acac) +
Pb(OAc)2:νS(CO)and (8)Ti(OPr)2(Acac)2/Zr(Acac)4:[ν(C-C) + ν(C-O:Acac)] +
Pb(OAc)2:νA(C=O)[26],[37].
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Figure 10. Phase transformations for 100 °C≤ T≤ 510 °C as registered by Raman (a) and FT-IR (b) vibrational spectros‐
copies; in this case, remnant vibrations due to the presence of acetate and chelated metal complexes are highlighted.

Until 225°C, IR spectra showed no variation; the intensity ratios between the detected modes
are almost the same and, on the other hand, Raman spectra featured no signal given the
strong presence of π-bonded organic species. Afterwards, IR spectra revealed the almost
complete decomposition of acetates and a decrement of Metal:Acac complexes while any no‐
ticeable Raman signal is still absent. Just after T = 450°C the active Raman modes normally
assigned to a PZT 53/47 started to show up. After treating at this temperature, the FT-IR
spectra reveals the formation and definition of the A1(3TO) vibrational mode (~600 cm-1)
which is also characteristic for this compound [38]-[41].

Another view of the whole process in this temperature range could be given, as seen in Fig‐
ure 11, by means of XRD characterization. XRD patterns clearly illustrate the phase transfor‐
mation exhibited by an amorphous material turning into crystalline; as for the Raman
spectra, crystallinity starts to get noticed at T = 450°C. However, these patterns revealed the
existence of well defined peaks near 28° that disappear almost entirely at 510°C.

These maxima are usually associated to an intermediate metastable phase belonging to the
Fluorite crystal system (F) which is mainly characterized by the spatial disarrangement of
the oxygen atoms, vacancies and metal cations while coexisting with some carbonates
and/or oxides that still remain in the material. Afterwards, when carbonates and oxides re‐
act, a new metastable phase is formed but this new arrangement tends to be more ordered
than the previous fluorite. This intermediate phase is considered as belonging to the Pyro‐
chlore crystal system (P or Pyr) and consisting of a 2 x 2 x 2 ordered fluorite cell with oxygen
and metallic vacancies or, from another point of view, consisting of a 2 x 2 x 2 non stoichio‐
metric Perovskite (Per) cell. This rigorous differentiation between Fluorite and Pyrochlore is
not always considered in literature and it can be subtle sometimes, especially when working
340 Advances in Ferroelectrics

with a well known compound as PZT is. Anyway, in Figure 11 we have denoted by F (Fluo‐
rite) and P (Pyrochlore) the diffraction maxima associated with each of these phases and ac‐
cording to the indexed cubic structures reported in reference [42] (a = 5.25 Å) and in
reference [43] (a = 10.48Å), respectively.

Up to this point, we have seen the almost complete elimination of organic ligands with heating
as well as the amorphous/crystalline phase transformation going through two intermediate
metastable phases. In the next subsection we will carry on a similar study for higher tempera‐
tures while exploring the formation of pure Perovskite phase with morphological quality.

Figure 11. Thermal evolution of PZT 53/47 precursor powders when100 °C≤ T≤ 510 °C as recorded by XRD patterns.

4.3. 550≤ T ≤ 900 °C

Figure 12 shows Raman (b) and FT-IR (b) spectra for heat treated powders in the 550 – 900
°C range. Unlike the previously studied temperature range, vibrational spectra did not show
drastic or very noticeable changes. The FT-IR spectra features the only IR active band for
aPZT-R3m in the 400-1500 cm-1 range (A1(3TO)); this band, associated to the extensional vi‐
brations of the Perovskite BO6 octahedra, shifts slightly to higher frequencies while gets nar‐
rower as temperature increases. This shifting suggests a more compact octahedral structure
while a narrower band could be the evidence of a better ‘environment’ around the octahe‐
dron or, in other words, a better local stoichiometry [44] that seems to be minimum for T =
800°C, an indicative of an optimum crystallization. Raman spectra featured vibrational
modes that tend to define better as temperature increases.
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Figure 12. Phase transformations for 550 °C≤ T≤ 900 °C as registered by Raman (a) and FT-IR (b) vibrational spectros‐
copies.

Figure 13. Thermal evolution of the powders under study when 550 °C ≤ T ≤ 900 °C as evidenced by XRD patterns in
the 20 - 60 deg. 2θ interval. Regions where the most intense Pyr peak showed up are denoted by P.
342 Advances in Ferroelectrics

XRD patterns depicted in Figure 13 allow us to notice the temperature evolution of the dis‐
tinctive Perovskite diffraction peaks. Peaks indexing has been done according to a PZT
53/47, FR(HT); sym: R3m. Besides, regions where the most intense Pyr peak showed up (~28.5°)
are denoted by P; the Pyr phase is present in a small percentage (%Pyr ~ 1 %) except for
powders treated at T = 800°C which must be chosen as the appropriate crystallization tem‐
perature for this material. The final Perovskite phase homogenizes and tends to be predomi‐
nant as temperature increases until lead losses become noticeable.

The rest of the PZT compositions that were chosen for this study, PZT (1-x)/x with C = 0.35
M and 2 months aged, were also treated at 800 °C in order to obtain the appropiate Perov‐
skite phase; Figure 14 shows the corresponding XRD patterns for each one of them. As seen
in the graph, all samples attained a perfect crystallization in the corresponding phase and
the proper pattern indexing as well as the phase indentification are also shown.

Figure 14. XRD patterns for PZT (1-x)/x under study: (a) PZT 25/75, (b) PZT 60/40, (c) PZT 80/20 and (d) PZT 95/05.
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On the other hand, Figure 15 shows SEM micrographs of crystallized PZT (1-x)/x powdered
samples. As illustrated, a granular structure of fair morphological uniformity is found in all
cases along with a remarkable submicrometric average grain size. Another interesting fea‐
ture is the low porosity found in all compositions, somehow resembling the granular struc‐
ture of sintered bulk samples, which certainly favors the formation of a high density
ferroelectric material.

As it was said at the beginning of this chapter, this kind of sub-micron granular structures,
or nanoceramics, allows the technological exploitation of dielectric and ferro/piezoelectric
size related features. It is not shown here, but that very same samples have been resynthe‐
sized a couple of times with starting reactants being bought to different companies and final
results showed almost the same granular and morphological quality. Repetitiveness is also a
bonus when working with chemical routes of synthesis that tend to be less straightforward,
even though cheaper, than physical ones.

Figure 15. SEM micrographs showing the morphological quality of the PZT (1-x)/x powders when crystallized at 800
°C: (a) PZT 25/75, (b) PZT 60/40, (c) PZT 80/20 and (d) PZT 95/05.
344 Advances in Ferroelectrics

5. Chapter remarks

Through this chapter, we tried to expose some relevant results directly concerned with a fea‐
sible ‘universal‘ controlled synthesis of nano/submicrometric grain-sized PZT (1-x)/x piezo‐
electric structures that, technically speaking, potentially enhance the performance of current
commercially bulk based devices by exploiting the size effects related phenomena that arise,
as is commonly accepted, for grain sizes below 1 μm. Under the light of this study, the tenta‐
tive bottom-up “design” of any desired nano/submicrometric PZT (1-x)/x structure seems to
be a plausible and successful task that, methodologically at least, could be expanded to more
complex materials systems.

Further reading regarding the work that has been shown here can be found in references
[45]-[48]. On the other hand, references [49]-[60] will also provide the reader with very re‐
cent research papers in this field that undoubtedly extend the applicability and versatility of
what has been discussed.

Author details

A. Suárez-Gómez1, J.M. Saniger-Blesa2 and F. Calderón-Piñar3

1 UdG-CUVALLES, Carr. Guadalajara-Ameca, Ameca, Jalisco, México

2 CCADET-UNAM, Cd. Universitaria, Coyoacán, México D.F., México

3 Fac. de Física/IMRE, San Lázaro y L, Univ. de la Habana, Habana , Cuba

References

[1] McCauley D, Newnham RE, Randall CA. Intrinsic size effects in a barium titanate
glass-ceramic. Journal of the American Ceramic Society1998;81(4)979-987.

[2] Frey MH, Xu Z, Han P, Payne DA. The role of interfaces on an apparent grain size
effect on the dielectric properties for ferroelectric barium titanate ceramics. Ferroelec‐
trics1998;206(1)337-353.

[3] Zhang L, Zhong LW, Wang CL, Zhang PL, Wang YG. Finite-size effects in ferroelec‐
tric solid solution BaxSr1-xTiO3. Journal of Physics D: Applied Physics 1999;32 546-551.

[4] Park Y, Knowles KM, Cho K. Particle-size effect on the ferroelectric phase transition
in PbSc1/2Ta1/2O3 ceramics. Journal of Applied Physics 1998;83(11)5702-5708.

[5] Desu S.B., Ramesh R., Tuttle B.A., Jones R.E., Yoo I.K., editors. Ferroelectric Thin
Films V (MRS Symposium Proceedings Series Vol. 433), San Francisco, CA, 1996.
 ‘Universal’ Synthesis of PZT (1-X)/X Submicrometric Structures Using Highly Stable Colloidal Dispersions... 345
http://dx.doi.org/10.5772/51996

[6] Wang ZL. The new field of nanopiezotronics. Materials Today 2007;10(5) 20-28.

[7] Budd K.D., Dey S.K., Payne DA. Sol-Gel Processing of PbTiO3-PbZrO3 and PLZT
Thin Films. Proceedings of the British Ceramic Society 1985;36107–121.

[8] Schneller T, Waser R. Chemical Solution Deposition of Ferroelectric Thin Films: State
of the Art and Recent Trends. Ferroelectrics 2002;267(1) 293–301.

[9] Majumder SB, Bhaskar S, Katiyar RS. Critical issues in sol-gel derived ferroelectric
thin films: A review. Integrated Ferroelectrics 2002:42(1)245–292.

[10] Besra L, Liu M. A review on fundamentals and applications of electrophoretic depo‐

sition (EPD). Progress in Materials Science 2007;52(1) 1-61.

[11] Shantha Shankar K, Raychaudhuri AK. Fabrication of nanowires of multicomponent

oxides: Review of recent advances. Materials Science and Engineering: C 2005;25(5–8)
738-751.

[12] Ogihara T, Kaneko H, Mizutani N, Kato M. Preparation of monodispersed lead zirco‐

nate-titanate fine particles. Journal of Materials Science Letters 1988;7(8) 867-869.

[13] Lakeman CDE, Payne DA. Processing Effects in the Sol–Gel Preparation of PZT
Dried Gels, Powders, and Ferroelectric Thin Layers. Journal of the American Ceramic
Society 1992;75(11) 3091-3096.

[14] Wang FP, Yu YJ, Jiang ZH, Zhao LC. Synthesis of Pb1−xEux(Zr0.52Ti0.48)O3 nanopow‐
ders by a modified sol–gel process using zirconium oxynitrate source. Materials
Chemistry and Physics 2003;77(1)10-13.

[15] Brunckova H, Medvecky L, Briancin J, Saksi K. Influence of hydrolysis conditions of

the acetate sol–gel process on the stoichiometry of PZT powders. Ceramics Interna‐
tional 2004;30(3) 453-460.

[16] Praveenkumar B, Sreenivasalu G, Kumar HH, Kharat DK, Balasubramanian M,Mur‐

ty BS. Size effect studies on nanocrystalline Pb(Zr0.53Ti0.47)O3 synthesized by mechani‐
cal activation route. Materials Chemistry and Physics 2009;117(2–3) 338-342.

[17] Livage J, Henry M, Sanchez C. Sol-gel chemistry of transition metal oxides. Progress
in Solid State Chemistry 1988;18(4)259–342.

[18] Sedlar M, Sayer M. Reactivity of titanium isopropoxide, zirconium propoxide and

niobium ethoxide in the system of 2-Methoxyethanol, 2,4-Pentanedione and water.
Journal of Sol–Gel Science and Technology 1995;5(1) 27–40.

[19] Nakamoto K. Infrared and Raman Spectra of Inorganic and CoordinationCom‐

pounds. John Wiley & Sons; 1997.

[20] Doeuff S, Henry M, Sanchez C, Livage J. Hydrolisis of titanium alkoxides: Modifica‐

tion of the molecular precursor by acetic acid. Journal of Non-Crystalline Solids
1987;89(1-2) 206–216.
346 Advances in Ferroelectrics

[21] Lewandowski H, Koglin E, Meier RJ. Computational study of the infrared spectrum
of acetic acid, its cyclic dimer, and its methyl ester. Vibrational Spectroscopy
2005;39(1) 15–22.

[22] Yang MM, Crerar DA, Irish DE. A Raman spectroscopic study of lead and zinc ace‐
tate complexes in hydrothermal solutions. Geochimica et Cosmochimica Acta
1989;53(2) 319–326.

[23] Tayyari SF, Milani-nejad F. Vibrational assignment of acetylacetone. Spectrochimica

Acta A: Molecular and Biomolecular Spectroscopy2000;56(14) 2679–2691.

[24] Schubert U, Husing N, Lorenz A. Hybrid Inorganic-Organic Materials by Sol-Gel

Processing of Organofunctional Metal Alkoxides. Chemistry of Materials 7(11) 2010–
2027.

[25] Accelrys Inc., San Diego, CA USA. http://accelrys.com/products/materials-studio/

[26] Schwartz RW, Voigt JA, Boyle TJ, Christenson TA, Buchheit CD,“Control of Thin
Film Processing Behavior Through Precursor Structural Modifications. Ceramic En‐
gineering and Science Proceedings 1995;16(5)1045–1056.

[27] Kolb U, Gutwerk D, Beudert R, Bertagnolli H. An IR- and EXAFS-study of the pre‐
cursor system lead(II) acetate trihydrate, dissolved in methanol and 2-methoxyetha‐
nol. Journal of Non-Crystalline Solids 1997;217(2-3) 162-166.

[28] Zeisgerber M, Dutz S, Lehnert J, Müller R. Measurement of the distribution parame‐

ters of size and magnetic properties of magnetic nanoparticles for medical applica‐
tions. Journal of Physics: Conference Series 2009;149(1) 012115.

[29] Ortega D, Garitaondia JS, Ramírez-del-Solar M, Barrera-Solano C, Domínguez M. Im‐

plications of nanoparticle concentration and size distribution in the superparamag‐
netic behaviour of aging-improved maghemite xerogels. The European Physics
Journal D: Atomic, Molecular, Optical and Plasma Physics 2009;52(1-3) 19-22.

[30] Maity D, Choo SG, Yi J, Ding J, Xue JM. Synthesis of magnetite nanoparticles via a
solvent-free thermal decomposition route. Journal of Magnetism and Magnetic Mate‐
rials 2009;321(9) 1256-1259.

[31] Brinker CJ, Scherer GW. Sol–gel Science: The Physics and Chemistry of Sol–gel Proc‐
essing. Academic Press Inc., San Diego; 1990.

[32] Das B, Hazra DK. Conductance of selected Alkali Metal Salts in Aqueous Binary Mix‐
tures of 2-Methoxyethanol at 25 °C. Journal of Solution Chemistry 1998;27(11)
1021-1031.

[33] Valdés-Solís T, Marbán G, Fuertes AB. Preparation of Nanosized Perovskites and

Spinels through a Silica Xerogel Template Route. Chemistry of Materials 2005;17(8)
1919-1922.
 ‘Universal’ Synthesis of PZT (1-X)/X Submicrometric Structures Using Highly Stable Colloidal Dispersions... 347
http://dx.doi.org/10.5772/51996

[34] Steinhart M, Jia Z, Schaper AK, Wehrspohn RB, Gösele U, Wendorff JH. Palladium
Nanotubes with Tailored Wall Morphologies. Advanced Materials 2003;15(9)
706-709.
[35] Limmer SJ, Hubler TL, Cao G. Nanorods of Various Oxides and Hierarchically Struc‐
tured Mesoporous Silica by Sol-Gel Electrophoresis. Journal of Sol–Gel Science and
Technology 2003;26(1-3) 577-581.
[36] Urban JJ, Yun WS, Gu Q, Park H. Synthesis of Single-Crystalline Perovskite Nano‐
rods Composed of Barium Titanate and Strontium Titanate. Journal of the American
Chemical Society 2002;124(7) 1186-1187.
[37] Hardy A, Van Werde K, Vanhoyland G, Van Bael MK, Mullens J, Van Poucke LC.
Study of the decomposition of an aqueous metal–chelate gel precursor for
(Bi,La)4Ti3O12 by means of TGA–FTIR, TGA–MS and HT-DRIFT. Thermochimica Ac‐
ta 2003;397(1-2)143-153.
[38] Petzelt J, Ostapchuk T. Infrared and Raman spectroscopy of some ferroelectric perov‐
skite films and ceramics. Journal of Optoelectronics and Advanced Materials
2003;5(3) 725-733.
[39] Meng JF, Katiyar RS, Zou GT, Wang XH. Raman Phonon Modes and Ferroelectric
Phase Transitions in Nanocrystalline Lead Zirconate Titanate. Physica Status Solidi
A: Applications and Materials Science 1997;164(2)851-862.
[40] Burns G, Scott BA. Raman Spectra of Polycrystalline Solids; Application to the PbTi1-
xZrxO3 System. Physical Review Letters 1970;25(17) 1191-1194.

[41] Camargo ER, Leite ER, Longo E. Synthesis and characterization of lead zirconate tita‐
nate powders obtained by the oxidant peroxo method. Journal of Alloys and Com‐
pounds 2009;469(1-2)523-528.
[42] Wilkinson AP, Speck JS, Cheetham AK, Natarajan S, Thomas JM. In Situ X-ray Dif‐
fraction Study of Crystallization Kinetics in PbZr1-xTixO3 (PZT, x = 0.0, 0.55, 1.0).
Chemistry of Materials 1994;6(6)750-754.
[43] Kwok CK, Desu SB. Pyrochlore to perovskite phase transformation in sol-gel derived
lead-zirconate-titanate thin films. Applied Physics Letters 1992;60(12)1430-1432.
[44] Lakeman CDE, Xu Z, Payne DA. Rapid Thermal Processing of Sol-Gel Derived PZT
53/47 Thin Layers. Proceedings of the Ninth IEEE International Symposium onAppli‐
cations of Ferroelectrics, 1994. ISAF '94. 1995404-407.
[45] Suárez-Gómez A, Sato-Berrú R, Toscano RA, Saniger-Blesa JM, Calderón-Piñar F. On
the synthesis and crystallization process of nanocrystalline PZT powders obtained by
a hybrid sol–gel alkoxides route. Journal of Alloys and Compounds 2008;450(1-2)
380-386.
[46] Suárez-Gómez A, Saniger-Blesa JM, Calderón-Piñar F. The effects of aging and con‐
centration on some interesting Sol-gel parameters: A feasibility study for PZT nano‐
348 Advances in Ferroelectrics

particles insertion on in-house prepared PAA matrices via electrophoresis. Journal of

Electroceramics 2009;22(1-3) 136-144.
[47] Suárez-Gómez A, Saniger-Blesa JM, Calderón-Piñar F. A study on the stability of a
PZT precursor solution based on the time evolutionof mean particles size and pH.
Materials Chemistry and Physics 2010;123(1) 304-308.
[48] Suárez-Gómez A, Saniger-Blesa JM, Calderón-Piñar F. A Crystallization Study of
Nanocrystalline PZT 53/47 Granular Arrays Using a Sol-Gel Based Precursor. Journal
of Materials Science & Technology 2011;27(6) 489-496.
[49] Meng Q, Zhu K, Pang X, Qiu J, Shao B, Ji H. Sol-hydrothermal synthesis and charac‐
terization of lead zirconate titanate fine particles. Advanced Powder Technology
2012;In Press DOI:10.1016/j.apt.2012.06.004.
[50] Chiolerio A, Quaglio M, Lamberti A, Celegato F, Balma D, Allia P. Magnetoelastic
coupling in multilayered ferroelectric/ferromagnetic thin films: A quantitative evalu‐
ation. Applied Surface Science 2012;258(20) 8072–8077.
[51] Bastani Y, Bassiri-Gharb N. Enhanced dielectric and piezoelectric response in PZT
superlattice-like films by leveraging spontaneous Zr/Ti gradient formation. Acta Ma‐
terialia 2012;60(3) 1346–1352.
[52] Stawski TM, Besselink R, Veldhuis SA, Castricum HL, Blank DHA, ten Elshof JE.
Time-resolved small angle X-ray scattering study of sol–gel precursor solutions of
lead zirconate titanate and zirconia. Journal of Colloid and Interface Science
2012;369(1) 184–192.
[53] Goel P, Vijayan N, Biradar AM. Complex impedance studies of low temperature syn‐
thesized fine grain PZT/CeO2 nanocomposites. Ceramics International 2012;38(4)
3047–3055.
[54] Yin Y, Ye H, Zhan W, Hong L, Ma H, Xu J. Preparation and characterization of unim‐
orph actuators based on piezoelectric Pb(Zr0.52Ti0.48)O3 materials. Sensors and Actua‐
tors A: Physical 2011;171(2) 332–339.
[55] Sachdeva A, Tandon RP. Effect of sol composition on dielectric and ferroelectric
properties of PZT composite films. Ceramics International 2012;38(2) 1331–1339.
[56] Bochenek D, Skulski R, Wawrzała P, Brzezińska D. Dielectric and ferroelectric prop‐
erties and electric conductivity of sol–gel derived PBZT ceramics. Journal of Alloys
and Compounds 2011;509(17) 5356–5363.
[57] Chen W, Zhu W, Chen XF, Sun LL. Preparation of (Ni0.5Zn0.5)Fe2O4/Pb(Zr0.53Ti0.47)O3
thick films and their magnetic and ferroelectric properties. Materials Chemistry and
Physics 2011;127(1–2) 70–73.
[58] Zhong C, Wang X, Li L. Fabrication and characterization of high curie temperature
BiSc1/2Fe1/2O3–PbTiO3 piezoelectric films by a sol–gel process. Ceramics International
2012;38(S1) S237–S240.
 ‘Universal’ Synthesis of PZT (1-X)/X Submicrometric Structures Using Highly Stable Colloidal Dispersions... 349
http://dx.doi.org/10.5772/51996

[59] Fuentes-Fernandez E, Baldenegro-Perez L, Quevedo-Lopez M, Gnade B, Hande A,

Shah P, Alshareef HN. Optimization of Pb(Zr0.53,Ti0.47)O3 films for micropower gener‐
ation using integrated cantilevers. Solid-State Electronics 2011;63(1) 89–93.

[60] Kim SH, Koo CY, Lee J, Jiang W, Kingon AI. Enhanced dielectric and piezoelectric
properties of low-temperature processed Pb(Zr,Ti)O3 thick films prepared by hybrid
deposition technique with chemical solution infiltration process. Materials Letters
2011;65(19–20) 3041–3043.
 Chapter 16

Phase Transitions, Dielectric and Ferroelectric

Properties of Lead-free NBT-BT Thin Films

N. D. Scarisoreanu, R. Birjega, A. Andrei, M. Dinescu,

F. Craciun and C. Galassi

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/ 52395

1. Introduction

Ferroelectric perovskites based on Na0.5Bi0.5TiO3 (NBT) are considered among the most
promising lead-free candidate materials to substitute Pb(Zr1-xTix)O3 (PZT) in devices de‐
signed to respect standards and environmental laws. Taking into account the toxicity of
lead-based systems, there are numerous lead-free piezoelectric materials under investigation
in worldwide spread laboratories for replacing PZT in future devices. Constant efforts are
made to find viable replacements for all these materials containing harmful elements.

Solid-solution systems based on lead-free perovskites like Na0.5K0.5NbO3 (NKN), BaTiO3

(BT), Na0.5Bi0.5TiO3 (NBT) or bismuth layered-structured SrBi2Ta2O9 (SBT), and SrBi2Nb2O9
(SBN) are considered as viable alternatives for replacing lead-based materials. For example,
(K,Na)NbO3–LiTaO3–LiSbO3 alkaline niobate ceramics exhibit a d 33 piezoelectric coefficient
up to 416 pC/N together with Curie temperature Tc around 526 K, as reported by Saito et al
[1]. Sodium/bismuth titanate (NBT) belongs to the bismuth-based perovskites in which the
A-site atom is replaced. The crystalline structure, phase transitions and physical properties
have been intensively studied since the discovery of the material in 1960 by Smolensky et al
[2]. NBT has a relatively high depolarization temperature, Td = 470 K, high remanent polari‐
zation, 38 μC/cm2 and piezoelectric coefficient d33 = 125 pC/N [3]. However, owing to the
high value of the coercive field and high electrical conductivity, NBT cannot be easily polar‐
ized, therefore different A-site substitutions have been attempted to avoid this drawback.

© 2012 Scarisoreanu et al.; licensee InTech. This is an open access article distributed under the terms of the
Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
352 Advances in Ferroelectrics

Figure 1. The end-members of perovskite NBT-BT: rhombohedral NBT and tetragonal BT. Cations Na+/Bi3+ and Ba2+
occupy the A-sites while Ti4+ occupies B-sites (oxygen octahedra centers).

The solid solution with BaTiO3, (1-x) NBT-x BT shows a morphotropic phase boundary
(MPB) between the rhombohedral and the tetragonal phase, at x between 0.06 and 0.07 for
which the material properties are considerably improved. Indeed d33 values up to 450 pC/N,
and huge electric field-induced strain have been reported [4, 5]. Figure 1 shows the crystal‐
line structures of the NBT and BT end members at room temperature. Perovskite structure
deformations include oxygen octahedral rotations around different axis and cation shifts,
therefore giving rise to a complex succession of ferroelastic and ferroelectric phase transfor‐
mations with temperature variation.

Due to this polymorphic structure, NBT and NBT-BT have been also intensively studied in
order to clarify their complicated phase transitions, which still pose questions [6].Structural
and polar transformations in NBT-BT are more complicated than in other perovskite solid
solutions, also due to the strong disorder of the A-sites occupied by Na+, Bi3+ or Ba2+ ions,
with different valence, mass and ionic radius. NBT transforms successively, from the high
temperature cubic paraelectric into tetragonal antiferroelectric (or ferrielectric) and further
into a rhombohedral ferroelectric phase [6]. In solid solution with BT, the ground ferroelec‐
tric phase changes from rhombohedral R3c to tetragonal ferroelectric P4mm, at the so-called
morphotropic phase boundary (MPB) (x ≈ 0.06-0.07) [5, 7, 8]. The phase diagram of NBT-BT
bulk material, mainly based on dielectric measurements, was completed by Cordero et al by
performing direct anelastic measurements, the border between tetragonal and cubic phases
being evidenced [9, 10, 11].

For NBT-BT thin films growth many techniques have been used. Guo et al. have investigated
NBT-BT-based tri-layered films prepared by chemical solution deposition as a possible solu‐
 Phase Transitions, Dielectric and Ferroelectric Properties of Lead-free NBT-BT Thin Films 353
http://dx.doi.org/10.5772/ 52395

tion to the problem of avoiding leakage currents under high electric fields [12, 13]. Using
pulsed laser deposition (PLD), Duclère et al. have reported the heteroepitaxial growth of
NBT thin films on epitaxial platinum electrodes supported on a sapphire substrate [14].
More recently, M.Bousquet et al have described the electrical properties of (110)- oriented
NBT thin films deposited by laser ablation on (110)Pt/(110) SrTiO3 substrates [15]. They re‐
ported the coexistence of two kinds of grains with different shapes in the films, flat and
elongated grains corresponding to (100) and (110) oriented NBT crystallites. The effects of
Bi- excess in target on the dielectric and ferroelectric properties of the films have been also
presented; the reported values for relative permittivity and remnant polarization were
εr≈225-410 and 14 μC/cm2, respectively. Furthermore, very recently, the electrical properties
of (100)-oriented Na0.5Bi0.5TiO3-BiFeO3 thin films deposited by sol-gel have been reported by
Qin et al, aiming to important applications such as photovoltaic devices [16].
However, despite the fact that ferroelectric materials with MPB have enhanced ferroelectric
and piezoelectric properties, it is difficult to transpose them in thin films since MPB is limit‐
ed to a small composition range. Almost all the physical parameters involved in thin films
deposition like the substrate type, the microstructure and stress have strong impact on their
physical properties [17]. In some previous papers we have investigated the role of different
deposition parameters on NBT-BT film growth and properties [18, 19]. In this chapter, we
discuss the role of certain experimental conditions like deposition temperature and substrate
type, as well as of the amount of BT present in the target on crystalline structure, microstruc‐
ture, dielectric properties, phase transition temperatures and stability limits of ferroelectric
phases in NBT-BT thin films produced by PLD.

2. Experimental method

Pulsed laser deposition (PLD) was used for the film growth. The targets with composition
(NBT)1-x(BT)x (x = 0.06-0.08), further called NBT-BT6 and NBT-BT8, have been prepared fol‐
lowing the mixed oxide route and sintered at 1150 oC for 2 h. The sintering was performed
in crucibles with the sample surrounded with NBT pack, in order to avoid the loss of Na
and Bi, which occurs at temperatures over 1000 oC; more details can be found in Ref.11. X-
ray diffraction analysis evidenced the obtaining of pure perovskite phase. The microstruc‐
ture of the sintered targets was investigated on polished and etched surfaces by scanning
electron microscopy. The observed grain sizes were 2-10 μm.
For the film deposition, a Surelite II Nd:YAG pulsed laser with wavelength of 265 nm, pulse
duration of 5 ns and frequency 10 Hz, has been employed. The laser fluence was set at 1.6
J/cm2. The films were grown on Nb:STO and Pt/TiO2/SiO2/Si substrates, placed at a distance
of about 4.3 cm from the target. Different sets of films have been grown at different substrate
temperatures, ranging between 650-730 oC. Deposition and after-deposition cooling were
performed in flowing oxygen atmosphere (0.3-0.6 mbar) to favour the formation of perov‐
skite phase without oxygen vacancies. Chemical composition was checked via SIMS techni‐
que using a Hiden SIMS/SNMS system. The thickness of the thin films, evaluated by
spectroellipsometry, was between 300-500 nm.
354 Advances in Ferroelectrics

For the investigation of the crystalline structure of the targets and films, a PANalytical
X’pert MRD diffractometer in Bragg-Brentano geometry was used. The measurements were
performed with a step size of 0.020 and with a scanning time on step of 25 s or 250 s, depend‐
ing on the angular range.

The film surface morphology was examined by AFM (model XE100, Park Systems). Piezo‐
electric force microscopy measurements were performed with a PFM system which includes
a lock-in amplifier SR-830 and a dc- high voltage amplifier WMA-280. Conductive all-metal
Pt tips were employed for these measurements were the switching characteristcs of the films
have been tested.

Several Au electrode dots with an area of about 0.22 mm2 have been evaporated through a
mask on the films for electrical characterization. Polarization hysteresis was measured by
using a Radiant Technology RT66A ferroelectric test system, in the virtual ground mode.
The dielectric measurements were carried out in a frequency range between 200 Hz and 1
MHz using an HP 4194A impedance analyzer and an HP 4284A LCR meter with a four wire
probe. The measurements were performed at 1.5 K/min between 300 and 570 K in a Delta
Design climatic chamber model 9023 A (on targets) and in a Linkam variable-temperature
stage (model HFS 600E) on films.

3. Results and discussion.

3.1. Growth mode of NBT-BT thin films.

The microstructure of ceramic thin films is one of the most important factors that influence
their physical properties. Since the growth mode of thin films is strongly dependent on the
substrate type, we investigated the deposition of NBT-BT thin films on two different types
of substrates:

1. single crystal SrTiO3: Nb (Nb:STO) and

2. Pt/TiO2/SiO2/Si.

The AFM pictures obtained on the two sets of films show important microstructural differ‐
ences, mainly due to different growth mechanisms. In Figure 2 we show AFM images taken
on a NBT-BT6 film deposited on Nb: STO monocrystalline substrate at 650 0C. It can be ob‐
served that a first stage of growth resulting into a continuous layer stops when the critical
thickness for misfit dislocations (probably a few tens of nm) is reached. After that, the
growth continues in platelet-like form (see details in Fig. 2 b). If the deposition temperature
is not sufficiently high to favor material exchange between platelets via surface migration,
successive layers will grow on the top of the first islands and the growth will result into a
discontinuous layer. This explains the platelet-like aspect of the film shown in Figure 2.
 Phase Transitions, Dielectric and Ferroelectric Properties of Lead-free NBT-BT Thin Films 355
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Figure 2. AFM images of NBT-BT6% films deposited on Nb:STO substrates at temperature of 650 oC. The displayed
surfaces are 20x20 μm2 (a) and 5x5 μm2 (b).

Figure 3. AFM images of NBT-BT6% films deposited on Nb:STO substrates at 700oC. The displayed surfaces are 20x20
μm2 (a) and 5x5 μm2 (b).
356 Advances in Ferroelectrics

However, raising the substrate temperature to 700 0C during the deposition of a second set
of films while keeping constant all the other parameters, including the number of laser puls‐
es, produces a uniform layer of continuous platelets, on top of which new islands nucleate
(Figure. 3).

A rather different morphology is displayed by NBT-BT films grown on Pt/TiO2/SiO2/Si (Fig.

4 and 5). In this case, the growth progresses from the beginning in island-like form since the
polycrystalline Pt layer provide the nucleation sites for their formation. Moreover, these
NBT-BT islands grow on the Pt layer without preserving a unique orientation, due to the
same reason. Instead films grown on Nb:STO monocrystalline structures are uniaxially
(001)-oriented, as it will be shown in the next section.

Figure 4. AFM images of NBT-BT6% films deposited on Pt/TiO2/SiO2/Si substrate at a temperature of 700 oC. The dis‐
played surfaces are 20x20 μm2 (a) and 5x5 μm2 (b).

A fine microstructure with grain size ranging from a few tens of nm up to a few hundred of
nm is displayed by NBT-BT6 films (Fig. 4). We note the striking difference with bulk sam‐
ples microstructures (not shown here), which consists of crystallites of 1-10 μm size.

A similar fine microstructure is displayed by NBT-BT8% films grown on Pt/TiO2/SiO2/Si

(Fig. 5 a). However, the enlarged AFM image displayed in Fig 5 b) reveales a somewhat dif‐
ferent aspect with triangular nanograins lying in plane.
 Phase Transitions, Dielectric and Ferroelectric Properties of Lead-free NBT-BT Thin Films 357
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Figure 5. AFM images of NBT-BT8% films deposited on Pt/TiO2/SiO2/Si substrate at a temperature of 700 o C. The dis‐
played surfaces are 20x20 μm2 (a) and 5x5 μm2 (b).

3.2. Crystalline structure

The XRD spectrum of NBT-BT6 target corresponds to a mixture of rhombohedral R3c and
tetragonal P4mm phases, as shown by the splitting of (111) and (200), (012) and (024) rhom‐
bohedral peaks in the bottom pattern in Fig. 6 [20]. The main Miller index of the rhombohe‐
dral phase are depicted horizontally on the bottom of the figures while those of the
tetragonal phase vertically above. On the same graph, the pattern corresponding to the
NBT-BT6 film grown on Pt/TiO2/SiO2/Si at 700 0C is given. The curve corresponding to NBT-
BT6/Pt/TiO2/SiO2/Si film deposited in the same conditions but at a substrate temperature of
6500 exhibits similar features as we had reported and is not presented here [18].The as de‐
posited thin films exhibit pure perovskite phase with symmetry congruent with that of the
target. The reflection peaks indicate a randomly oriented structure, consistent with the poly‐
crystalline nature of the films.
358 Advances in Ferroelectrics

Figure 6. XRD spectra of NBT-BT6% deposited on Pt/TiO2/SiO2/Si substrate. The bottom pattern corresponds to the
target

Figure 7 displays the XRD patterns of NBT-BT6 films deposited at two temperatures, 650 0C
and 700 0C, around the (100)/(001) and (200)/(002) reflections of the Nb:STO substrate. The
spectra indicate the epitaxial growth of NBT-BT6% films on the Nb:STO substrate at the two
temperatures. This feature is congruent with the microstructure shown in the previous sec‐
tion (Fig. 2 and Fig. 3), consisting of large platelet-like crystallites which preserve the same
axis of orientation with the monocrystalline substrate.

Figure 7. XRD spectra of NBT-BT6% /Nb:STONb:STO films deposited at 650 oC and 700 oC. The grey pattern represents
the Nb:STONb:STO target reflection peaks.
 Phase Transitions, Dielectric and Ferroelectric Properties of Lead-free NBT-BT Thin Films 359
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Figure 8 shows the XRD patterns of NBT-BT8 films grown on Pt/TiO2/SiO2/Si and Nb:STO
substrates at 700 0C. The grey pattern represents the NBT-BT8 target spectrum, which cor‐
responds to the tetragonal P4mm symmetry. It can be observed that, similar to the previ‐
ous composition, the growth on single crystal Nb:STO substrate produces an epitaxial film,
while the growth on Pt/TiO2/SiO2/Si substrate results into a polycrystalline randomly ori‐
ented film.

Figure 8. XRD spectra of NBT-BT8% deposited on Pt/TiO2/SiO2/Si and on Nb:STONb:STO substrates

3.3. Dielectric and ferroelectric properties

The dielectric and ferroelectric properties of NBT-BT thin films have been evaluated on ca‐
pacitors formed by evaporating through a mask an array of gold electrode dots with an area
of about 0.22 mm2 on the surface of films grown on Pt/TiO2/SiO2/Si and Nb:STO substrates.
The bottom electrode was formed by the Pt layer in the first case or by the Nb:STO substrate
itself in the second case.

The piezoresponce force microscopy results are presented in Figure 9. The full-Pt tips were
brought in contact with the surface of the sample and then a dc bias and test ac bias were
applied between the tip and the bottom electrode of the samples. The dc bias was generated
by a high voltage amplifier and the ac bias was generated by a lock-in amplifier. The same
lock-in amplifier was used to analyse the vertical deflection signal from the PSPD, in order
to extract the amplitude and the phase of the cantilever oscillations induced by the local de‐
360 Advances in Ferroelectrics

formation of the sample due to the applied dc bias. The NBT-BT6/Pt/Si thin films show good
switching behavior, the piezoelectric hysteresis and pronounced imprint (not showed here)
confirming the piezoelectric and ferroelectric characteristics. The dependence of effective
piezoelectric coefficient d33 eff
on the applied electric field is given in Figure 9. The locally
measured values with the highest being around d33 eff
≈ 83 pm/V, are even higher then for
previouslly reported values for pure NBT or lead-based thin films, such as Pb(ZrTi)O3 or
PbTiO3 [21, 22]. However, these d33 eff are a bit smaller then NBT-BT6 ceramics which are re‐
ported to be more than 100 pm/V [21]. The reasons for these smaller values are related with
the film’s porosity, but also with the clamping effect which occurs because the PFM tip- ap‐
plied electric field will piezoelectrically deform only a small fraction of the film. The rest of
the sample will restrict the relative deformation of this small fraction, resulting a lower val‐
ue for d33 eff [5, 22].

Figure 9. The piezoresponse measurements performed on NBT-BT6 thin films.

In Fig. 10 the room temperature dielectric properties of NBT-BT6 films deposited on Pt/
TiO2/SiO2/Si at different substrate temperatures, 650 0C and 730 0C, have been compared in
the frequency range 100 Hz-1 MHz. Films grown at 650 0C show a higher dielectric constant
(ε’ ~ 1000), in the order of magnitude of the bulk values (ε’bulk ~ 1900), while films grown at
730 0C show lower values (ε’ ~ 700). The dielectric loss values are instead comparable in the
two samples, and similar to bulk values.
 Phase Transitions, Dielectric and Ferroelectric Properties of Lead-free NBT-BT Thin Films 361
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Figure 10. Room temperature dielectric constant ε’ and loss tanδ variation with frequency for NBT-BT6% films depos‐
ited at different temperatures on Pt/TiO2/SiO2/Si.

Figure 11 displays the room temperature dielectric constant and dielectric loss in the fre‐
quency range 100 Hz-1 MHz for NBT-BT8 films grown on Pt/TiO2/SiO2/Si at different tem‐
peratures: 650, 700 and 730 0C. Unlike the previous composition, in this case growth at
higher substrate temperatures was beneficial for the improvement of dielectric properties, at
least in the frequency domain up to a few hundred kHz. Above this frequency there is a
strong increase of dielectric loss. Since an increase is registered also in the dielectric con‐
stant, this could be caused by a relaxation mechanism which is active at room temperature
at these frequencies, like e.g. free charge relaxation.
362 Advances in Ferroelectrics

Figure 11. Room temperature dielectric constant and loss variation with frequency for NBT-BT8% films deposited at
different temperatures on Pt/TiO2/SiO2/Si

Polarization hysteresis measurements on NBT-BT6 films grown on Pt/TiO2/SiO2/Si are

shown in Fig. 12. Spontaneous polarization was about 30 μC/cm2 and the remnant polariza‐
tion was about 10 μC/cm2. The rather high value of coercive field (100 kV/cm) could be ex‐
plained by the presence of intrinsic strain and pinning defects.

Dielectric and ferroelectric properties measurements on films deposited on Nb:STO sub‐

strates have been less reliable, probably due to the presence of a non-ohmic contact at the
NBT-BT film – semiconductor Nb:STO interface. However PFM measurements (not shown
 Phase Transitions, Dielectric and Ferroelectric Properties of Lead-free NBT-BT Thin Films 363
http://dx.doi.org/10.5772/ 52395

here) evidenced good piezoelectric response, which indicates good intrinsic dielectric and
ferroelectric properties, although quantitative values are difficult to extract.

Figure 12. Polarization-electric field hysteresis loop measured on a NBT-BT6% film deposited on Pt/TiO2/SiO2/Si

3.4. Phase transitions

Phase transitions in ferroelectric materials are accompanied by anomalies of complex dielec‐

tric permittivity variation with temperature, generally narrow peaks or steps, depending on
the type of phase transformation. However NBT-BT compositions near the morphotropic
phase boundary behave as relaxors, due to the cation disorder. This is evidenced in Fig. 13
for NBT-BT8 bulk material. The main characteristic of a relaxor ferroelectric is a broad
dielectric peak at a temperature Tm which is not related to a structural transformation. This
is due to a wide distribution of relaxation times which characterizes the dielectric re‐
sponse of polar nanoregions. This peak shifts with the increasing of the measurement fre‐
quency toward higher temperatures. Thus the dielectric maximum of NBT-BT8 shifts from
about 497 K at 200 Hz to about 512 K at 100 kHz. A similar dependence is obeyed also by
the dielectric loss.

In Fig. 14 the variation of dielectric constant and loss with temperature for a NBT-BT8 film
deposited on Pt/TiO2/SiO2/Si is shown. The maximum of the dielectric constant occurs at
about 485 K, not far from bulk Tm. However the anomaly is characteristic of a well-behaved
phase transition, since the peak temperature Tm does not shift with frequency. A similar
qualitative behavior was observed also on the dielectric permittivity variation with tempera‐
ture for NBT-BT6 films (not shown here).
364 Advances in Ferroelectrics

Figure 13. The dielectric permittivity and loss variation with temperature measured on a NBT-BT8% bulk sample at
different frequencies. The long arrows mark the increasing of frequency.

While the dielectric permittivity peak position Tm ~ 485 K does not shift with measuring fre‐
quency, peak height is strongly dependent on it, decreasing for higher frequencies. This can
be attributed to the possible presence of a non-polar dielectric layer, which does not influ‐
ence the general behavior at phase transition, but can modify the value of the dielectric con‐
stant [23]. Generally these interface layers can have strong frequency-dependent dielectric
properties which influence the overall properties of the heterostructures. However we stress
again that the dependence on temperature and phase transition temperatures can be influ‐
enced only in the limits of a monotonous contribution, since the dielectric behaviour of non-
polar layers is free of temperature anomalies. Indeed the stronger variation with
 Phase Transitions, Dielectric and Ferroelectric Properties of Lead-free NBT-BT Thin Films 365
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temperature of the peak intensity at Tm could be attributed to the non-polar layer contribu‐
tion at higher temperatures due to conductivity variation.

The temperature Td where a strong increase of dielectric loss and dielectric constant occurs
marks the ferroelectric – antiferroelectric phase transition which, in bulk samples with the
same composition is visible only in the poled state. It is called also depolarization temperature.

Figure 14. The dielectric permittivity and loss variation with temperature measured on a NBT-BT8% thin film at differ‐
ent frequencies. The long arrows mark the increasing of frequency.

An apparent frequency dependence of the step increase in tanδ which marks Td is visible on
the lower curves in Fig. 14. This could be attributed to a partial relaxor behavior due to
mixed nanodomains-normal ferroelectric domains, which can be find also, but in proportion
displaced to the nanodomain limit, in bulk samples. We must remark that the films were not
366 Advances in Ferroelectrics

poled, since no bias electric field was applied. Therefore the occurrence of a ferroelectric
ground state in the NBT-BT films, in striking contrast with relaxor bulk samples with the
same composition, must be generated by some intrinsic differences between ceramic bulk
samples and ceramic thin films. The first and most obvious reason could be related to the
constraining stress of the substrate on the thin films. This is strong in epitaxially grown thin
films with a thickness generally below 100 nm, but it should be almost absent in polycrystal‐
line films, randomly oriented and with a thickness of several hundreds of nm. This last one
is the case for NBT-BT thin films deposited on Pt/TiO2/SiO2/Si substrates. The second reason
could be related to the strong differences in the microstructures of ceramic thin films and
bulk materials with the same composition. Therefore the occurrence of a ferroelectric
ground state instead of a relaxor state in NBT-BT films, as well as the occurrence of a true
ferroelectric phase transition could be due to the constrainig imposed by the nanograin
boundaries on the ensemble of polar nanoregions.

4. Conclusions

In summary, we have investigated the role of deposition temperature and substrate type as
well as the amount of BT present in the target on crystalline structure, microstructure, die‐
lectric properties, phase transition temperatures and stability limits of ferroelectric phases in
NBT-BT thin films grown by pulsed laser deposition. We have successfully deposited pure
perovskite epitaxial films on single-crystal Nb:STO substrates. Successful growth of NBT-BT
films on platinized silicon substrates has been achieved. Good dielectric and ferroelectric
properties, comparable with bulk values, have been obtained. The NBT-BT6/Pt/Si thin films
show a classic switching behavior, the piezoelectric hysteresis and pronounced imprint con‐
firming the piezoelectric and ferroelectric characteristics. The locally measured value of ef‐
fective piezoeletric coefficient d33 eff was around 83 pm/V, higher to the previouslly reported
values for pure NBT or lead-based thin films. An enhanced stability of ferroelectric phase in
thin films with respect to bulk has been observed and explained by their peculiar nanocrys‐
talline microstructure.

Author details

N. D. Scarisoreanu1*, R. Birjega1, A. Andrei1, M. Dinescu1, F. Craciun2 and C. Galassi3

*Address all correspondence to: [email protected]

1 NILPRP, National Institute for Laser, Plasma & Radiation Physics, Bucharest, Romania

2 CNR-ISC, Istituto dei Sistemi Complessi, Area della Ricerca Roma-Tor Vergata, Roma, Ita‐
ly

3 CNR-ISTEC, Istituto di Scienza e Tecnologia dei Materiali Ceramici, Faenza, Italy

 Phase Transitions, Dielectric and Ferroelectric Properties of Lead-free NBT-BT Thin Films 367
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References

[1] Saito, Y., Takao, H., Tani, T., Nonoyama, T., Takatori, K., Homma, T., Nagaya, T., &
Nakamura, M. (2004). Lead-free piezoceramics. Nature, 432, 84.
[2] Smolenski, G. A., Isupov, V. A., Agranovskaya, A. I., & Krainik, N. N. (1961). New
ferroelectrics of complex composition, Sov. Phys. Solid State, 2, 2651-196.
[3] Chiang, Y. M., Farrey, G. W., & Soukhojak, A. N. (1998). Lead-free high-strain single-
crystal piezoelectrics in the alkaline-bismuth-titanate perovskite family. Appl. Phys.
Lett, 73, 3683.
[4] Takenaka, T., & Nagata, H. (1999). Present Status of Non-Lead-Based Piezoelectric‐
Ceramics. Key Engineering Materials, 157/158, 57.
[5] Takenaka, T, Maruyama, K.-I., & Sakata, K. (1991). (Bi1/2Na1/2)TiO3-BaTiO3 System
for Lead-Free Piezoelectric Ceramics. Jpn. J. Appl. Phys, 30, 2236-2239.
[6] Jones, G. O., & Thomas, P. A. (2002). Investigation of the structure and phase transi‐
tions in the novel A-site substituted distorted perovskite compound Na0.5Bi0.5TiO3,
Acta Crystallogr. Sect. B: Struct. Sci, 58, 168 -178 .
[7] Hiruma, Y., Watanabe, Y., Nagata, H., & Takenaka, T. (2007). Phase Transition Tem‐
peratures of Divalent and Trivalent Ions Substituted (Bi1/2Na1/2)TiO3 Ceramics, Key
Eng. Mater, 350, 93.
[8] Glazer, A. M. (1972). The classification of tilted octahedra in perovskites, Acta Crys‐
tallogr. Sect. B: Struct. Sci, 28, 3384.
[9] W.-van, B., Eerd, D., Damjanovic, N., Klein, N., Setter, , & Trodhal, J. (2010). Structur‐
al complexity of (Na0.5Bi0.5)TiOP3BaTiO3 as revealed by Raman spectroscopy. Phys.
Rev. B, 82, 104112.
[10] Ma, C., & Tan, X. (2010). Phase diagram of unpoled lead-free (1-x)(Bi/sub 1/2/Na/sub
1/2/)TiO/sub 3-x/BaTiO/sub 3/ ceramics. Solid State Commun, 150, 1497-1500.
[11] Cordero, F., Craciun, F., Trequattrini, F., Mercadelli, E., & Galassi, C. (2010). Phase
transitions and phase diagram of the ferroelectric perovskite (Na0.5Bi0.5)1−xBaxTiO3
by anelastic and dielectric measurements. Phys. Rev. B, 81, 144124.
[12] Guo, Y. P., Akai, D. S., Sawada, K., & Ishida, M. (2008). Dielectric and ferroelectric
properties of highly (100)-oriented (Na0.5Bi0.5)0.94Ba0.06TiO3 thin films grown on
LaNiO3/γ-Al2O3/Si substrates by chemical solution deposition. Solid State Sciences,
10, 929.
[13] Guo, Y. P., Akai, D. S., Sawada, K., Ishida, M., & Gu, M. Y. (2009). Structure and elec‐
trical properties of trilayered BaTiO3/(Na0.5Bi0.5)TiO3BaTiO3/BaTiO3 thin films de‐
posited on Si substrate. Solid State Communications, 149, 14.
[14] Duclère, J.R., Cibert, C., Boulle, A., Dorcet, V., Marchet, P., Champeaux, C., Catheri‐
not, A., Députier, S., & Guilloux-Viry, M. (2008). Lead-free Na0.5Bi0.5TiO3 ferroelec‐
368 Advances in Ferroelectrics

tric thin films grown by Pulsed Laser Deposition on epitaxial platinum bottom
electrodes. Thin Solid Films, 517, 592.

[15] Bousquet, M., , J., Ducle`re, R., Gautier, B., Boulle, A., Wu, A., De´, S., putier, D., Fas‐
quelle, F., Re´mondie`, re. D., Albertini, C., Champeaux, P., Marchet, M., Guilloux- ,
Viry, & Vilarinho, P. (2012). Electrical properties of (110) epitaxial lead-free ferroelec‐
tric Na0.5Bi0.5TiO3 thin films grown by pulsed laser deposition: Macroscopic and
nanoscale data. J. Appl. Phys, 111, 104 -106.

[16] Qin, W., Guo, Y., Guo, B., & Gu, M. (2012). Dielectric and optical properties of Bi‐
FeO3-(Na0.5Bi0.5)TiO3 thin films deposited on Si substrate using LaNiO3 as buffer
layer for photovoltaic devices. J. Alloys Compd, 513, 154-158.

[17] Shaw, T. M., Trolier Mc Kinstry, S., & Mc Intyre, P. C. (2000). The properties of ferro‐
electric thin films at small dimensions. Annu. Rev. Mater. Sci, 30, 263.

[18] Scarisoreanu, N., Craciun, F., Chis, A., Birjega, R., Moldovan, A., Galassi, C., & Di‐
nescu, M. (2010). Lead-free ferroelectric thin films obtained by pulsed laser deposi‐
tion. Appl. Phys A, 101, 747 -751 .

[19] Scarisoreanu, N., Craciun, F., Ion, V., Birjega, S., & Dinescu, M. (2007). Structural and
electrical characterization of lead-free ferroelectric Na/sub 1/2/Bi/sub 1/2/TiO/sub 3/-
BaTiO/sub 3/ thin films obtained by PLD and RF-PLD. Appl. Surf. Sci, 254, 1292.

[20] Picht, G., Töpfer, J., & Henning, E. (2010). Structural properties of
(Bi0.5Na0.5)1−xBaxTiO3 lead-free piezoelectric ceramics. J. Eur. Ceram. Soc, 30, 3445.

[21] Takenaka, T. (1999). Piezoelectric Properties of Some Lead-Free Ferroelectric Ceram‐

ics. Ferroelectrics, 230, 87-98.

[22] Morelli, A., Sriram, Venkatesan, Palasantzas, , Palasantzas, Kooi, G, & De Hosson, J.
Th. M. (2009). Piezoelectric properties of PbTiO3 thin films characterized with pie‐
zoresponse force and high resolution transmission electron microscopy. J. Appl. Phys,
105, 064106.

[23] Craciun, F., & Dinescu, M. (2007). Piezoelectrics”, in “Pulsed laser deposition of thin
films: applications-led growth of functional materials”. edited by R. Eason (Wiley-Inter‐
science, John Wiley & Sons, Hoboken, New Jersey, U.S.A.,), 487-532.
 Chapter 17

Thin-Film Process Technology

for Ferroelectric Application

Koukou Suu

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/54360

1. Introduction

Recently thin-film ferroelectrics such as Pb(Zr, Ti)O3 (PZT) and (Ba, Sr)TiO3 (BST) have been
utilized to form advanced semiconductor and electronic devices including Ferroelectric Ran‐
dom Access memory(FeRAM), actuators composing gyro meters, portable camera modules,
and tunable devices for smart phone applications and so on. Processing technology of ferro‐
electric materials is one of the most important technologies to enable the above- mentioned
advanced devices and their productions.
In this paper, we will report our development results of ferroelectric thin film processing tech‐
nologies including sputtering, MOCVD and plasma etching as well as manufacturing process‐
es for FeRAM, MEMS(actuators, tunable devices) and ultra-high density probe memory.

2. FeRAM technology

Ferroelectric Random Access Memory (FeRAM) is a main candidate of next generation non-
volatile random access memory. As its density has been continuously increasing, its applica‐
tions have spread from RFID card to Nonvolatile latch circuit with low power consumption.
FeRAM has a ferroelectric thin films sandwiched by rare metal electrodes and we have estab‐
lished mass production capability on integrated FeRAM solution, consisting of electrode film
deposition, PZT thin-film deposition, etching/ashing, anneal and passivation deposition.

2.1. Mass productive sputtering technology for perovskite oxide thin-film

We have been developing mass production technology for perovskite oxide thin-film such
as PZT for a long period [1-5], since we consider these materials as the most promising can‐

© 2012 Suu; licensee InTech. This is an open access article distributed under the terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
370 Advances in Ferroelectrics

didate for ferroelectric material used in FeRAMs (Ferroelectric Random Access Memories)
as a non-volatile memory device, piezoelectric MEMS (Micro Electro Mechanical System)
devices due to its longer period of research, existence of actual production, manufacturing
capability within the tolerable temperature range of general Si LSI technology.

The sputtering was selected for mass production technology of perovskite oxide thin-
films owing to the following factors: (1) Good compatibility with conventional Si LSI
processes. (2) Superb controllability of film quality (e.g. film composition), which enabled
relatively easy thin film deposition. (3) Better possibilities of obtaining uniform surfaces in
large diameter substrates (e.g. 6-8 inch). (4) Sputtering was plasma processing which was
promising for deposition and heat treatment at low temperature. (5) Feasibility of high-
speed deposition. (6) Same deposition method as electrodes (Pt, Ir, Ru, etc.), which will
facilitate in-situ integration. (7) Present difficulties and lack of future potentialities in oth‐
er technologies.

With emphasis on both mass production capability and advanced process capacity of perovskite
oxide thin-film sputtering, we consider the following factors as important for development:
1. Throughput

Compared to the other processes (e.g. electrode deposition), the deposition speed of perov‐
skite oxide material sputtering was considerably slower and thereby limited the throughput.
Though two ways for improving the throughput, high-speed deposition and thinner film
deposition, are considered, the former is more promising for the improvement of through‐
put, while the latter is apt to cause deterioration of film characteristics.

2. Control of film composition

Film composition determines other film qualities (crystal structure, electric characteristics).
Since volatile elements were included in the perovskite oxide materials, they were sensitive
and easily fluctuated according to temperature or plasma status. Film composition control is
the fundamental factor in this process.

3. Uniformity over large diameter substrates

Large diameter substrates up to 8 inch were expected to be used for mass production of per‐
ovskite oxide thin-film. Film thickness and uniformity of film quality were the keys to mass
production.

4. Process stability / reliability

Under the circumstances where there were many unknown factors such as new materials,
ceramic targets, insulator sputtering, etc., process stability / reliability was the more perti‐
nent factor. In fact, there was a problem in film composition that changed over time.

5. Prevention of particles

While the characteristics, such as ceramic targets or insulating thin film, increased the me‐
chanical factors (e.g. adherence, thermal expansion) for particle occurrence, they were also
 Thin-Film Process Technology for Ferroelectric Application 371
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producing electric factors (e.g. dielectric breakdown due to charge-up) and made the meas‐
ures difficult to obtain.

2.2. Optimization of sputtering processes for perovskite oxide thin-film

We adapted the RF magnetron sputtering method for perovskite oxide thin-film sputtering.
As for the PZT thin-films, sputtering methods included high-temperature deposition, where
film deposition was made at substrate temperatures above 500°C [6, 7], and low tempera‐
ture deposition, where the films were deposited at room temperature and then crystallized
by post-annealing process. The improvement in high-speed deposition, film composition
control, and stability of sputtering processes is described in the following.

If the ceramic target with inferior thermal conductivity is used, application of high power
leads to the destruction of the target. By adopting the backing plate with high cooling effi‐
ciency and high-density target, higher deposition rate by an increase in sputtering power is
achieved.

The film composition control can be translated into the volatile element (e.g. Lead) control
within film. Various factors that influence the volatile element within film are thought to ex‐
ist (Fig. 1) and we have investigated the influence of sputtering conditions, strength of mag‐
netic field and electric potential of substrate.

Magnetic field

Zr O Pb Ti O Pb O Ti Zr Pb O Pb Zr
Target Content
(or Pb O )
Ar+
Pb Incident energy (sputtering power)
Ar Pressure Ar+ Number of Pb (or PbO)(Target surface)
Binding energy (substrate condition etc.)
Pb re-sputtering
Pb re-sputtering
(Plasma radiation)
Pb (Substrate temp.,Plasma radiation)
Zr Ti O Pb Ti Zr Pb Ti Pb Ti

Shields etc.
Substrate potential
A. Introducing Thermal energy (Plasma radiation)
Large-sized Shields (Substrate temp., Plasma radiation)
B. Controlling
Substrate Temperature

Figure
Figure 1. Various factors1.thatVarious
influencefactors
content that
with influence
PZT Film. content with PZT Film.
372 Advances in Ferroelectrics

In addition to the known characteristics in perovskite oxide thin-film sputtering that volatile
elements easily fluctuate, it was confirmed that volatile elements within film were unstable
even when the deposition was performed under identical conditions. The conceivable caus‐
es for that phenomenon were the instability of the target, fluctuation of temperature in the
sputtering chamber, and variation of plasma status over time.

Main problem in perovskite oxide thin-film is the change in the volatile element content
with the passage of sputtering time. As for the PZT, continuous sputtering of 2.0 kWh
showed approximately a 30% decline in lead content compared to that at the beginning. It
was determined that the reason for this problem was the change in plasma status. As shown
in Fig. 2, when insulating PZT film adhered to the shields of the ground potential, charge-up
occurred, the impedance of the system changed, plasma was pushed to the center of the
chamber, exposure to plasma was enhanced, and as a consequence, Pb content within film is
reduced. In order to stabilize the status of plasma, we installed a stable anode, that is, an
anode that avoided charge-up due to the adhesion of insulating PZT film and maintained
the role as an anode. Consequently, as can be seen in Fig. 3, stability of Pb content within
film in continuous sputtering has been confirmed.

Figure 2. Change in plasma status which is responsible for Pb content variation.

Fig. 4 shows an example of thickness and Pb content uniformity in a PZT film on 8” sub‐
strate. Both thickness and Pb content uniformity varied according to the deposition condi‐
tion and was minimized around the sputtering pressure of 1.0 Pa. Thickness and Pb content
uniformity represent good result as low as ±1.9% and ±1.1%, respectively. These uniformi‐
ties were also confirmed as stable, thereby satisfactorily meeting the requirements of mass
production.
 Thin-Film Process Technology for Ferroelectric Application 373
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Figure 3. Stable transition of Pb content within film in continuous sputtering.

Figure 4. Uniformity in 8 inch area.

2.3. Sputtered PZT thin-films for non-volatile memory application

In this section, we introduce one of its achievements, the ferroelectric characteristics of PLZT
capacitors for FeRAM. We used the multi chamber type mass production sputtering system
equipped with an exclusive sputtering module for ferroelectric materials, CERAUS ZX-1000
from ULVAC. This system has the following features in addition to features such as easy
maintenance, short exhausting time, short down time, etc.
374 Advances in Ferroelectrics

1. Can mount 300 mm (12 inch) in diameter targets and process large diameter substrates
of 200 mm. At present, deposition of PZT thin-films on 6 and 8 inch substrates are per‐
formed using 12 inch single ceramic target.
2. Including the heat chamber, this system has five process chambers, thereby achieving
high flexibility. The system is presently executing the following in-situ processes as
standard: pre-heating of substrate → substrate sputtering (e.g. Ti, TiN, Pt) → ferroelec‐
tric material sputtering.
3. As a substrate heating mechanism, this system was capable of precise and rapid heating
in a wide range from low to high temperatures, with the aid of an electrostatic chuck
type hot plate, in addition to lamp heating.
4. This system used RF sputtering for ferroelectric deposition and counters RF noises.

Fig. 5 shows the transition of switching charge (QSW) and saturation characteristics of a Pt/
PZT(200 nm)/Pt capacitor measured at 5 V. QSW with 5 V applied was approximately 34
μC/cm2 and saturation voltage of 90% (V90%) was 3.1-3.2 V. The composition of PLZT film,
which contained added Ca and Sr for the improvement of retention and imprint characteris‐
tics, was excellent.

Figure 5. Transition of switching charge of Pt/PZT(200 nm)/Pt capacitor.

Fig. 6 shows the stability of QSW in continuous sputtering of 1000 substrates. The result
showed high stability sufficient for mass production. Also, reference data was the data be‐
fore chamber cleaning. The fact that it was equivalent to the data after chamber cleaning
demonstrates the reliability of the system process.
 Thin-Film Process Technology for Ferroelectric Application 375
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Figure 6. Stability of Qsw in continuous sputtering of 1000 substrates.

Figure 7. Transition of switching charge of IrOx/PZT(80 nm)/Pt capacitor.

Further improvement of ferroelectric performancs is needed because scaled thinner capaci‐

tor (sub 100 nm) is demanded for next generation. Pb deficient surface layer is confirmed to
be responsible for degradation of ferroelectric performance. Bottom electrode and PZT dep‐
osition process were modified to further improve the ferroelectric performance and achieve
376 Advances in Ferroelectrics

thinner capacitor with good performances. [8]. Fig. 7 shows the QSW transition curve of a Ir‐
Ox/PZT(80 nm)/Pt capacitor measured at 3 V. QSW with 1.8 V applied was approximately 24
μC/cm2 and V90% was 1.4 V. Fig. 8 also shows the fatigue characteristics of voltage applica‐
tion at 2 V. QSW was not decreased even after switching in 109 cycles.

Figure 8. Fatigue characteristics of IrOx/PZT(80 nm)/Pt capacitor.

From above results, sputter-derived PZT capacitor was proved to be suitable for 0.18 μm
technology node.

2.4. MOCVD technology for non-volatile memory application

For next-generation FeRAMs beyond 0.18 μm, because it is necessary to achieve further larg‐
er packing densities and integration with logic devices, thinner films of ferroelectric associ‐
ated with shrinking of the thickness of ferroelectric capacitors and the three-dimensional
structures associated with shrinking of the capacitor areas are demanded. In addition, it is
necessary to achieve thinner films of ferroelectric in parallel with its higher quality in order
to meet the demand of still lower voltage drives for device performance. It is said that
MOCVD (Metal organic chemical vapor deposition) technology can meet these demands.
While depositions are physically made by plasma collision in sputtering processes, deposi‐
tions are made on heated substrates by chemical reaction among source gases in MOCVD.
Therefore, denser crystalline films are easily obtainable, and it is possible to achieve thinner
films and higher quality. In addition, uniform deposition can be obtained also on three-di‐
mensional structure, and it is considered that good step coverage can be obtained. Because
of these features, MOCVD is the prime candidate of deposition technologies for next-genera‐
tion FeRAMs in mass production, and its development is making progress.
 Thin-Film Process Technology for Ferroelectric Application 377
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First, the features of MOCVD are briefly explained. In the method of MOCVD, raw material
that was changed into organic metal with high vapor pressure is led to a substrate, and is
thermally reacted with a reactant gas (such as oxygen) on the substrate to form a deposition.
Methods for the gasification of organic metals are classified into two groups. One of them is
the sublimation of solid raw materials (sublimation method). After a certain vapor pressure
is obtained by heating a solid raw material using a heater, it is transported with carrier gas.
In the second method, a liquid raw material or solid raw material is melted in an organic
solvent. Then, after the solution is vaporized, it is transported with carrier gas (vaporization
method). In the case of the former, the deposition rate is small. In the case of the latter, there
is a problem of the instability of vaporization. For the target of mass-production system de‐
velopment, we adopted the latter vaporization method from the beginning of the develop‐
ment. The problems that need to be resolved are as follows (see Fig. 9):

Figure 9. Features of MOCVD Module

1. Vaporization and transport of multi-element raw materials In MOCVD using the vapor‐
ization of a ferroelectric solution, because a multi-element organic metal material is va‐
porized and transported, stable vaporization is difficult, and there is a possibility that
precipitation or decomposition may occur in a pipe during transport.

2. Mixture of gases whose molecular weights are mutually different It is difficult to uni‐
formly mix a reactant gas such as oxygen and an organic raw material whose molecular
weights are vastly different.

3. Uniformity of large-diameter substrates For the film thickness and the composition of a
multi-element oxide thin film PZT, in-plane uniformity in 8 inches is required.
378 Advances in Ferroelectrics

4. PTZ film properties Because of high-temperature processes and in-situ crystallization in

the processes, the correlation between the kind of a raw material and a process is sensi‐
tive, and the control of a film composition and crystalline orientation is difficult. There‐
fore, necessary performance of films is difficult to obtain.

In order to establish MOCVD mass-production technology, it is absolutely necessary to re‐

solve the above problems in parallel, and advanced vaporization technology, mixing tech‐
nology, and reaction control technology are simultaneously required. We combined
ferroelectric deposition technology for FeRAMs, module design technology, and CVD
equipment technology, which were provided to users until now, and completed full-fledged
MOCVD equipment for mass production. The major features include the following four
points:

1. The reproducibility in the continuous operation of vaporization and the gas transport to
a substrate that controls condensation and decomposition were achieved by accurate
temperature control for each part of equipment and the optimization of vaporization
conditions. Consequently, film thicknesses within ±2% and the reproducibility of the
PZT composition were kept with no mechanical maintenance, and a running test for
1,000 substrates was successful as shown in Fig. 10. [9]

Figure 10. Reproducibility in MOCVD system (film thickness and PZT composition)

2. Because the design of the equipment was conducted in consideration of the flow of gas‐
es and the mixture between a raw material gas and a reactant gas on the basis of simu‐
lations, film thickness distribution within ±3% on 8 inch substrates was achieved as
shown in Fig. 11.
 Thin-Film Process Technology for Ferroelectric Application 379
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Figure 11. In-plane uniformity of PZT film thickness

3. Because of the development of a new heater, including the optimization of the shape of
the heater, the temperature distribution of 8 inch substrates can be continually control‐
led within ±3ºC. Consequently, in-plane uniformity within ±3% was achieved for both
film thicknesses and the composition as shown in Fig. 12. [10]

Figure 12. In-plane uniformity of PZT composition

380 Advances in Ferroelectrics

4. By taking advantage of the progress of the equipment hardware as described above, the
optimization of processes was conducted, and PZT thin films can be controlled to en‐
sure preferential orientation in the <111> direction as shown in Fig. 13. Consequently,
the formation of PZT films within 100 nm that have capacitor properties with a 1.5 V
low voltage drive is achieved as shown in Fig. 14. [11,12] In addition excellent endur‐
ance properties which are over 1010cycles were obtained for 73nm-PZT in Fig 15.

Figure 13. XRD spectrum for various thickness PZT

Figure 14. Characteristics of MOCVD-PZT film (applied voltage dependence of switching charge)
 Thin-Film Process Technology for Ferroelectric Application 381
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Figure 15. Endurance properties of MOCVD-PZT films

Recently mass production tool for 300mm Si wafer was developed and excellent in-plane
uniformity less than 1.5% for thickness and PZT composition were obtained.

2.5. Etching technology

2.5.1. Issues of ferroelectric etching technology

Conventionally, the piezoelectric elements have been fabricated by chemical wet etching
[13] or argon ion milling. With the miniaturization of MEMS, there have been increasing de‐
mands for dry etching with the excellent shape controllability as semiconductor technology.
Recently dry etching technique for MEMS using PZT was reported. [14,15] The Pt, Ir and
other rare metal electrodes and the PZT ferroelectric thin films that compose piezoelectric
elements react poorly with halogen gases and their halides have low vapor pressures. For
these reasons, these materials are called hard-to-etch materials. The following technical is‐
sues are important for dry etching of the PZT ferroelectric thin films for not only FeRAM but
also MEMS productions:
1. Etching selectivity to resist mask and the bottom rare metal electrode
A piezoelectric element film consists of PZT with a thickness of several micrometers and the
rare metal electrodes with a thickness of about 100 nm. Generally, the bottom electrode is
left after the PZT etching. Therefore, a low etching rate for the bottom electrode, the so-
called high etching selectivity, is important as a PZT etching condition.
2. Adhesion of conductive deposit to the pattern sidewalls and damage to PZT
The materials are hard to etch, and their etching products easily adhere to the pattern side‐
walls, and result in leaks between the top and bottom electrodes. What is worse, the pattern
382 Advances in Ferroelectrics

sidewalls are exposed to reactive gas plasma during etching, and tend to suffer lead and
oxygen coming out and other damages.
3. Plasma stability during continuous processing

Adhesion of etching products to chamber walls, especially the RF introduction window that
generates plasma, causes instabilities of plasma and deteriorates the etching rate and the
shape reproducibility. Avoiding of adhesion of etching products to chamber walls is impor‐
tant for mass production.

4. Uniformity of etching rate within wafer

As in the case of (1), to stop the thick PZT at the thin bottom electrode after etching, the uni‐
formity of etching rate within wafer is important.

2.5.2. Ferroelectric etching systems and process for mass production

As the piezoelectric PZT etching systems, this section explains about Apios NE series made by
ULVAC, Inc. The etching module is equipped with the ISM (Inductively Super Magnetron)
plasma source that can generate low-pressure and high-density plasma. Fig. 16 shows a draw‐
ing of the etching module. Table I shows the comparison between the normal ICP type plas‐
ma source and the ISM plasma source. The RF antenna is mounted in the upper part of the
etching chamber, so that RF is introduced through the quartz window into the etching cham‐
ber to generate plasma. The uniformity of the etching rate within wafer can be easily opti‐
mized by positioning permanent magnets under the antenna. Fig. 17 shows the uniformity of
PZT etching rate within 6 inch wafer. A high uniformity (<+/-5%) was realized by means of op‐
timization to permanent magnet layout. A STAR electrode is provided between the antenna
and the quartz window to control adhesion of etching products to the quartz window by ap‐
plying RF to the STAR electrode. The substrate is held on the electrostatic chuck. The sub‐
strate temperature is controlled by introducing Helium to the backside of the substrate. The
ion energy is controlled by applying RF power to the substrate. The materials to be etched are
non-volatile, and the etching products adhere to the shield located in the chamber. The tem‐
perature of the shield is kept constant by heater, so process is high stability.

ISM ICP
Plasma density (cm-3) 1×1010 ~ 1×1011 5×109 ~ 5×1010
Operating pressure (Pa) 0.07<P<7 0.5<P<50
Uniformity Optimized magnetic layout Determined by chamber structure
Plasma density and substrate bias can be
Damage
controlled independently.
Less re-deposition results in Low-pressure High pressure process causes re-
Repeatability, stability
etching -> better repeatability deposition.
Chamber structure is simple for easy
Maintenance
maintenance.

Table 1. Inductively super magnetron (ISM) plasma performances.

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Figure 16. Etching chamber with inductively super magnetron (ISM) plasma performances

Figure 17. PZT etching uniformity

2.5.3. Mass productive high temperature etching technology for high dense FeRAM

Dry etching techniques are used for the patterning of FeRAM device. It is difficult to etch
the material of FeRAM such as the noble metal and PZT, because these have low reactivity
384 Advances in Ferroelectrics

with halogen gas plasma and these halides have low vapor pressure. The photo-resist is
used as etching mask for the patterning of FeRAM memory cell. But the etching selectivity
to photo-resist is low. Therefore the etching profile becomes low taper angle. Since FeRAM
device shrinks down recently(0.35-μm-design rule or lower), high temperature etching was
developed for high density FeRAM device. Furthermore, FeRAM device changed to the
stack structure from planer structure. At that time, the top electrode, PZT and the bottom
electrode are etched in a series by using of hard-mask (Fig. 18). [16]

Figure 18. Necessity of high-temperature etch

This section explains high temperature etching system ULHITE series made by ULVAC, Inc.
This etching module is equipped with ISM plasma source. Most important feature is the
novel electro-static-chuck (ESC) type hot plate stage at a temperature up to 450°C, and this
stage can be supplied high bias power. The process chamber, variable conductance valve,
pumps and gas exhaust are heated up. The deposition shields equipped in process chamber
are also heated up to 200°C. The effect is reducing the deposition during the etch process,
and high process stability is achieved.

Fig. 19 shows repeatability of Ir etching time for 300-wafers running test. The plasma clean‐
ing were carried out in every 25-wafers. Excellent stability was confirmed. For next genera‐
tion FeRAM devices, the continuous etching among the top electrode, ferroelectrics and
bottom electrode by use of one mask is need. And the high taper angle and no sidewall dep‐
osition are needed for etching process.

Fig. 20 shows the results of FeRAM capacitor etching of stack structure dependence of the
stage temperature. The halogen gases were used in etching process. Thus the higher profile
can be obtained by higher stage temperature. Fig. 21 shows repeatability of etching profile
for 300-wafers running test. Excellent repeatability of etching profile was confirmed.
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Figure 19. Repeatability of Ir etching time for 300-wafers running test

Figure 20. Stage temperature dependency of taper angle ( (a) 300°C, (b) 400°C)

Usually, high density device is required for non-volatile memory. Therefore the high tem‐
perature etching technique contributes to realize the next generation FeRAM devices pro‐
duction.

3. Technology for MEMS application

3.1. Sputtered PZT piezoelectric films for MEMS application

A multi-chamber type mass production sputtering systems for electronic devices SME-200
equipped with an exclusive sputtering module described above. PZT films have been depos‐
ited on 6 inch diameter silicon substrates.
386 Advances in Ferroelectrics

Figure 21. Repeatability of etching profile for 300-wafers running test

The platinum bottom electrodes, whose orientation is (111), were deposited on the substrate.
The PZT films were deposited under Ar/O2 mixed gas atmosphere of 0.5 Pa. Substrate temper‐
ature was heated up to around 550°C. After the deposition, PZT films were conducted with no
thermal treatments such as post-annealing. PZT films were deposited with relatively high
growth rate about 2.1 μm/h and these thicknesses were from 0.5 to 3.0 μm in consideration of
piezoelectric MEMS applications. The ceramic target with Zr/Ti ratio of 52/48, in which 30 mol
% excess PbO was added for the compensation of the lead re-evaporation from the films, was
used in order to obtain PZT films near the stoichiometric composition. After the PZT deposi‐
tion, top electrode 100-nm-thick Pt was deposited by the dc sputtering method.
For the measurement of the piezoelectric properties of the PZT films, Rectangular beams
(cantilevers) with the size of about 30 mm (3 cm) × 3 mm were prepared. Polarization and
displacement in these films were simultaneously observed using the laser doppler vibrome‐
ter (Graphtec AT-3600) and the laser interferometer (Graphtec AT-0023) which were attach‐
ed to a ferroelectric test system.
Fig. 22 shows relationship between Pb composition, deposition rate and repeatability. As a
result, stable transition of Pb content within film in continuous sputtering has been con‐
firmed. As can be seen from the figure, the change in the deposition rate was 2.1 μm±1.4%,
and changing Pb composition was 1.0±0.1% in the short running for 35 pieces (total thick‐
ness; 105 μm).
Fig. 23 shows XRD patterns of as-sputtered PZT film. No pyrochlore phase can be confirmed
and the film appears to be almost perovskite phase with the preferred orientation to (001) or
(100). It confirmed that the uniformity of the crystalline property were good in 6 inch area.
In addition, the dielectric constant of these samples was measured as shown in Fig.24. As a
result, excellent properties with the dielectric constant over 1000 and its uniformity of ±4.7%
were confirmed.
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Figure 22. Relationship between Pb composition, deposition rate and repeatability

Figure 23. Crystallization uniformity of PZT films Deposited on 6-inches substrate

388 Advances in Ferroelectrics

Figure 24. Dielectric constant of PZT films deposited on 6 inch substrate

Piezoelectric properties were finally confirmed for PZT films by checking the cantilever as
shown in Fig. 25. Large piezoelectric coefficient from -60 to -120 pm/V was observed in our
PZT films.

Figure 25. Relationship between piezoelectric coefficient and PZT film thickness
 Thin-Film Process Technology for Ferroelectric Application 389
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3.2. Etching technology of PZT piezoelectric Films for MEMS application

Additionally etching technology for mass production is developed. Since high etching rate is
required in MEMS PZT process because of large PZT thickness, etching selectivity to the
bottom electrode(Pt) and uniformity are important. In Fig. 26 we show etching rate profile
of both electrode(Pt) and PZT film. It has been found that etching rate of Pt is smaller than
PZT over whole wafers, implying that Pt film is the role of an etch stop layer.

Figure 26. Etching rate and in-plane uniformity of Pt & PZT

Figure 27. SEM image of Pt/PZT etching profile

390 Advances in Ferroelectrics

Fig. 27 shows the SEM image after the piezoelectric element was etched and the resist mask
was removed. The film composition is Pt/PZT/Pt=100 nm/3 μm/100 nm, and the top Pt elec‐
trode and PZT were continuously etched by using a 5-μm-thick photo resist as a mask.
Chlorine and fluorine mixed gases are used for PZT etching. The etching shape (taper angle)
is about 65º, and nothing adhered to the pattern sidewalls. Despite 20% of over etching, the
bottom Pt electrode was hardly etched. This indicates that a high etching selectivity to Pt
was achieved. Fig. 28 shows the dependency of the etching rate and the taper angle on the
bias power. As the bias power increases, the etching rate increases linearly. When 400 W
was applied, the PZT etching rate of 190 nm/min. was achieved. The taper angle also in‐
creased gradually as the bias power increased.

Figure 28. Dependence of PZT etching rate and taper angle on the substrate bias power

Figure 29. Pt/PZT etching profile of ϕ50mm piezoelectric element array

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Fig. 29 shows a 50-μm-diameter actuator element array fabricated by dry etching. Fig. 30
shows that the remanent polarization (Pr value) of the piezoelectric thin-film actuator with a
3-μm-thick PZT film was 40.5-42.8 μC/cm2 and the coercive electric field (Ec value) was
44.5-46.0 kV/cm at an applied voltage of 30 V, and the characteristics without the dependen‐
cy on element size (30-300 μm diameter) were obtained. The damage to the PZT piezoelec‐
tric thin-film actuator caused by the dry etching is considered to be negligible. The
displacement of the PZT thin-film actuator was measured by contact-AFM. Fig.31 shows
that a displacement of about 4 nm was obtained at 3-μm-thick PZT film, 30-μm-diameter el‐
ement size, and an applied electric field of 100 kV/cm. It was clarified that the processing of
PZT piezoelectric thin-film actuators by dry etching is very effective.

Figure 30. Dependence of ferroelectric properties on piezoelectric actuator size

Figure 31. Ferroelectric and displacement properties of Pt/PZT/Pt element with 30mm diameter etching rate and tap‐
er angle on the substrate bias power
392 Advances in Ferroelectrics

PZT(002)/ (200)
PZT(001)/ (100)

PZT(001)/ (100)
PZT(002)/ (200)
Pt(111)

Pt(111)
Intensity (a.u)
Intensity (a.u)

Edge

Middle

Center
20 25 30 35 40 45 50 20 25 30 35 40 45 50
2theta (deg.) 2theta (deg.)
(Conventional process) (Improved process)

Figure 32. XRD Patterns of PZT film before and after improvement on 8inch Pt/Ti/SiO2/Si Substrate

3.3. Further development for MEMS application

We also note that post in-situ treatment [17] has been recently established, aiming to im‐
prove crystalline property and piezoelectric coefficient in our PZT films. Fig. 32 shows the
results before and after improvement of crystalline properties. Peak intensity of a/c axis of
PZT film deposited by improved process is approximately two times higher of peak intensi‐
ty of PZT film deposited by conventional process uniformity over 8 inch wafers. As a conse‐
quence good piezoelectric coefficient (12.9C/m2) and large breakdown voltage (68V) were
obtained for PZT film deposited by improved sputtering process in Fig 33.

Figure 33. Improvement of piezoelectric coefficient(Left) and break down voltage(Right)

 Thin-Film Process Technology for Ferroelectric Application 393
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Good piezoelectric performance which is based on mass production technology including

excellent in-plane uniformity and process rate of sputtering and etching was obtained in
above evaluation.

3.4. Sputtered BST thin-films for capacitor and RF tunable devices

(Ba,Sr)TiO3 (BST) is expected to use as the thin film capacitor, RF tunable component [18, 19]
on-chip capacitor [20] for its excellent dielectric behavior. In these applications, decoupling,
high permittivity and high tunability are required as dielectric characteristics. High permit‐
tivity is thought to be primarily important character as dielectric characteristics. BST thin
films have been deposited by some deposition techniques. Among these techniques, RF
magnetron sputtering is thought to be suitable for mass-production because of its stability
and reproducibility as well as good film performances. In this section, BST films deposition
by RF magnetron sputtering and an approach to deposit BST films with higher permittivity
were described.

BST films were also deposited by an RF magnetron sputtering method using sintered BST
ceramic targets. Basic sputtering conditions such as RF power, deposition temperature and
so on were varied. As a top electrode, Pt dot with 0.5 mm in diameter was deposited by DC
magnetron sputtering. After top electrode deposition, BST capacitors were post-annealed for
1 hour in oxygen atmosphere under 1 atm using resistive heat furnace.

Fundamental properties of BST thin films such as dielectric constant, crystalline quality
(XRD), surface morphology (SEM) were investigated. Agilent 4284A LCR meter was used
for dielectric properties measurement and measuring cycle and volts alternating current
were 1 kHz and 1 Vrms, respectively.

Figure 34. Relationship between dielectric constant and deposition temperature

The relationship between dielectric constant and deposition temperature was investigated
as shown in Fig. 34. Ba/Sr ratio of BST target was 50/50. RF power was 1500 W. Ar/O2 flow
394 Advances in Ferroelectrics

ratio was 3. Sputtering pressure was 2.0 Pa. BST film thickness was 100 nm. As a result, dep‐
osition rate was 4.8 nm/min and almost constant irrespective of deposition temperature. As
can be seen in this figure, dielectric constant is strongly dependent on deposition tempera‐
ture and increasing with deposition temperature increasing. XRD patterns of these films are
also shown in Fig. 35. We can see in this figure, BST grains are randomly orientated and
XRD peak intensities from BST films are increasing with deposition temperature increasing.
So, it is thought that this represents the relationship between dielectric constant and deposi‐
tion temperature.

Figure 35. Relationship between XRD pattern and deposition temperature

Figure 36. Relationship between dielectric constant, deposition rate and RF power temperature
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The relationship between dielectric constant, deposition rate and RF power is shown in Fig.
36. Deposition temperature was 650°C in this relationship, while other conditions were not
changed. We can see in this figure, there is trade-off relationship between dielectric constant
and deposition rate and higher dielectric constant can be obtained at low sputtering power of
500 W in this experiment. BST morphology (SEM photographs) dependence on RF power is
also shown in Fig. 37. As can be seen in this figure, BST film deposited at 500 W (b) has dense
and uniform columnar structure. Possibly it represents some relationship between dielectric
constant and RF power. It is speculated that there is a long time for atomic migration and the
growth of BST crystal is encouraged under such low deposition rate around 1 nm/min.

Figure 37. BST morphology dependence on RF power

Figure 38. Relationship between dielectric constant and BST film thickness

Furthermore, the relationship between dielectric constant and BST film thickness is shown
in Fig. 38. Ba/Sr ratio of BST target was 70/30 in this experiment. Deposition temperature
was varied from 700°C to 800°C as a parameter, while other conditions were not changed.
396 Advances in Ferroelectrics

We can see in this figure, dielectric constant is also strongly and non-linearly dependent on
BST film thickness.

If BST capacitor is assumed to be a simple series connected capacitor between transition layer
near BST/Pt bottom electrode interface and main layer which represents BST film excluding
transition layer, it is speculated that there have been the transition layer in this BST film. [21]

As a simple experiment, effects of gas flow sequence for BST deposition was investigated.
Gas flow sequence, that is ON/OFF step was changed, while Ar/O2 flow ratio was not
changed. Dielectric constant was improved by introducing of oxygen gas before BST deposi‐
tion. It is speculated in this experiment that BST/Pt interface was improved because the oxy‐
gen vacancies of BST in this region were reduced. Therefore, dielectric properties are
noticeably influenced by gas flow sequencing variation.

4. Technology for ferroelectric probe memory

Technology for ferroelectric probe memory was developed with the deposition technology
for FeRAM manufacturing. Hard-disk using the magnetic recording is the one of the major
storage device, but the recording density will reach the limit in the near future by exteriori‐
zation of the magnetization disappearance by the heat disturbance. Ferroelectric probe
memory is ultrahigh-density memory applied Scanning Probe Microscope (SPM) and ferro‐
electric property.

Ferroelectric perovskite Pb(Zr, Ti)O3 (PZT) is polarized by electric field. For scanning probe
memory device, ferroelectric layer required atomically-smooth surface and low leakage cur‐
rent to achieve large recording density by forming polarized domains as unit cell size. There‐
fore it is necessary to grow the epitaxial ferroelectric thin films oriented to c-axis direction.

In this time we prepared epitaxial growth PZT/ SrRuO3 (SRO) thin films on single crystal
SrTiO3 (STO) substrate for probe memory device, and evaluated the film properties and the
recording density with Piezoresponse force microscopy (PFM). The SRO films were deposit‐
ed on STO (100) single crystal substrate with DC sputtering. After that, the PZT film was
deposited by MOCVD process.

Fig. 39 shows the AFM image of PZT / SRO / STO deposited at the optimal Pb flux. The sur‐
face morphology of PZT has step structure and smooth terraces similar to SRO/STO sub‐
strate before PZT deposition. This surface profile indicates layer-by-layer growth of PZT on
SRO / STO substrate [22] [23] [24]. Fig. 40 shows XRD spectrum of PZT deposited at Pb flux
of 0.160ml/min. There are only PZT, SRO and STO peaks. The fringe pattern appears around
PZT (001) and (002) peaks because of the smooth interface between PZT and SRO. Full-
width at half-maximum (FWHM) of PZT (002) with X-ray rocking curve is 0.129degree for
optimal Pb flux of 0.160ml/min. Rms of surface roughness and PZT(002) FWHM of X-ray
rocking curve have a similar trend relative to Pb flux.
 Thin-Film Process Technology for Ferroelectric Application 397
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Figure 39. AFM image of PZT at Pb flux of 0.160ml/min (Scanning range is 2um square)

STO 200
1.E+07
STO 100

SRO 200
SRO 100

1.E+06
PZT 001

PZT 002
XRD Intensity [cps.]

1.E+05

1.E+04

1.E+03

1.E+02

1.E+01

1.E+00
15 20 25 30 35 40 45 50 55
2theta [deg.]

Figure 40. XRD spectrum of PZT / SRO /STO

Figure 41. Writing Voltage & Writing Time Dependency of Dot diameter – [Small diameter (22nm) of recording-dot
was obtained for 5V & 1ms writing condition. (PZT/SRO/c-STO)  Estimated Recording density: 1.4Tbit/inch2. ]
398 Advances in Ferroelectrics

PFM measurement is carried out with various biases between 4V and 8V and pulse widths
between 1msec and 100msec with PtIr5 coatedprobe (tip diameter is 25nm). Fig. 41 shows
PFM write-condition and PFM image of the result. Polarization-inverted dot diameter has a
minimum of 20nm at the bias of 5V and pulse width of 1msec. Recording density is estimat‐
ed on the assumption that this tiny dot is arrayed with pitch of 20nm. From the calculation
result, device sample deposited under the optimal growth condition achieves large bit den‐
sity of 1.4Tb/inch2.

5. Conclusion

We have been developing thin film process technologies for ferroelectric application of ad‐
vanced semiconductor and electronics usage for 20 years or more, and completed the ferro‐
electric thin film solutions (sputtering, MOCVD, and etching) that became a de facto
standard. These technologies will support a wide variety of convenient energy-saving devi‐
ces such as FeRAM, MEMS production (actuators composing gyro meters, portable camera
modules for smart phone applications, tunable devices and so on), and ultra-high density
probe memory.

Author details

Koukou Suu

Institute of Semiconductor and Electronics Technologies, ULVAC, Inc., Shizuoka, Japan

References

[1] K. Suu, A. Osawa, N. Tani, M. Ishikawa, K. Nakamura, T. Ozawa, K. Sameshima, A.

Kamisawa and H. Takasu: Jpn. J. Appl. Phys. 35 (1996) 4967.
[2] K. Suu, A. Osawa, N. Tani, M. Ishikawa, K. Nakamura, T. Ozawa, K. Sameshima, A.
Kamisawa and H. Takasu: Integr. Ferroelectr. 14 (1997) 59.
[3] K. Suu, A. Osawa, Y. Nishioka and N. Tani: Jpn. J. Appl. Phys. 36 (1997) 5789.
[4] K. Suu, Y. Nishioka, A. Osawa and N. Tani: Oyo Buturi 65 (1996) 1248. (in Japanese)
[5] K. Suu: Proc. Semicon Korea Tech. Symp., 1998 p. 255.
[6] N. Inoue, Y. Maejima and Y. Hayashi: Int. Electron Device Meet. Tech. Dig., 1997 p.
605.
[7] N. Inoue, T. Takeuchi and Y. Hayashi: Int. Electron Device Meet. Tech. Dig., 1998 p.
819.
 Thin-Film Process Technology for Ferroelectric Application 399
http://dx.doi.org/10.5772/54360

[8] F. Chu, G. Fox, T. Davenport, Y. Miyaguchi and K. Suu: Integr. Ferroelectr. 48 (2002)
161.

[9] T. Yamada, T. Masuda, M. Kajinuma, H. Uchida, M. Uematsu, K. Suu and M. Ishika‐

wa : IFFF2002 abstract, 4 (2002) 37.

[10] T. Masuda, M. Kajinuma, T. Yamada, H. Uchida, M.Uematsu, K. Suu and M. Ishika‐

wa : Integr. Ferroelectr., 46 (2002) 66

[11] Y. Nishioka, T. Jinbo, T. Yamada, T. Masuda, M. Kajinuma, M. Uematsu, K. Suu and

M. Ishikawa: Integr. Ferroelectr., 59 (2003) 1445

[12] Y. Nishioka, T. Masuda, M. Kajinuma, T. Yamada, M. Uematsu and K. Suu: MRS Fall
Meeting Proceedings, 784-C7 (2003) 6

[13] K. Zheng, J. Lu, and J. Chu: Jpn. J. Appl. Phys. 43 (2004) 3934.

[14] Y. Kokaze, M. Endo, M. Ueda, and K. Suu: 17th Int. Symp. Integrated Ferroelectrics,
2005, 5-26-P.

[15] Y. Kokaze, I Kimura, M. Endo, M. Ueda, S. Kikuchi, Y. Nishioka, and K. Suu: Jpn. J.
Appl. Phys. 46 (2007) 282.

[16] M. Endo, M. Ueda, Y. Kokaze, M. Ozawa, T. Nakamura, K. Suu: SEMI Technology

Symposium 2002; December 5, 2002

[17] Suu et.al in preparation

[18] I. P. Koutsaroff, T. Bernacki, M. Zelner, A. Cervin-Layry, A. Kassam, P. Woo, L.

Woodward, A. Patel, Mat. Res. Soc. Symp. Proc. Vol. 762, C5.8.1 (2003).

[19] X. H. Zhu, J. M. Zhu, S. H. Zhou, Z. G. Liu, N. B. Ming, S. G. Lu, H. L. W. Chen, C. L.

Choy, Journal of Electronic Materials, 32 (2003) 1125.

[20] M. C. Werner, I. Banerjee, P. C. McIntyre, N. Tani, M. Tanimura, Appl. Phys. Lett., 77

(2000) 1209.

[21] T. Jimbo, I. Kimura, Y. Nishioka and K. Suu, Mat. Res. Soc. Symp. Proc. Vol. 784,
C7.8.1 (2003).

[22] P.-E. Janolin, B. Fraisse, F. Le Marrec, and B. Dkhil, Appl. Phys. Lett. 90, 212904
(2007)

[23] Keisuke Saito, Toshiyuki Kurosawa, Takao Akai, Shintaro Yokoyama, Hitoshi Morio‐
ka, Takahiro Oikawa, and Hiroshi Funakubo, Mater. Res. Soc. Symp. Proc. 748,
U13.4.1-U13.4.6 (2003).

[24] H. Hu, C. J. Peng and S. B. Krupanidhi, Thin Solid Films, 223 (1993) 327 333I. G. Baek,
et al,: Tech. Dig. Int. Electron Devices Meet., San Francisco, 2004, 23, 6, p58
 Provisional chapter
Chapter 18

Ferroelectrics at the Nanoscale: A First Principle

Ferroelectrics at the Nanoscale: A First Principle
Approach
Approach
Matías Núñez

Matías Núñez
Additional information is available at the end of the chapter

Additional information is available at the end of the chapter

10.5772/52268

http://dx.doi.org/10.5772/52268

1. Introduction
The field of ferroelectric materials is driven by its possible use in various micro-electronic
devices that take advantage of their multifunctional properties. The existence of a switchable
spontaneous polarization (see Figure 1) is at the basis of the design of non volatile
ferroelectric random access memories (FERAMs), where one bit of information can be
stored by assigning one value of the Boolean algebra ("1" or "0") to each of the polarization
states. Also, the high dielectric permitivity of ferroelectrics makes them possible candidates
to replace silica as the gate dielectric in metal-oxide-semiconductor field effect transistors
(MOSFETs). Their piezoelectric behavior enables them to convert mechanical energy in
electrical energy and vice versa. Their pyroelectric properties are the basis for highly sensitive
infrared room temperature detectors.
The current miniaturization of microelectronic technology, imposed by the semiconductor
industry, raises the question of possible size effects on the properties of the components.
Except for the case of the gate dielectric problem in MOSFET’s, the thickness of the films
used in contemporary applications is still far away from the thickness range where size effects
become a concern; therefore the question at the moment is merely academic. Nevertheless,
it is very possible that the fundamental limits of materials might be reached in the future.
Despite the efforts and advancement in the field, both theoretically and experimentally (see
a recent review in Ref.[1]), many questions still remain open. The main reason for the poor
understanding of some of the size effects on ferroelectricity is the vast amount of different
effects that compete and might modify the delicate balance between long range dipole-dipole
electrostatic interactions and the short range forces, whose subtle equilibrium is known to be
at the origin of the ferroelectric instability.

©2012 Núñez, licensee InTech. This is an open access chapter distributed under the terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
© 2012 Núñez;
distribution, licensee InTech.
and reproduction Thismedium,
in any is an open accessthe
provided article distributed
original work is under thecited.
properly terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
402 Advances in Ferroelectrics
2 Advances in Ferroelectrics

Figure 1. Tetragonal ferroelectric structure of BaTiO3 . Solid, shaded and empty circles represent Ba, Ti, O atoms, respectively.
The arrows indicate the atomic displacements, exaggerated for clarity. The origin has been kept at the Ba site. Two structures,
with polarization along [001], are shown. Application of a sufficiently large electric field causes the system to switch between
the two states, reversing the polarization. in principle, we can assign one value of the Boolean algebra ("1" or "0") to each of
the polarization states.

The next section will give an overview of the main concepts involved in the modern theory
of polarization. A definition of a local polarization will be given in terms of the centers of
the wannier functions associated with the band structure of the system. Next, some basic
electrostatic notions related with ferroelectric films will be given, in particular the concept
of depolarization field and screening by metal contacts. Finally, the results of this research
work: applying the layer polarization concept, where we show the hidden structure of the
polarization at the nanoscale.

2. Modern theory of polarization

Classically, the macroscopic polarization in dielectric media is defined to be an intensive
quantity that quantifies the electric dipole moment per unit volume [2–4]. Definitions along
these lines work well for finite systems but have important conceptual problems when
applied to periodic crystalline systems because there is no unique choice of cell boundaries
[5].
In the early 1990s a new viewpoint emerged and lead to the development of a microscopic
theory [6–8]. It starts by recognizing that the bulk macroscopic polarization cannot be
determined, not even in principle, from a knowledge of the periodic charge distribution
of the polarized crystalline material. This establishes a fundamental difference between
finite systems (e.g., molecules, clusters, etc.) and infinite periodic ones. For the first case,
the dipole moment can be easily expressed in terms of the charge distribution. While for
periodic systems one focuses on differences in polarization between two states of the crystal
that can be connected by an adiabatic switching process [6]. The polarization difference is
then equal to the integrated transient macroscopic current that flows through the sample
during the switching process.
Therefore, the macroscopic polarization of an extended system is, according to the modern
viewpoint, a dynamical property of the current in the adiabatic limit. The charge density
is a property connected with the square modulus of the wavefunction, while the current
also has a dependence on the phase. Indeed, it turns out that in the modern theory of
polarization [7–9], the polarization difference is related to the Berry phase [10, 11], defined
over the manifold of Bloch orbitals. The theory not only defines what polarization really is,
 Ferroelectrics at the Nanoscale: A First Principle Approach 403
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but also proposes a powerful algorithm for computing macroscopic polarizations from first
principles.
The modern theory can be equivalently reformulated using localized Wannier functions
[12–15] instead of extended Bloch orbitals. The electronic contribution to the macroscopic
polarization P is then expressed in terms of the dipole of the Wannier charge distribution
associated with one unit cell. In this way, P is reformulated as a property of a localized
charge distribution which goes back to the classic definition of polarization. However, one
has to bear in mind that the phases of the Bloch orbitals are essential for building the
Wannier functions. They are needed to specify how the periodic charge distribution should
be decomposed into localized ones. The knowledge of the periodic charge distribution of the
polarized dielectric is not enough to determine the wannier functions.

The main concepts

Here I will review the central topics uncovered in the early 1990s, often known as the modern
theory of polarization. Understanding this background is necessary in order follow this
chapter. The general idea is to consider the change in polarization of a crystal as it undergoes
a slow change and relate this to the current that flows during this adiabatic evolution of the
system. These ideas will lead to an expression for the polarization that does not take the
form of an expectation value of an operator, but takes the form of a Berry phase, which is
a geometrical phase property of a closed manifold (the Brillouin zone) on which a set of
vectors, the occupied Bloch states, are defined.
As a classical example of a Berry phase, lett’s think of the paralel transport of a vector
along a loop on a shpere ( for instance a compass needle carried in a car traveling on the
surface of the Earth). After completing a closed path, or loop, the vector will be back at the
original starting point but it will be rotated with respect to the direction it was pointing at
when it started the trip. The reason for this rotation is purely geometrical topological and
intrinsicaly connected to the curvature of the sphere and would not exist if the the vector
would be parallel transported along a flat manyfold, like a plane, or cylinder. This rotation
angle is related to the integral of the curvature on the surface bounded by the loop.
Now lets see the quantum counterpart and its connection to the definition of Polarization
in a solid. Let’s assume that the crystal Hamiltonian Hλ depends smoothly on parameter
λ and has Bloch eigenvectors obeying Hλ |ψλ,nk i = Eλ,nk |ψλ,nk i and that λ changes slowly
with time, so that it is correct to use the adiabatic approximation.
  
Since the spatially averaged current density is just j = dP dt =
dP
dλ
dλ
dt we can write the
change in polarization during some time interval as

Z
△P = j(t)dt (1)

and is phrased in terms of the current density that is physically flowing through the crystal
as the systems traverses some adiabatic path. It can also be written in terms of the parameter
λ as:
404 Advances in Ferroelectrics
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Z
dP
△P = dλ. (2)
dλ

Then, from Ref.[7]

Z
dP ie dunk
dλ
=
(2π )3 ∑ BZ
dkh∇k unk |
dλ
i + c.c. (3)
n

and the rate of change of polarization with λ is a property of the occupied bands only. This
expression can be integrated with respect to λ to obtain

Z
ie
P( λ ) =
(2π )3 ∑ BZ
dkhuλ,nk |∇k |uλ,nk i. (4)
n

It can be verified by taking the λ derivative of both sides of Eq.4 and comparing with Eq.3.
The result is independent of the particular path of λ(t) in time, and depends only on the final
value of λ as long the change is adiabatically slow. We can associate the physical polarization
of state λ with P(λ) and drop the λ label. Eq. 4 can be written then as

Z
e
P= Im ∑ dkhunk |∇k |unk i, (5)
(2π )3 n BZ

and this is the electronic contribution to the polarization. To obtain the total polarization it
must be added the nuclear (or ionic) contribution

1
Pion =
Ω ∑ Zs rs ,
s

where the sum is over atoms s having core charge Zs and spatial position rs in the unit cell
of volume Ω.
The equation 5 is the main result of the modern theory of polarization It states that the
electronic contribution to the polarization of crystalline insulator may be expressed as a
Brillouin zone integral of an operator i ∇k . However, it is not a common quantum mechanical
operator, the result of its action on the wavefunctions (i ∇k |unk i) depends on the relative
phases of the Bloch functions at different k.
To understand the nature of the integrand in Eq.5 I want to recall the fundamental paper by
Zak [16] in which he postulates the existence of a Berry phase associated with each one of
the bands of a one dimensional crystalline solid. He shows how the variation of k over the
entire Brillouin zone produces the appearance of a Berry phase. Moreover, he associates this
phase, that is a characteristic feature of the whole band, with the band center operator [17].
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Figure 2. From Ref.[18] Mapping of the distributed charge density onto the centers of charge of the Wannier functions.

Its eigenvalues turn out to give the average positions of an electron in different bands which
coincide with the symmetry centers of the space group of the solid [17] These previous ideas
set the stage for the crucial meaning of the expression in Eq.5.
In three dimensions, the Brillouin zone can be regarded as a closed 3-torus obtained by the
identifying points unk = un,k+Gj where G j are the three primitive reciprocal lattice vectors.
Then, the electronic polarization contribution of each band can be written as

−e
Pn =
2πΩ ∑ Φnj Rj (6)
j

where R j is the real space primitive translational corresponding to G j , and the Berry phase
for band n in direction j is

Z
Ω
Φnj = − Im d3 khunk |G j .∇k |unk i. (7)
(2π )3 BZ

More details and discussion, including the equivalent of Eq.7 for the case of connected
multiple bands, may be found in Refs.[7] and [8].

Reformulation in terms of Wannier Functions.

We can rewrite Eq.5 in terms of the Wannier functions (WF’s), which brings an alternative
and more intuitive way of thinking about it. The WF’s and Bloch functions can be regarded
as two different orthonormal representations of the same occupied Hilbert space. The WF’s
are localized functions wnR (r) that are labeled by band n and unit cell R and constructed
by carrying out a unitary transformation of the Bloch states ψnk . They are constructed via a
Fourier transform of the form

Z
Ω
|wnR i = dkeik.R |ψnk i (8)
(2π )3 BZ
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where the Bloch states are normalized in one unit cell. There is some freedom in the choice
of the these WF’s, as the transformation is not unique. In particular, a set of Bloch functions

|ψnk′ i = e−iβ n (k) |ψnk i (9)

results in WF’s wnR′ which are different from the wnR . Usually, this "gauge" is set by some
criterion that keeps the WF’s well localized in real space, such as the minimum quadratic
spread criterion introduced by Marzari and Vanderbilt [19]. However, it is expected that any
physical quantity, such as the electronic polarization arising from band n, should be invariant
with respect to the phase change β n (k).
Once we have obtained the WF’s, we can locate the "wannier centers" rnR = hwnR |r|wnR i. It
can be shown that
φnj
rnR = R + ∑ Rj , (10)
j
2π

where φnj is given by Eq.7. In simple words, the location of the n’th Wannier center in the
unit cell is just given by the three Berry phases φnj of band n in the primitive lattice vector
directions R j . The key result, is that the polarization is just related to the Wannier centers by

e
P=−
Ω ∑ rnO . (11)
n

The Berry Phase theory can then be regarded as providing a mapping of the distributed
quantum mechanical electronic charge density onto a lattice of negative point charges −e
(see Fig.2).

3. Layer polarization definition

One issue that has received much attention theoretically is how to quantify the concept of
local polarization. This can be very useful in understanding the enhancement or suppression
of spontaneous polarization; or even to find new spatial patterns of polarization that would
remain hidden otherwise, as is the case that I will show in a following section. It can also be
essential for characterizing and understanding interface contributions to such properties.
But first I will give a review of the concept introduced in 2006 by Wu.et al. [20] which is
the one used here. As explained in the previous section, the modern theory of polarization
establishes that the polarization of a crystal is expressed in the Wannier representation as the
contribution of the ionic and electronic charge:

1 2e
P=
Ω ∑ Q s Rs − Ω ∑ rm , (12)
s m
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where s and m run over ion cores (of charge Qs located at Rs ) and Wannier centers (of charge
-2e located at rm ), respectively, in the unit cell of volume Ω.
They defined the Layer polarization (LP) along z for superlattices built from II-VI ABO3
perovskites such as BaTiO3 , SrTiO3 , and PbTiO3 . For these cases, they were able to
decompose the system into neutral layers (that is AO and BO2 subunits) and define a layer
polarization

1 2e
pj = ∑
S s∈ j
Qs Rsz −
Ω m∑
zm , (13)
∈j

in which the sums are restricted to entities belonging to layer j. S is the basal cell area and we
are now focusing only on z components. The LP p j thus defined has units of dipole moment
per unit area. The total polarization, with units of dipole moment per volume, is exactly
related to the sum of LP’s via

1
Pz =
c ∑ pj (14)
j

Ω
where c = S is the supercell lattice constant along z.
They propose two conditions to be able to associate a physical meaning to the LP definition:
(i) resolve the arbitrariness associated with the positions of the Wannier centers, and (ii)
associate without ambiguity the right number of Wannier centers to each layer.
As it will be shown in the next section, we applied this concept to thin ferroelectric films
sandwiched between metal contacts. These kind of systems, in which metals and oxides
coexist, bring new challenges. Condition (i) was satisfied using maximally localized wannier
functions plus a disentanglement procedure (Ref.[21]) and (ii) was satisfied, even close to the
metal oxide interfaces.

4. Depolarization field
When dealing with ferroelectric thin films, a finite polarization normal to the surface will
give rise to a depolarizing field and a huge amount of electrostatic energy, enough to be able
to suppress the ferroelectric instability. In order to preserve ferroelectricity and minimize the
total energy, the depolarization field must be screened, either by free charges coming from
metallic electrodes or by breaking into a domain structure. I will go into more details about
this, but first a basic electrostatic background will be given.

Influence of the electrical boundary conditions

In the case of a free standing slab of a ferroelectric material, a uniform polarization P with
an out of plane direction will appear and originate a surface polarization charge density
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Figure 3. Schematic representation of the planar averaged electrostatic potential (fill line) of a slab with polarization
perpendicular to the surface under (a)D = 0 boundary conditions (vanishing external field) and b) a vanishing internal electric
field E = 0. Plannar averages are taken on the ( x, y) planes parallel to the surface. Dashed lines represent an average over unit
cell of the planar averages. An estimate of the macroscopic internal field inside the slab can be obtained from their slope. m
stands for the dipole moment parallel to the surface normal and e for the electron charge. From Ref.[23]

σpol = P.b
n, (15)

where n b is a unit vector normal to the surface pointing outward. The charge density
is proportional to the magnitude of the normal component of the polarization inside the
material [22] and is positive one one side of the slab and negative on the other one. In order
the determine the electric fields generated by the surface charge density, we need to know
the electrical boundary conditions of the problem and solve the Poisson equation. For the
general case, let’s suppose that an external electric field Eext , perpendicular to the surface,
is applied in the vacuum region. There, the electric displacement D = E + 4πP equals the
applied electrical field D = Eext as the polarization is zero. The normal component of D is
conserved across the ferroelectric/vacuum interface,

E + 4πP = Eext (16)

Now we can see two extreme cases. One of them is that of zero external electric field,
Eext = 0, in which case the displacement vector is null while the internal field inside the slab
is E = −4πP (see Fig.3a). The absence of an external electric field and the presence of the
surface polarization charges produce an internal field that points in the direction opposite
to that of the polarization. Therefore, it tends to restore the paraelectric configuration and
that is the reason of its name, Depolarization field. The coupling between the polarization and
this internal field is so big, that any atomic relaxation under these circumstances will end up
with the atoms back in the centrosymmetric non polar configuration.
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Figure 4. Depolarization field for an isolated free standing slab in the absence of an external electric field (a), and for a
ferroelectric capacitor with perfect screening (ideal metal) (b) and a real metallic electrode (c) under short circuit boundary
conditions. From Ref.[1]

Another case, a vanishing internal electric field E = 0 corresponds to a case where no field
opposes the polarization and a spontaneous polarization might arise (Fig.3b). In this case, it
is the continuity of the normal component electric displacement vector that establishes the
value of it,

Eext = 4πPs . (17)

These two cases illustrate how a polarization perpendicular to the surfaces can exist or
not depending on the electrical boundary conditions. For simulating a real system, the
mechanical boundary conditions should be included via atomic relaxations. These cases have
been extensively analyzed [23–26] and have opened the ground for more realistic systems..

Metal contacts
The next level of approximation to a real case,is the case of having the ferroelectric thin film
sandwiched between metal contacts ( short circuit boundary conditions). In the case of a
perfect metal, the surface charges σpol will be exactly compensated at the interfaces by the
compensation charges σcom and we will have a null depolarization field (see Fig.4b). In this
case, both σ′ s will lie in a sheet right at the interface between the metal and the ferroelectric
electrode. However, in the case of real electrodes, the compensation of the polarization charges
will be incomplete. In this case,the compensation charge σcom will be spread over a finite
distance inside the electrode and will create an interface dipole density at each of the
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ferroelectric/metal interfaces (see Fig.4c). Due to the short circuit boundary conditions, an
amount of charge must flow from one interface to the other, creating a residual depolarization
field inside the thin film. There are various models for expressing this field [24, 27–29], shown
below is one described in Ref.[30]:

8πPλ
Edep = − (18)
d

where d is the film length, and λ is the effective screening length, proportional to the spatial
spread of the interface dipole.

Electrostatic energy of the thin film

In the presence of a residual depolarizing field the energy of the thin film U can be
approximated by

E ( P0 ) = U ( P0 ) + Eelec ( P0 ) , (19)

where U is the internal energy under zero field. If we assume that the interface effects are
hidden in the screening length parameter, then they only appear through the depolarization
field. This is a rough approximation but we will introduce later a model that will relax this
condition, but let’s keep it for now. Following this, then

U ( P0 ) = mUFE ( P0 ) (20)

where m stands for the number of unit cells of the film. UFE can be calculated from bulk
DFT calculations. Its dependence on P0 has typically the shape of a double well.
The electrostatic energy Eelec ( P0 ) can be approximated by [1, 31]

   2
Eelec ( P0 ) = mΩ − Edep .P0 + O Edep (21)

The depolarization field can be calculated from first principles by taking the electrostatic
average [32, 33] or can be expressed using Eq.18. In this case, Eq.19 can be rewritten as

8πλP02  
E ( P0 ) = U ( P0 ) + + O P04 . (22)
d

The electrostatic energy, the second term, is positive, meaning that the effect of the
depolarization field is to suppress the ferroelectric instability by rescaling the quadratic term
of the double well. This simple model has been implemented [34, 35] in order to extend the
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Figure 5. Evolution of the c/a ratio with the film thickness for monodomain PbTiO3 films grown epitaxially on top of Nb-doped
SrTiO3 . With circles and squares, the experimental results. The dashed line is the phenomenological theory prediction. Solid
lines correspond to the first principles model Hamiltonian results. From Ref. [35].

Figure 6. Theoretical predictions of the thickness dependence of the normal average polarization P, the tetragonality c/a, and
the out of plane piezoelectric constant d33 at room temperature for PbTiO3 thin films grown on a SrRuO3 /SrTiO3 substrate.
Values of the quantities at the bulk level are represented by dashed lines for the unstrained configuration, and with dotted lines
for a geometry under the strain imposed by the substrate. The evolution of the system, from a monodomain configuration at
large thickness, (where the depolarization field Ed is small), to a 180◦ stripe domain structure in order to minimize the energy
associated with Ed , is represented in the inset. From [37]

first principle model Hamiltonian to thin films. It also has been used with the result of first
principle calculations in Ref.[30]. In this work, we will use it as a starting point for a toy
model that would mimic the result of our first principle calculations.

4.1. Effects of the depolarization field

There are two ways to minimize the energy due to the depolarization field , i) a reduction
of the polarization, ii) a reduction of the depolarization field itself. This can be seen by
inspecting the first term in Eq.21.
As an example of case i) it is shown in Fig.5 the experimental results for the tetragonality
in function of the film thickness for monodomain PbTiO3 epitaxially grown on Nb-doped
SrTiO3 [35]. The polarization is strongly coupled to strain in perovskites oxides [36],
therefore a reduction of the polarization must be accompanied by a reduction of the
tetragonality of the system. The incomplete screening of the depolarization field is the
driving force for the reduction of the polarization. The structure remains in a monodomain
at all thickness.
Case ii) might arise when there are no compensation charges provided by the electrodes
or when the compensation charges do not provide an efficient enough screening of the
polarization charges. In this case the system might break up into 180◦ stripe domains to
reduce the magnitude of the surface dipole density (see Fig.6).
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Figure 7. We simulated ferroelectric films at different thicknesses, sandwiched between metal contacts.

The reason why some systems remain in a monodomain configuration while other similar
heterostructure break up into domains remains an open question that requires further
clarification.
In a seminal theoretical paper, Junquera et al.[30] has suggested that the appearance of
ferroelectricity in thin films of BaTiO3 , with SrRuO3 contacts, should be limited to a
thicknesses of more than six unit cells. Below that limit, ferroelectricity would effectively
be canceled by the strength of the depolarization field (DF) inside the oxide produced by
unscreened charges at the interfaces, which, in that work, were calculated for the first time
in a first principles framework. More recently this picture has been broadened, and a variety
of studies have shown both experimentally and with more realistic ab initio simulations that
thin oxide films can indeed maintain some ferroelectricity at thicknesses even smaller than
six unit cells.[37–40]

5. The hidden nature of ferroelectricity at the nanoscale

The size limit of ferroelectricity in ultrathin films can be understood using a simple
electrostatics argument: as the thickness of the oxide film is reduced, the intensity of the DF
is made stronger,[30] thus increasing the electrostatic energy of the system. In a ferroelectric
crystal, this energy contribution can be minimized in two ways: either by breaking the
polarization pattern in 180o stripe domains [41–44] to reduce the magnitude of the surface
dipole density, or by a reduction of the ionic polarization while the system remains in a
monodomain state.[35, 45] The final polarization pattern depends on the individual material
and/or structure, and understanding which system modification will occur under what
conditions is still a matter of debate.
At small dimensions, the spatial confinement and the interface details become extremely
relevant since they determine the spatial localization of the electrons and thus influence
directly the ferroelectric characteristics and, more in general, all the electronic properties of
the system.[46] Therefore, to clarify the behavior of ferroelectric thin films in the nanometer
regime it is crucial to obtain a precise description not only of the geometry and electronic
properties of the film but first and foremost of the polarization profile inside the oxide.
In order to obtain a complete description of ferroelectricity at the nanoscale we have exploited
the notion of layer polarization (LP). This idea, based on modern theory of polarization and
the concept of maximally localized Wannier functions (see Sec.2), was recently introduced to
describe the layer-by-layer modulation of polarization in ferroelectric superlattices (Sec.3) .
We have applied this method to a model metal-ferroelectric system (BaTiO3 /Pt) (see Fig.7)
and obtained a detailed spatial profile of the polarization in the oxide region in the direction
of growth that accounts not only for the ionic displacements but also for the spatial
rearrangement of the electron density. It is important to note that using more standard
methods to evaluate macroscopic polarization, this information would have remained hidden
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Figure 8. The thin film oxide develops a ferrielectric [47] pattern of polarization that exhibits antiferroelectric properties along
the growth axis and with a net total polarization. This pattern would remain hidden by using more standard methods for
calculating the local polarization.

by the averaging procedure, or would have produced misleading results. In fact, by

considering exclusively the ionic displacements (rumpling) as a measure of polarization, we
do not account for the full electronic contributions to the local polarization and, depending
on the system size, we might obtain results that would not describe accurately the physical
behavior of the thin film.
Here, we show that the ferroelectric structures associated with small length-scales are more
complex than previously thought, mainly due to the redistribution of the electrons under
the constraints imposed by the interfaces. In particular, the oxide develops a ferrielectric
[47] pattern of polarization that exhibit antiferroelectric properties along the growth axis and
with a net total polarization (see Fig.8).
This unbalanced dipole structure is particularly evident in Fig.10A, where we show how
positive rumpling on all the atomic layers of a thin BaTiO3 film correspond actually to layer
dipoles of opposite signs. This is a consequence of the interplay between the orientation
and magnitude of the dipoles with the DF, their mutual interaction and the nature of the
interfaces. A simple analytic model of a ferroelectric thin film, where these effects are
explicitly taken into account, can capture all these features and it will be discussed in detail
at the end.
We have simulated thin films of BaTiO3 between Pt metal contacts in a (001) stack, where
the oxide is terminated with a BaO plane at both interfaces. In this configuration, the
metal atoms are directly bonded to the O atoms of the oxide plane.[30, 48] The different
supercell constructed in this way can be labeled as Pt/(BaO-TiO2)m-BaO/Pt with m=1,2,4,6.
Nine atomic planes of Pt have been found to be sufficient to simulate the contacts under
short-circuit boundary conditions. The in plane lattice constant of the supercell is set equal
to that of BaTiO3 at 0 K (3.991)[38], and kept it fixed in all calculations while all other
geometrical parameters (atomic positions and intra-layer distances) were fully relaxed. All
simulations have been performed using Density Functional Theory (DFT) within the Local
Density Approximation, with ultrasoft pseudopotentials and a plane waves basis set.
414 Advances in Ferroelectrics
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Figure 9. The set of MLWFs so obtained cluster around each atomic layer in sets containing the correct number of Wannier
function needed to keep the layer charge neutral. Here we can see the z position (horizontal lines lines ) of the centers of the
Wannier functions and the position of the ions (indicated with circles). To calculate the LP of each layer, we use Eq.12.

We used the expression of Eq.12 to calculate the LP for each plane of the thin film. A is the in
plane area of the cell, and we are only interested on the z components (parallel to the growth
direction). It is important to stress that in the definition of the LP we have explicitly included
the full ionic and electronic information necessary to define unambiguously the local value
of the polarization. The essential step for the evaluation of the layer polarizations p j is the
determination of the Wannier centers zm . We used the maximally localized Wannier functions
(MLWFs) algorithm originally proposed by Marzari and Vanderbilt[19] as implemented in
the WanT code1 . Since the valence bands of the oxide and the bands of the metal are mixed
in the full supercell calculation, a disentanglement procedure (Ref.[21]) was applied before
starting the localization algorithm[19, 49].
The set of MLWFs so obtained cluster around each atomic layer in sets containing the correct
number of Wannier function needed to keep the layer charge neutral (Fig.9). This is a crucial
condition for the validity of the definition of LP‘s in Eq.12 and might not be attainable
in systems with more covalent nature.[20] In fact, the meaningful use of this concept is
based on the condition of being able to decompose the system into neutral layers (TiO and
BaO2 units in the case of perovskite BaTiO3 ) and resolve the arbitrariness associated with the
positions of the Wannier centers. This allows us to associate each sets of Wannier centers to
the corresponding crystal plane without ambiguity. By doing so we go back to the classic
idea of defining dipoles in spatial neutral units, along the lines of the Clausius-Mossotti
limit.v Moreover, we can associate each LP value p j with its correspondent (dimensionally
correct) dipole p j A, which gives precise information about the orientation and magnitude of
the atomic layer dipoles inside the crystal.

1
code by A. Ferretti, B. Bonferroni, A. Calzolari, and M. Buongiorno Nardelli, (http://www.wannier-transport.org).
In the non-self-consistent calculation for obtaining the MLWFs we used MP k meshes 2x2xN with N=16,14,12,10 for
m=1,2,4,6 respectively. I. Souza, N. Marzari, and D. Vanderbilt, Phys. Rev. B 65, 035109 (2001). ote
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The LP profile calculated for the metal-oxide systems provides a detailed local description of
the polarization, which is superior and even contradictory to the information obtained from
empirical evaluations based solely on ionic displacements. As an illustration, in Fig.10A we
display the rumpling profile (cation-oxygen normal distance within each atomic layer.) for
a thin film comprised of six BaTiO3 unit cells (m6). From the ionic displacement profile
one would be tempted to conclude that the film is in a ferroelectric domain configuration,
since the rumpling values (and hence the classical local dipoles) associated to each plane are
positive. Instead, if the correspondent LP profile is analyzed, a completely different picture
emerges, where the main feature is an alternation of positive and negative values of the LP in
the individual atomic layers of the oxide film. This is clearly shown in Fig.10B, where we plot
the LPs values computed for m6. Here the central BaO planes (the BaO planes at the interface
behave differently and will be discussed later) have positive dipoles while the TiO2 planes
have negative ones. The first are aligned with the direction of the DF, while latter oppose it.
A schematic illustration of the associated dipoles is drawn above the plot. This result implies
that what could have been interpreted as a ferroelectric domain using standard geometrical
information, in fact displays a much more complex spatial pattern of polarization. We
believe that this effect is comparable to the onset of the formation of two-dimensional domain
islands commonly observed both theoretically and experimentally in ferroelectric films.[37]
In that case, the domains are composed of adjacent 180◦ domains in order to minimize
the electrostatic energy associated with the DF. Here, our results show that the system can
reduce its electrostatic energy in an alternative way: the energetic interplay between the
dipoles, the DF and the interface bonding drives the individual atomic layer dipoles to
arrange themselves in an uncompensated dipole pattern along the growth direction (see
inset of Fig.10A), or, in other words, the system undergoes a ferroelectric-to-ferrielectric
phase transition. Similarly to the formation of two-dimensional islands, we also predict
the existence of a critical thickness (CT) above which the system exists in a true ferroelectric
domain with all the dipoles pointing in the same direction (see Fig8B, where the LP‘s values
for bulk BaTiO3 are shown with triangles).
As the thickness is reduced, the magnitude of all the dipoles is diminished by the increase of
the DF that opposes them. Due to the different physical properties of consecutive layers (BaO
and TiO2), their associated dipoles reduce their magnitude at different rates. At the CT, the
BaO layers will have null dipoles and eventually they will flip layer polarization direction,
aligning with the DF in order to minimize the associated internal energy and creating a
ferrielectric dipole pattern (FDP).
The formation and characteristics of the FDP are determined by the bonding properties of the
interfaces that pin the LP values of the outer layers of the oxide film. At small film thicknesses
the interface effects become dominant and induce the overall spatial variation of the LP‘s that
determines the orientation and magnitude of the layer dipoles along the structure. We can
see how the FDP observed in the m6 geometry is increasingly influenced by the locality of the
interfaces as the thickness is reduced to m4, m2 and m1 (see Fig.10C,D,E respectively). The
middle crystal planes become more and more influenced by the interface environment, while
the FDP becomes irregular, and finally disappear when the film is comprised by just 3 layers
(i.e. one unit cell, m1), leaving instead a centro-symmetric paraelectric structure (Fig.10E). It
is important to note that exclusively electronic effects drive this series of regime transitions.
In fact, the ionic polarization, directly proportional to the ionic rumpling, remains almost
416 Advances in Ferroelectrics
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Figure 10. A. Rumpling (cation-oxygen perpendicular distance (in Å) within each atomic layer) profile for six unit cells (m6)
of BaTiO3 sandwiched between Pt contacts. (on the horizontal axis Ti and Ba indicate the position of the individual TiO2 and
BaO planes). B. Solid circles (blue on line): layer polarization (LP) profile for the same system m6 in units of 10− 10C/m. The
values for the equivalent planes in bulk BaTiO3 are shown with black triangles. The orientation of the individual layer dipoles is
displayed by arrows in the bottom of the panel. C.D.E. LP profiles for m4, m2 and m1. As the thickness is reduced the FDP is
modified by the increasingly dominant interface effects.

constant for all the thicknesses considered, and it is only the electronic polarization that
changes its values in the different systems.
These results show that the ferroelectric response of a thin film is indeed critically influenced
by the interface properties of the system and that the analysis of the local variation of layer
polarization captures completely the physical characteristics of the ferroelectric. As the size
of the film is increased, the DF decreases and the dipoles that are oriented along the DF
direction get smaller, while the interface effects lose relevance. At the critical size, the dipoles
flip direction and a ferroelectric domain structure is established again. Eventually, the dipoles
will relax to the bulk structure, showed with triangles in Fig.10

Model
We further illustrate these physical principles by developing a simple classical model of
a ferroelectric thin film that reproduces the appearance of a FDP. We extended the model
introduced in Ref. ([30]) by discretizing the thin film along the growth direction in each of its
component unit cells in order to introduce a local spatial description of the polarization
with the introduction of the local polarization, Pi . Each individual crystal unit cell is
comprised of two consecutive layers of BaO and TiO2, therefore Pi could be obtained by
adding each individual LP and dividing by the lattice constant in the stacking direction,
c. The full polarization profile of the film is completely specified by the full set of LPs
( p1 , p2 , ..., p2M−1 , p2M ) associated with each crystal plane of the oxide film (see Fig.11). We
can write the total energy of the thin film composed by M unit cells as:
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Figure 11. Each individual crystal unit cell is comprised of two consecutive layers of BaO and TiO2. A local polarization Pi can
be associated with it. It is calculated by adding both individual LP’s and dividing by the lattice constant in the stacking direction,
c. We can associate a dipole pi A to each plane i, separated from its next neighbors by distance dij . The full polarization profile
of the film is completely specified by the full set of dipoles ( p L , p2 , ..., p2M−1 , p R ). The LP at the interfaces (p L and p R ), are kept
fixed. Two distinct interaction parameters θ L and θ R , establish the locality of the interface environment.[50] The interaction
parameter θij for the internal dipoles is arbitrarily chosen to be unity.

M M
E= ∑ (−aPi2 + bPi4 ) + ∑ (−ΩPi .E) + Uint ( p L , p2 , ..., p2M−1 , pR ), (23)
i =1 i =1

where each term of the first sum accounts for the internal energy of the individual unit cells
under zero electric field. The parameters a and b are obtained from an ab initio calculation of
the total energy of a BaTiO3 bulk for different ionic displacements along the soft mode.[51]
The contribution from the depolarization field E is included in the second sum [22, 30] where
Ω is the volume of the unit cell. Each one of its terms favors energetically the local dipoles
that follow the same direction than the DF. The third sum represents the classical electrostatic
energy for a series of dipoles separated by a distance dij ,

2M
A2 θij p j pi
Uint = −
8πǫ ∑ d3ij
(24)
i,j=1

The above sum can be separated in three contributions: two that account for the interaction
between the interface dipoles with the internal ones, and another one that accounts for the
mutual electrostatic interaction between the internal dipoles. We have chosen to assign
a fixed magnitude and direction to the interface layer dipoles (p L and p R ), with two
distinct interaction parameters θ L and θ R , thus establishing the locality of the interface
environment.[50] The interaction parameter θij for the internal dipoles is arbitrarily chosen
to be unity.
With the constraint imposed by the simplicity of the model, we look for the energetically
more favorable spatial polarization profile as a function of the film thickness. The
spatial profile of polarization that characterize the film can be expressed as the vector
( p L , p TiO2 , p BaO , p TiO2 , ..., p BaO , p TiO2 , p R ) where a ferroelectric domain and a FDP will have all
E
dipoles parallel or antiparallel respectively. Note that the total energy per unit cell ( E′ = M )
an be expressed as function of only two single variables p TiO2 and p BaO in the form:
418 Advances in Ferroelectrics
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p TiO2 + p BaO 2 p TiO2 + p BaO 4 p TiO2 + p BaO

     
E′ ( p TiO2 , p BaO ) = − a +b + ΩE
c c c
  (25)
A2  αp BaO pR pL 1 2M−1 p L pi 1 2M−1 pi p R 1 2M−2 pi p j 
M i∑ M i∑ 2M i,j∑
− + + + +
4πǫ Mc3 M (2M − 1) c3 =3 d Lj
3 3
=3 diR =4 dij
3

where we used Eqs.2324 and we define an overall interface parameter α = (θ R p R + θ L p L ) .

Note that the thickness of the film is given by the number of unit cells M and directly affects
the magnitude of the depolarization field E. The DF is calculated from an ab initio calculation
for a supercell with the same size M and using a well-established averaging technique for
the electrostatic potential inside the film.[50]
As M → ∞ , the terms in Eq.25 that describe the mutual interaction between the dipoles
converge to constant values, the DF vanishes and only the first two terms remain in E?,
recovering the bulk properties. Only for small M these terms contribute appreciably to the
total energy of the system. This is true in particular for the interface term that contains the
parameter (fourth term in Eq. 25) that carries the information that defines the interfaces. We
can estimate the interface parameters θ R , θ L , p L , p R from our ab initio simulations2 and we
assume that their numerical values will not depend upon the film thickness (as observed in
the actual calculations, at least to first order).
As we vary the thickness of the ferroelectric film, we observe a change of the total energy
landscape consequence of the interplay between the different energetic contributions. This is
clearly seen in Fig. 12, where we show contour plots of E‘( p TiO2 , p BaO ) for different values of
M. On the left, a diagram with the correspondent spatial distribution of dipoles is indicated.
For thick films, the spatial distribution of dipoles that minimizes the total energy forms
a domain (both LP’s in the BaO and TiO2 planes have the same sign), as can be seen in
the position of the minimum in the contour plot in Fig.12A. As the number of unit cells is
lowered, the minimum shifts to lower values of p BaO until at a critical thickness (Fig. 12B) it
becomes zero. Further reduction of the number of layers M flips only the dipoles belonging
to BaO planes thus establishing a FDP (see Fig. 12D). In conclusion, this simple toy model
captures the general physics of the thin film, and illustrates the intimate relation between the
interface characteristics, the thickness of the film, and the existence of an FDP.
Thus, by exploiting the concept of layer polarization in the description of ferroelectric thin
films between metal contacts, we have been able to obtain detailed information on the
modulation of polarization at the nanoscale and to understand the constraining effects of
the interfaces in the determination of the ferroelectric response of the system. Our results
shows that when film thicknesses reach a critical value, the ferroelectric system responds
via a transition from the bulk ferroelectric structure to a ferrielectric antidipole pattern,
where individual atomic layers acquire uncompensated opposing dipoles. This state arises as
2
The DF does not change much for the films thicknesses considered in this work. Therefore the value used as input
for the model was calculated from the m6 averaged electrostatic potential (E = 2.14101 4V/m). The values for both
interface layer dipoles used are ( p R + p L )/c = 1.0C/m2 ). In the model we also chose c/a = 0.98, respecting the
tetragonal structure of the internal cells of the oxide film.
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Figure 12. Energy landscape E‘( p TiO2 , p BaO ) for different values of θ/M (film thickness). The interaction parameters for both
interfaces were considered equal, theta R = θ L = θ and were kept fixed as the film size M is varied. The remaining parameters
of the model have been derived from our ab initio calculations. A. θ/M = 0, bulk limit where the usual double well potential
produces two equivalent minima with all the layer dipoles parallel. B.θ/M = 3, as the thickness is reduced the interface
effects gain relevance and start to modify the energy landscape. The layer dipoles associated with the BaO planes reduce their
magnitude in order to minimize the total energy. C. At θ/M = 5 the system reaches a critical thickness where these dipoles
become zero and eventually flip orientation. D. For θ/M = 10 the system display a ferrielectric dipole pattern.

consequence of the complex energetic competition between the interface effects, the DF, and
orientation and mutual interaction of the layer dipoles. The appearance of this particular
ferrielectric state can be understood using a simple phenomenological model where the
interface effects are explicitly taken into account.
These results suggest the possibility that such FDPs could be the normal state of a
ferroelectric thin film at the nanoscale, even combined with the formation of two-dimensional
island domains. It would be tempting to link the formation of such FDPs to the appearance
or not of two-dimensional island below the critical thickness, and to understand the ultimate
dependence upon the detailed interface structure and the nature of the metal contact. The
next section will explore in detail the former point.

6. Tuning of polarization in metal-ferroelectric junctions

In this section we study the paradigmatic case of a BaTiO3 film between Pt contacts, already
introduced in the previous section, where we modify the ferroelectric properties by a selective
control of the chemical species present at the interface. In particular, by inserting a single
layer of a different metal (Au,Cu) we demonstrate that we are able to tune the polarization of
the ferroelectric film via the modification of the screening properties of the composite metal
contacts and through the change in the geometrical constraints at the interface.

6.1. Methods and discussion

We have simulated thin films of BaTiO3 between Pt metal contacts in a (001) supercell. The
oxide is terminated with a BaO plane at both interfaces, with the metal atoms directly bonded
to the O atoms of the oxide planei,ii. The supercells constructed in this way can be labeled
as Pt/( M)/( BaO − TiO2)m − BaO/( M )/Pt with m=1,2,4,6 and M=(Pt, Au or Cu). Nine
420 Advances in Ferroelectrics
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Figure 13. Normalized polarization for different number of oxide layers and interface phases. The local polarization is calculated
for each oxide layer, added up and divided by the BaTiO3 bulk polarization calculated in the same way with equivalent numbers
of layers.

atomic metal planes (including the intralayer) have been found to be sufficient to simulate the
contacts under short-circuit boundary conditions. We used the experimental in-plane lattice
parameter of BaTiO3 (3.99Å), and kept it fixed in all calculations. All simulations have been
performed using Density Functional Theory (DFT) within the Local Density Approximation,
using ultrasoft pseudopotentials and a plane waves basis set.[52]
A detailed analysis of the polarization at the nanoscale is critical for a complete description
of the physical properties of the ferroelectric thin film. We have used Modern Theory of
Polarization [6, 8, 18, 53, 54] and in particular the concept of layer polarization (LP)[20] to
evaluate the polarization of the different structures and extract the information on the local
profile of polarization at the nanoscale.
Turning to the results, in Fig.13 we show the total polarization (normalized to the bulk value)
in BaTiO3 films of different thickness between composite metal contacts. These results clearly
elucidate our claim: the polarization of the film is critically affected by the contact geometry
at all the thicknesses we have considered and a residual polarization can be observed in films
as thin as one unit cell.
In fact, a one unit cell thick BaTiO3 film between plain Pt contacts is still in a ferroelectric state
with a polarization 10% of the ideal bulk, and the introduction of a Au intralayer enhances
this value up to 70% of that! In contrast, thicker (6 unit cells) oxide films display similar
ferroelectric characteristics with 50% of the bulk polarization, a clear indication of the rapid
decay of the interface effects with the film thickness. It is worth to note that at variance with
the previous cases, a Cu intralayer induces a paraelectric (or almost paraelectric) behavior
for all thicknesses. We will come back to this point later in the discussion.
In order to understand better the behavior of ferroelectricity in such ultrathin films, we
computed the layer-resolved spatial profile of the polarization, which is quantified by values
of the layer polarization along 3 the structure. This is shown in Fig.14 for m4 films. When
only Pt is present at the contact, the oxide develops a pattern of polarization composed of
pj
3
The local polarization is defined as Pj = cj for each layer j where c j is half the distance between neighboring cations
and pi is the calculated layer polarization[20]. For the outermost layers, we had to make a somewhat arbitrary choice
for c j and used the distance between the outermost cation and the opposite metal plus half the distance between the
cation and the one belonging to the second oxide layer.
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Figure 14. Local Polarization for a unit cell of size m4. Only one layer of Cu at the interface betwen the BaTiO3 and Pt is
enough to drive the system from a ferroelectric structure (squared dots) into a paraelectric one (red triangular dots).

consecutive alternated signs along the direction perpendicular to the interface (see Section 5)
From the behavior of the local polarization it is clear that while the pristine Pt (curve with
black squares) interface display a distinct ferroelectric behavior, a single layer of Cu (red
triangular dots) at the interface between BaTiO3 and Pt is sufficient to stabilize the system
in a paraelectric (non polar) structure (the character of the structure correlates with the
symmetry of the polarization profile: an asymmetric pattern correspond to a polar geometry
and hence to a ferroelectric behavior; a centro-symmetric pattern on the contrary gives rise
to a paraelectric behavior). If we exchange Cu for Au (curve with green triangles), the
polarization is restored, although smaller that in the Pt case, and the whole polarization
profile is substantially changed.
These effects vary as the size of the film changes. In thinner films the local interface details
have strong effects, while they are smoothed out in thicker systems. This can be seen in Fig.15
A-D where we have plotted the LP profile for different sizes of the oxide and different metal
intralayers at the interfaces. In general we notice that the Pt contact maintain the system in
a ferroelectric state for all the sizes although the polarization profiles vary greatly with the
system size. The same effect is observed with the addition of an Au intralayer. These changes
are more noticeable in the thinner systems (m1 and m2) while for the thicker samples both
systems share a similar polarization profile with a higher overall polarization in the Au case.
This behavior can be directly associated with the screening of the depolarization field 4 at the
metallic contacts. We have estimated the depolarization field from the macroscopic average of
the electrostatic potential.[30] Indeed we observed a decrease of the DF with the introduction
of the Au layer. This clearly demonstrate that Au has better screening properties compared
to Pt and in consequence a Au intralayer enhances the overall polarization of the system. A
similar reasoning is more difficult to do in the smaller systems due to the strong asymmetry

4
We used the maximally localized Wannier functions (N. Marzari, and D. Vanderbilt, Phys. Rev. B 56, 12847
(1997)) as implemented in the WanT code (A. Ferretti, B. Bonferroni, A. Calzolari, and M. Buongiorno Nardelli,
http://www.wannier-transport.org) for the determination of the Wannier centers. The disentanglement procedure
(I. Souza, N. Marzari, and D. Vanderbilt, Phys. Rev. B 65, 035109 (2001)) was applied before starting the localization
algorithm, since the bands of the metal and the valence bands of the oxide are mixed in the full supercell calculation.
422 Advances in Ferroelectrics
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Figure 15. Layer polarization for different metal interfaces and films thicknesses A)m1, B)m2, C)m4, D)m6. As reference, the
LPs for bulk BaTiO3 are indicated with blue circles and dotted lines for each case. Metals intralayers used are Cu, Au, Pt. Case
of m6 with Cu layer: this result is in fact an artificial effect due to the known LDA underestimation of the band gap. The Fermi
level of the system overlaps the conduction band and starts filling states that should be empty. We expect the same issue for
m > m6, or with the use of metals with a higher work function. The calculations for m < m6 are be correct under the DFT?LDA
framework, as the Fermi level is safely below the conduction band.

introduced by the proximity of the interfaces and the uncertainty in the evaluation of the
macroscopic averages. However, the qualitative behavior remains the same.
Contrary to Pt and Au, Cu intralayer do not stabilize any ferroelectric distortion at any
thickness . This is a strong indication that Cu screening is weaker and not sufficient to
reduce the depolarization field inside the oxide.
The above behavior is obviously correlated with the redistribution of charge across the
interfaces in the different cases. The latter is quantified by the modification of the band
alignment induced by the metal intralayer, and its influence on the screening properties
of the metal contact. In fact, the knowledge of the band alignment, or Schottky barrier
Height (SBH), allows us to define the properties of the interface phase between the metal
and oxide. In a previous work,[51] we have demonstrated the correlation between the local
structure of the interface composed by a crystalline oxide (BaO) and a d metal, and how
we can tune the SBH by controlling the relative overlap of the local density of states of the
different atoms close to the interface. Indeed we have found an almost complete similarity
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between that BaO/metal interface and the BaTiO3 /metal interface of this work. In both cases
we considered a BaO terminated oxide slabs, that show very similar characteristics (as also
indicated by the fact that the interfaces between BaO and BaTiO3 have almost zero valence
band offset[52]).
Indeed, we find similar behaviors for the band offsets of the interfaces BaO/M/Pd (see Ref.
[52]) and BaTiO3 /M/Pt when Au, Cu and Pt are used as interlayer M. Furthermore, the SBH
for the BaTiO3 /metal interfaces follow the same ascending order for each metal intralayer
(Au (0.8 eV) < Pt (1.1 eV) < Cu (1.4 eV)) in both systems (values given correspond to the
case of m4)5 This trend suggests a relation between the band offsets of the interfaces and
the screening properties of the metals, that is to be expected given the strong correlation
between the charge transfer at the interface and the SBH.[51] In particular, if a strong dipole
is established at the interface, due to a high SBH, as in the case of Cu, fewer charges will be
available for screening the depolarization field and the system will not support a ferroelectric
distortion. Following Ref. [51] we can state the following phenomenological rule: metal
intralayers that reduce the SBH at the interfaces will enhance the screening properties of the
contact and stabilize the ferroelectric distortion.
We have used Density Functinal Theory and the layer polarization concept to analyze the
effect of the interface structure on thin ferroelectric films between metal contacts. As the
size of the film is reduced, the interface effects become strong and influence dramatically
the spatial polarization profile of the system. We monitored these changes as different metal
layers were introduced at the interface, modifying the local structure of the interface, the
band alignment and in turn affecting the screening nature of the metal contact. In this way
we are able to tune the ferroelectric state by carefully choosing the metal interlayer.

Author details
Matías Núñez
Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET), Argentina
Centro Atomico Bariloche, U-A Tecnologia de Materiales y Dispositivos, Division Materiales
Nuclkheares, Argentina
Instituto de Ciencias Basicas, Universidad Nacional de Cuyo, Argentina
Previously at North Carolina State University, Raeligh, North Carolina, USA

References
[1] P. Ghosez and J. Junquera. First-Principles Modeling of Ferroelectric Oxide
Nanostructures. ArXiv Condensed Matter e-prints, May 2006.

[2] L. D. Landau and E. M. Lifshitz. Electrodynamics of Continuous Media. Pergamon Press,

Oxford, 1984.

[3] C. Kittel. Introduction to Solid State Physics. Wiley, New York, 7 edition, 1996.
5
We obtained the SBH values of the BaTiO3 /metal interfaces by calculating the energy difference between the Fermi
level and the upper edge of the valence band, by direct inspection of the LDOS of the systems projected on of each
crystal plane.
424 Advances in Ferroelectrics
24 Advances in Ferroelectrics

[4] N. W. Ashcroft and N. D. Mermin. Solid State Physics. Saunders, Philadelphia, 1976.

[5] Richard M. Martin. Comment on calculations of electric polarization in crystals. Phys.

Rev. B, 9(4):1998–1999, Feb 1974.

[6] R. Resta. Theory of the electric polarization in crystals. Ferroelectrics, 136, 1992.

[7] R.D. King-Smith and David Vanderbilt. Theory of polarization of crystalline solids.
Phys. Rev. B, 47(3):1651–1654, Jan 1993.

[8] Raffaele Resta. Macroscopic polarization in crystalline dielectrics: the geometric phase
approach. Rev. Mod. Phys., 66(3):899–915, Jul 1994.

[9] Raffaele Resta. Quantum-mechanical position operator in extended systems. Phys. Rev.
Lett., 80(9):1800–1803, Mar 1998.

[10] A. Shapere and F. Wilczek. Geometric Phases in Physics. World Scientific, Singapore, 1989.

[11] Raffaele Resta. Manifestations of berry’s phase in molecules and condensed matter.
Journal of Physics: Condensed Matter, 12(9):R107–R143, 2000.

[12] Gregory H. Wannier. The structure of electronic excitation levels in insulating crystals.
Phys. Rev., 52(3):191–197, Aug 1937.

[13] W. Kohn. Analytic properties of bloch waves and wannier functions. Phys. Rev.,
115(4):809–821, Aug 1959.

[14] E.I. Blount. Formalism of band theory. Solid State Physics, 13(305), 1962.

[15] Nicola Marzari and David Vanderbilt. Maximally localized generalized wannier
functions for composite energy bands. Phys. Rev. B, 56(20):12847–12865, Nov 1997.

[16] J. Zak. Berry’s phase for energy bands in solids. Phys. Rev. Lett., 62(23):2747–2750, Jun
1989.

[17] J. Zak. Band center—a conserved quantity in solids. Phys. Rev. Lett., 48(5):359–362, Feb
1982.

[18] D. Vanderbilt and R. Resta. Conceptual foundations of materials properties: A standard

model for calculation of ground- and excited-state properties., chapter Quantum electrostatics
of insulators: Polarization, Wannier functions, and electric fields. Elsevier, The
Netherlands, 2006.

[19] N. Marzari and D. Vanderbilt. Maximally localized generalized wannier functions for
composite energy bands. Phys. Rev. B, 56(20):12847–12865, 1997.

[20] X. Wu, O. Dieguez, K. M. Rabe, and D. Vanderbilt. . Phys. Rev. Lett., 97(107602), 2006.

[21] I. Souza, N. Marzari, and D. Vanderbilt. Maximally localized wannier functions for
entangled energy bands. Phys. Rev. B, 65(035109), 2001.
 Ferroelectrics at the Nanoscale: A First Principle Approach 425
Ferroelectrics at the Nanoscale: A First Principle Approach 25
http://dx.doi.org/10.5772/52268
10.5772/52268

[22] J.D. Jackson. Classical electrodynamics. Wiley, 3 edition, 1998.

[23] B. Meyer and David Vanderbilt. Ab initio study of batio3 and pbtio3 surfaces in external
electric fields. Phys. Rev. B, 63(20):205426, May 2001.

[24] Ph. Ghosez and K. M. Rabe. Microscopic model of ferroelectricity in stress-free pbtio[sub
3] ultrathin films. Applied Physics Letters, 76(19):2767–2769, 2000.

[25] T. Maruyama, M. Saitoh, I. Sakai, T. Hidaka, Y. Yano, and T. Noguchi. Growth and
characterization of 10-nm-thick c-axis oriented epitaxial pbzr[sub 0.25]ti[sub 0.75]o[sub
3] thin films on (100)si substrate. Applied Physics Letters, 73(24):3524–3526, 1998.

[26] Lennart Bengtsson. Dipole correction for surface supercell calculations. Phys. Rev. B,
59(19):12301–12304, May 1999.

[27] Batra I. P. and Silverman B. D. Sol. State Comm., 11(291), 1972.

[28] P.B.Littlewood M.Dawber1, P.Chandra and J.F. Scott. Depolarization corrections to the
coercive field in thin-film ferroelectric. J. Phys.: Condens. Matter, 15:L393–L398, 2003.

[29] A. M. Bratkovsky and A. P. Levanyuk. Very large dielectric response of thin ferroelectric
films with the dead layers. Phys. Rev. B, 63(13):132103, Mar 2001.

[30] J. Junquera and P. Ghosez. . Nature, 422(506), 2003.

[31] Na Sai, Karin M. Rabe, and David Vanderbilt. Theory of structural response to
macroscopic electric fields in ferroelectric systems. Phys. Rev. B, 66(10):104108, Sep 2002.

[32] Alfonso Balderschi, Stefano Baroni, and Raffaele Resta. Band offsets in lattice-matched
heterojunctions: A model and first-principles calculations for gaas/alas. Phys. Rev. Lett.,
61(6):734–737, Aug 1988.

[33] L. Colombo, R. Resta, and S. Baroni. Valence-band offsets at strained si/ge interfaces.
Phys. Rev. B, 44(11):5572–5579, Sep 1991.

[34] Igor Kornev, Huaxiang Fu, and L. Bellaiche. Ultrathin films of ferroelectric solid
solutions under a residual depolarizing field. Phys. Rev. Lett., 93(19):196104, Nov 2004.

[35] Celine Lichtensteiger, Jean-Marc Triscone, Javier Junquera, and Philippe Ghosez.
Ferroelectricity and tetragonality in ultrathin pbtio[sub 3] films. Physical Review Letters,
94(4):047603, 2005.

[36] R.E. Cohen. Nature, 358(136), 1992.

[37] V. Nagarajan, J. Junquera, J. Q. He, C. L. Jia, R. Waser, K. Lee, Y. K. Kim, S. Baik, T. Zhao,
R. Ramesh, Ph. Ghosez, and K. M. Rabe. Scaling of structure and electrical properties in
ultrathin epitaxial ferroelectric heterostructures. Journal of Applied Physics, 100(5):051609,
2006.

[38] C.-G. Duan, R.F. Sabirianov, W.-N. Mei, S.S. Jaswal, and E.Y. Tsymbal. Interface effect
on ferroelectricity at the nanoscale. Nano Letters, 6(3):483–487, 2006.
426 Advances in Ferroelectrics
26 Advances in Ferroelectrics

[39] G. Gerra, A. K. Tagantsev, N. Setter, and K. Parlinski Parlinski. Ionic Polarizability of

Conductive Metal Oxides and Critical Thickness for Ferroelectricity in BaTiO3. Physical
Review Letters, 96(10):107603–+, March 2006.

[40] N. Sai, A. M. Kolpak, and A. M. Rappe. . Phys. Rev.B, 72(020101(R)), 2005.

[41] Toshito Mitsui and Jiro Furuichi. Domain structure of rochelle salt and kh2po4. Phys.
Rev., 90(2):193–202, Apr 1953.

[42] Zhongqing Wu, Ningdong Huang, Zhirong Liu, Jian Wu, Wenhui Duan, Bing-Lin Gu,
and Xiao-Wen Zhang. Ferroelectricity in pb ( zr0.5 ti0.5 ) o3 thin films: Critical thickness
and 180o stripe domains. Phys. Rev. B, 70(10):104108, Sep 2004.

[43] M. Sepliarsky, S. R. Phillpot, D. Wolf, M. G. Stachiotti, and R. L. Migoni. Atomic-level

simulation of ferroelectricity in perovskite solid solutions. Applied Physics Letters,
76(26):3986–3988, 2000.

[44] S. K. Streiffer, J. A. Eastman, D. D. Fong, Carol Thompson, A. Munkholm, M. V.

Ramana Murty, O. Auciello, G. R. Bai, and G. B. Stephenson. Observation of nanoscale
180◦ stripe domains in ferroelectric pbtio3 thin films. Phys. Rev. Lett., 89(6):067601, Jul
2002.

[45] Y. S. Kim, D. H. Kim, J. D. Kim, Y. J. Chang, T. W. Noh, J. H. Kong, K. Char, Y. D.

Park, S. D. Bu, J.-G. Yoon, and J.-S. Chung. Critical thickness of ultrathin ferroelectric
batio[sub 3] films. Applied Physics Letters, 86(10):102907, 2005.

[46] R. A. McKee, F. J. Walker, M. Buongiorno Nardelli, W. A. Shelton, and G. M. Stocks. The

Interface Phase and the Schottky Barrier for a Crystalline Dielectric on Silicon. Science,
300(5626):1726–1730, 2003.

[47] C. F. Pulvari. Phys. Rev., 120(1670), 1960.

[48] Nicola A. Spaldin. MATERIALS SCIENCE: Fundamental Size Limits in Ferroelectricity.

Science, 304(5677):1606–1607, 2004.

[49] K.S. Thygensen, L. B. Hansen, and K. W. Jacobsen. Partly Occupied Wannier Functions.
Phys. Rev. Lett., 94(026405), 2005.

[50] S. Baroni, R. Resta, A. Baldereschi, and M. Peressi. Spectroscopy of Semiconductor

Microstructures, chapter "Can we tune the band offset at semiconductor
heterojunctions?", pages 251–271. Plenum, London, 1989.

[51] Matias Nunez and Marco Buongiorno Nardelli. First-principles theory of metal-alkaline
earth oxide interfaces. Physical Review B (Condensed Matter and Materials Physics),
73(23):235422, 2006.

[52] J. Junquera, M. Zimmerman, P. Orejon, and P. Ghosez. First-principles calculation of the

band offset at BaO/BaTiO3 and SrO/SrTiO3 interfaces. Phys. Rev. B, 67(153327), 2003.
 Ferroelectrics at the Nanoscale: A First Principle Approach 427
Ferroelectrics at the Nanoscale: A First Principle Approach 27
http://dx.doi.org/10.5772/52268
10.5772/52268

[53] R. Raffaele. Macroscopic polarization in crystalline dielectrics: the geometric phase

approach. Rev. Mod. Phys., 66(3):899–915, Jul 1994.

[54] R.D. King-Smith and D. Vanderbilt. Theory of polarization of crystalline solids. Phys.
Rev. B, 47(3):1651–1654, Jan 1993.
 Chapter 19

The Influence of Vanadium Doping on the Physical

and Electrical Properties of Non-Volatile Random
Access Memory Using the BTV, BLTV, and BNTV
Oxide Thin Films

Kai-Huang Chen, Chien-Min Cheng, Sean Wu,

Chin-Hsiung Liao and Jen-Hwan Tsai

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52203

1. Introduction

Recently, the various functional thin films were widely focused on the applications in non-
volatile random access memory (NvRAM), such as smart cards and portable electrical devi‐
ces utilizing excellent memory characteristics, high storage capacity, long retention cycles,
low electric consumption, non-volatility, and high speed readout. Additionally, the various
non-volatile random access memory devices such as, ferroelectric random access memory
(FeRAM), magnetron memory (MRAM), resistance random access memory (RRAM), and
flash memory were widely discussed and investigated [1-9]. However, the high volatile pol‐
lution elements and high fabrication cost of the complex composition material were serious
difficult problems for applications in integrated circuit semiconductor processing. For this
reason, the simple binary metal oxide materials such as ZnO, Al2O3, TiO2, and Ta2O5 were
widely considered and investigated for the various functional electronic product applica‐
tions in resistance random access memory devices [10-12].

The (ABO3) pervoskite and bismuth layer structured ferroelectrics (BLSFs) were excellent
candidate materials for ferroelectric random access memories (FeRAMs) such as in smart
cards and portable electric devices utilizing their low electric consumption, nonvolatility,
high speed readout. The ABO3 structure materials for ferroelectric oxide exhibit high rem‐
nant polarization and low coercive filed. Such as Pb(Zr,Ti)O3 (PZT), Sr2Bi2Ta2O9 (SBT),
SrTiO3 (ST), Ba(Zr,Ti)O3 (BZ1T9), and (Ba,Sr)TiO3 (BST) were widely studied and discussed

© 2012 Chen et al.; licensee InTech. This is an open access article distributed under the terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
430 Advances in Ferroelectrics

for large storage capacity FeRAM devices. The (Ba,Sr)TiO3 and Ba(Ti,Zr)O3 ferroelectric ma‐
terials were also expected to substitute the PZT or SBT memory materials and improve the
environmental pollution because of their low pollution problem [9-15]. In addition, the high
dielectric constant and low leakage current density of zirconium and strontium-doped Ba‐
TiO3 thin films were applied for the further application in the high density dynamic random
access memory (DRAM) [16-20].

Bismuth titanate system based materials were an important role for FeRAMs applications.
The bismuth titanate system were given in a general formula of bismuth layer structure fer‐
roelectric, (Bi2O2)2+(An-1BnO3n+1)2- (A=Bi, B=Ti). The high leakage current, high dielectric loss
and domain pinning of bismuth titanate system based materials were caused by defects, bis‐
muth vacancies and oxygen vacancies. These defects and oxygen vacancies were attributed
from the volatilization of Bi2O3 of bismuth contents at elevated temperature [21-23].

1.1. ABO3 pervoskite structure material system

For ABO3 pervoskite structure such as, BaTiO3 and BZ1T9, the excellent electrical and ferro‐
electric properties were obtained and found. For SOP concept, the ferroelectric BZ1T9 thin
film on ITO substrate were investigated and discussed. For crystallization and grain grow of
ferroelectric thin films, the crystal orientation and preferred phase of different substrates
were important factors for ferroelectric thin films of MIM structures.

The XRD patterns of BZ1T9 thin films with 40% oxygen concentration on Pt/Ti/SiO2/Si sub‐
strates from our previous study were shown in Fig. 1 [24-25]. The (111) and (011) peaks of
the BZ1T9 thin films on Pt/Ti/SiO2/Si substrates were compared with those on ITO sub‐
strates. The strongest and sharpest peak was observed along the Pt(111) crystal plane. This
suggests that the BZ1T9 films grew epitaxially with the Pt(111) bottom electrode. However,
the (111) peaks of BZ1T9 thin films were not observed for (400) and (440) ITO substrates.
Therefore, we determined that the crystallinity and deposition rate of BZ1T9 thin films on
ITO substrates differed from those in these study [24-27].

Figure 1. a) XRD patterns of as-deposited thin films on the ITO/glass and Pt substrates, and (b) p-E curves of thin films.
 The Influence of Vanadium Doping on the Physical and Electrical Properties 431
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The polarization versus applied electrical field (p-E) curves of as-deposited BZ1T9 thin films
were shown in Fig. 1(a). As the applied voltage increases, the remanent polarization of thin
films increases from 0.5 to 2.5 μC/cm2. In addition, the 2Pr and coercive field calculated and
were about 5 μC/cm2 and 250 kV/cm, respectively. According to our previous study, the
BZ1T9 thin film deposited at high temperature exhibited high dielectric constant and high
leakage current density because of its polycrystalline structure [24].

1.2. Bismuth Layer Ferroelectric Structure material system

The XRD patterns of as-deposited Bi4Ti3O12 thin films and ferroelectric thin films under
500~700 °C rapid thermal annealing (RTA) process were compared in Fig. 2(a). From the re‐
sults obtained, the (002) and (117) peaks of as-deposited Bi4Ti3O12 thin film under the opti‐
mal sputtering parameters were found. The strong intensity of XRD peaks of Bi4Ti3O12 thin
film under the 700 °C RTA post-treatment were is found. They were (008), (006), (020) and
(117) peaks, respectively. Compared the XRD patterns shown in Fig. 2, the crystalline inten‐
sity of (111) plane has no apparent increase as the as-deposited process is used and has ap‐
parent increase as the RTA-treated process was used. And a smaller full width at half
maximum value (FWHM) is revealed in the RTA-treated Bi4Ti3O12 thin films under the 700
°C post-treatment. This result suggests that crystal structure of Bi4Ti3O12 thin films were im‐
proved in RTA-treated process.

Figure 2. a) XRD patterns of as-deposited Bi4Ti3O12 thin films, and (b)the SEM morphology of as-deposited Bi4Ti3O12
films.

The surface morphology observations of as-deposited Bi4Ti3O12 thin films under the 700 °C
RTA processes were shown in Fig. 2(b). For the as-deposited Bi4Ti3O12 thin films, the mor‐
phology reveals a smooth surface and the grain growth were not observed. The grain size
and boundary of Bi4Ti3O12 thin films increased while the annealing temperature increased
to 700 °C. In RTA annealed Bi4Ti3O12 thin films, the maximum grain size were about 200
nm and the average grain size is 100 nm. The thickness of annealed Bi4Ti3O12 thin films
were calculated and found from the SEM cross-section images. The thickness of the depos‐
ited Bi4Ti3O12 thin films is about 800 nm and the deposited rate of Bi4Ti3O12 thin films is
about 14 nm/mim.
432 Advances in Ferroelectrics

2. Experimental Detail

S. Y. Wu firstly reported that an MFS transistor fabricated by using bismuth titanate in 1974
[28-29]. The first ferroelectric memory device was fabricated by replacing the gate oxide of a
conventional metal-oxide-semiconductor (MOS) transistor with a ferroelectric material.
However, the interface and interaction problem between the silicon substrate and ferroelec‐
tric films were very important factors during the high temperature processes in 1TC struc‐
ture. To overcome the interface and interaction problem, the silicon dioxide and silicon
nitride films were used as the buffer layer. The low remnant polarization and high operation
voltage of 1TC were also be induced by gate oxide structure with double-layer ferroelectric
silicon dioxide thin films. Sugibuchi et al. provided a 50 nm silicon dioxide thin film be‐
tween the Bi4Ti3O12 layer and the silicon substrate [30].
The ferroelectric ceramic target prepared, the raw materials were mixed and fabricated by
solid state reaction method. After mixing and ball-milling, the mixture was dried, grounded,
and calcined for some time. Then, the pressed ferroelectric ceramic target with a diameter of
two inches was sintered in ambient air. The base pressure of the deposited chamber was
brought down 1×10-7 mTorr prior to deposition. The target was placed away from the
Pt/Ti/SiO2/Si and SiO2/Si substrate. For metal-ferroelectric-metal (MFM) capacitor structure,
the Pt and the Ti were deposited by dc sputtering using pure argon plasma as bottom elec‐
trodes. The SiO2 thin films were prepared by dry oxidation technology. The metal-ferroelec‐
tric-insulator-semiconductor (MFIS) and metal-ferroelectric-metal (MFM) structures were
shown in Fig. 3.

Figure 3. a) Metal-ferroelectric-insulator-semiconductor (MFIS) structure, and (b) Metal ferroelectric-metal (MFM)

structure.

For the physical properties of ferroelectric thin films obtained, the thickness and surface
morphology of ferroelectric thin films were observed by field effect scanning electron micro‐
scopy (FeSEM). The crystal structure of ferroelectric thin films were characterized by an X-
ray diffraction (XRD) measurement using a Ni-filtered CuKα radiation. The capacitance-
voltage (C-V) properties were measured as a function of applied voltage by using a Hewlett-
Packard (HP 4284A) impedance gain phase analyzer. The current curves versus the applied
voltage (I-V characteristics) of the ferroelectric thin films were measured by a Hewlett-Pack‐
ard (HP 4156) semiconductor parameter analyzer.
 The Influence of Vanadium Doping on the Physical and Electrical Properties 433
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3. Results and Discussion

3.1. Large memory window in the vanadium doped Bi4Ti3O12 (BTV) thin films
The XRD pattern was used to identify the crystalline structures of as-deposited BTV thin
films, labeled “vanadium doped at 550 °C,” with various depositing parameters. From the
XRD pattern, we found that the optimal deposition parameters of as-deposited BTV thin
films were RF power of 130 W, chamber pressures of 10 mtorr and oxygen concentrations of
25%. The crystalline orientations of (117), (008) and (200) planes were apparently observed
in the films. It was found that all of the films consisted of a single phase of a bismuth lay‐
ered structure showing the preferred (008) and (117) orientation. Both films were well c-axis
oriented, but BTV thin film was more c-axis oriented than BIT, labeled “undoped at 550 °C”.
For the polycrystalline BTV thin films, the (117) peak was the strongest peak and the intensi‐
ty of the (008) peak was 10% of (117) peak intensity. An obvious change in the orientation
due to the substitution was observed except for the degree of the (117) orientation for BTV
films. In addition, the XRD patterns of the as-deposited BTV thin films deposited using opti‐
mal parameters at room and 550 °C substrate temperatures were observed in Fig. 2. This re‐
sult indicated that the crystalline characteristics of BTV thin films deposited at 550 °C were
better than those of BTV thin films at room temperature. The crystalline and dielectric char‐
acteristics of as-deposited BTV thin films were influenced by substrate temperatures. The
electrical characteristics of as-deposited BTV thin films at substrate temperatures of 550 °C
under optimal parameters will be further developed.

Figure 4. The XRD patterns of (a) undoped at 550 °C (b) vanadium doped at R.T. and (c) vanadium doped at 550 °C
thin films deposited using optimal parameters.

In Fig. 5, circular-like grains with 150 nm width were observed with scanning electron mi‐
croscopy (SEM) for as-deposited BTV thin films. From the cross-sectional SEM image, film
thicknesses were measured to be 742 nm. As the depositing time increases from 30 and 60,
434 Advances in Ferroelectrics

to 120 min, the thickness of as-deposited BTV thin films increases linearly from 197 and 386,
to 742 nm, respectively, as the depositing rate decreases from 6.57 and 6.43, to 6.18 nm.

Figure 5. The surface micro structure morphology of the BTV thin films deposited using optimal parameters.

Figure 6(a) compares the change in the capacitance versus the applied voltage (C-V) for the
un-doped and vanadium doped thin films. Based on Fig. 4, the capacitances of the BIT thin
films appear to increase due to the vanadium dopant. We found that the capacitances of
BTV thin films increased from 1.3 to 4.5 nF. As suggested by Fig. 4, the improvement in the
dielectric constants of the BTV thin films can be attributed to the compensation of the oxy‐
gen vacancy and the improvement in the B-site substitution of the ABO3 phase in the BTV
thin films [31-34].

Figure 6. a) The P-E characteristics of vanadium doped and undoped thin films, and (b) The normalization C-V curves
of vanadium doped and undoped thin films.

Figure 6 shows ferroelectric hysteresis loops of BIT and as-deposited BTV thin film capaci‐
tors measured with a ferroelectric tester (Radiant Technologies RT66A). The as-deposited
BTV thin films, labeled “vanadium doped,” clearly show ferroelectricity. The remanent po‐
 The Influence of Vanadium Doping on the Physical and Electrical Properties 435
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larization and coercive field were 23 μC/cm2 and 450 kV/cm. Comparing the vanadium dop‐
ed and undoped BIT thin films, the remanent polarization (2Pr) would be increased form
16μC/cm2 for undoped BIT thin films to 23 μC/cm2 for vanadium doped. However, the coer‐
cive field of as-deposited BTV thin films would be increased to 450 kV/cm. These results in‐
dicated that the substitution of vanadium was effective for the appearance of ferroelectricity
at 550 °C. The 2Pr value and the Ec value were larger than those reported in Refs. [35-36],
and the 2Pr value was smaller and the Ec value was larger than those reported in [37]. Based
on above results, it was found that the simultaneous substitutions for B-site are effective to
derive enough ferroelectricity by accelerating the domain nucleation and pinning relaxation
caused by B-site substitution [31-37].
The leakage current density versus applied voltage curves of as-deposited BTV thin films for
different depositing time on the MFIS structure were be found. We found that the leakage
current density of undoped BIT thin films, labeled “undoped,” were larger than those of va‐
nadium-doped BIT thin films. This result indicated that the substitution of B-site in ABO3
perovskite structure for BTV thin films was effective in lowering leakage current density.
Besides, the thickness of BTV thin films has an apparent influence on the leakage current
density of BTV thin films, and that will have an apparent influence on the other electrical
characteristics of BTV thin films. At an electric field of 0.5 MV/cm, the leakage current densi‐
ty critically decreases from the 3.0 ×10-7 A/cm2 for 30 min-deposited BTV thin films to
around 3×10-8A/cm2 and 2×10-8 A/cm2 for 60 and 120 min-deposited BTV thin films.
Figure 7(a) show the capacitance versus applied voltage (C-V) curves of as-deposited vana‐
dium doped BTV and un-doped BIT thin films. The applied voltages, which are first changed
from -20 to 20 V and then returned to -20 V, are used to measure the capacitance volt‐
age characteristics (C-V) of the MFIS structures. For the vanadium doped thin films, the mem‐
ory window of MFIS structure increased from 5 to 15 V, and the threshold voltage decreased
from 7 to 3 V. This result demonstrated that the lower threshold voltage and decreased oxy‐
gen vacancy in undoped BIT thin films had been improved from the C-V curves measured.

Figure 7. a) The P-E characteristics of vanadium doped and undoped thin films, and (b) The normalization C-V curves
of vanadium doped and undoped thin films.

Figure 7(b) shows the C-V curves of 30 min-deposited BTV thin films, and Figure 7(b) com‐
pares the C-V curves of BTV thin films deposited at different depositing time. Figure 7(b)
also shows that the capacitance at the applied voltage value of 0 V critically increases as the
436 Advances in Ferroelectrics

depositing time increases. The memory window would be decreased from 15.1 and 13.4, to
10.6 V as the depositing time increased. Two reasons may be the cause that the increases ca‐
pacitance of as-deposited BTV thin films in the MFIS structure for the different depositing
time. First, the decrease leakage current density was attributed to the increase thickness of
as-deposited BTV thin films in Fig. 4. Second, the different thickness and high dielectric con‐
stant of as-deposited BTV thin films are also an important factor. In Fig. 7, the capacitance of
as-deposited BTV thin films for MFIS structure could be calculated from Eq. 1 and Eq. 2:

(1)

(2)

The ε1 and d1 are the effective dielectric constant and the total thickness of silicon and SiO2
layer. The ε2 and d2 are the effective dielectric constant and the thickness of as-deposited
BTV thin film layer. The relative dielectric constants of Si and SiO2 are 11.7 and 3.9. The εr
value (ε1) of silicon and SiO2 layer is much smaller than that (ε2) of as-deposited BTV thin
films. The ε1×d2 is the unchanged value and the ε2×d1 value increases with the increase of
depositing time. In Eq. (2), the ε1×d2 increases more quickly as d2 increases. In Eq. (1), the C
value will increase as the εr value increases.

For memory window characteristics at applied voltage of 0 volts, the upper and lower ca‐
pacitance values of as-deposited BTV thin films for 30 min depositing time were 0.056 and
0.033 nF, respectively. For 60 min and 120 min depositing time, they were 0.215~0.048 nF
and 1.515 ~0.105 nF, respectively. The change ratios at zero voltage were defined in Eq.(3)
from these experimental results:

(3)

where Cu and Cl are the upper and lower capacitance values.

The capacitance change ratios of as-deposited BTV thin films for different depositing time
were 41, 73 and 93%, respectively. From above statements, the good switching characteris‐
tics of ferroelectric polarization could be attributed to memory windows ratio and the thin‐
ner thickness of as-deposited BTV thin film for the depositing time of 30 min. These results
indicted the upper and lower capacitance of memory window would be decreased by lower‐
ing the thickness of SiO2 layer.
 The Influence of Vanadium Doping on the Physical and Electrical Properties 437
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3.2. The Influence of Lanthanum Doping on the Physical and Electrical Properties of BTV
(BLTV) Ferroelectric Thin Films

For MFM structures, the crystal orientation and preferred phase of ferroelectric thin films on
Pt/Ti/SiO2/Si substrates was important factor. The x-ray diffraction (XRD) patterns of BLTV
and BTV thin films prepared by rf magnetron sputtering were be found. From the XRD pat‐
tern, the BLTV and BTV thin film were polycrystalline structure. The (004), (006), (008), and
(117) peaks were observed in the XRD pattern. All of thin films consisted of a single phase of
a bismuth layered structure showing the preferred (117) orientation. All of thin films were
exhibited well c axis orientation. The change in the orientation of BLTV thin films due to the
substitution was not observed. The degree of the (117) orientation relative to the (001) orien‐
tation of BLTV thin films dominant was shown.

Figure 8. The surface micro structure of as-deposited (a) BTV and (b) BLTV thin films.

Figure 9. a)The C-V characteristics of as-deposited BTV and BLTV thin films. (b) The polarization versus electrical field
characteristics of as-deposited BTV and BLTV thin films.

In Fig. 8a, rod-like and circular-board grains with 250 nm length and 150 nm width were
observed with scanning electron microscopy (SEM) for as-deposited BTV films. The small
grain was gold element in preparation for the SEM sample. However, the BLTV thin films
exhibited a great quantity of 400 nm length and 100 nm width rod-like grain structure in Fig
8 b. The rod-like grain size of BLTV thin films was larger than those of BTV. We induced
438 Advances in Ferroelectrics

that the bismuth vacancies of BTV thin films compensate for lanthanum addition and micro-
structure were improved in BLTV thin films. From the cross-sectional SEM image, average
thin film thicknesses for MFIS structure were about 610 nm. The average thickness of thin
films for MFM structure was about 672 nm.

Figure 9(a) shows the change in the capacitance versus the applied voltage (C-V) of the BTV
and BLTV thin films in MFM structure measured at 100 kHz. The applied voltages, which
were first changed from -20 to 20 V and then returned to -20 V, were used to measure the
capacitance voltage characteristics (CV). The BLTV thin films exhibited high capacitance
than those of BTV thin films. We found that the capacitances of the lanthanum-doped BTV
thin films were increased from 2.38 to 2.42 nF.

Figure 9(b) shows the p-E curves of the different ferroelectric thin films under applied volt‐
age of 18V from the Sawyer−Tower circuits. The remanent polarization of non-doped, vana‐
dium-doped, and lanthanum-doped ferroelectric thin films linearly was increased from 5, 10
to 11 μC/cm2, respectively. The coercive filed of non-doped, vanadium-doped, and lantha‐
num-doped ferroelectric thin films were about 300, 300, and 250 kV/cm, respectively. The
ferroelectric properties of lanthanum-doped and vanadium-doped BIT thin films were im‐
proved and found.

Figure 10. a)The C-V characteristics of as-deposited BTV and BLTV thin films. (b) The polarization versus electrical field
characteristics of as-deposited BTV and BLTV thin films.

The fatigue characteristics for ferroelectric thin films were the time dependent change of the
polarization state. After a long time, the polarization loss of ferroelectric thin films was af‐
fected by oxygen vacancies, defect, and space charge in the memory device. Figure 10 shows
the polarization versus electrical field (p-E) properties of the different ferroelectric thin films
before and after the switching of 109 cycles. The remnant polarization loss of BLTV and BTV
thin films were about 9% and 15% of initial polarization value, respectively. The remnant
polarization of BLTV thin films were little changed after the switching cycles. The fatigue
behavior and domain pinning were improved by lanthanum and vanadium addition in BIT
thin films. To reduce bismuth defect and oxygen vacancy, the high-valence cation substitut‐
ed for the A-site of BLTV thin films were observed.
 The Influence of Vanadium Doping on the Physical and Electrical Properties 439
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Figure 11. a) The (J/T2) and (J/E) versus E1/2 curves of as-deposited BIT, BTV, and BLTV thin films. (b) The normalization
capacitance versus applied voltage curves of as-deposited BTV and BLTV thin films.

From the J-E curves, the conduction mechanism of as-deposited thin films was also proved
the bismuth defect and oxygen vacancy results. For MFIS structure, the interface and inter‐
action problem between of the silicon and ferroelectric films was serious important. The ef‐
fect of the bound polarization charge from the carrier in the silicon substrate was observed.
To overcome this problem, the insulator films of buffer layer were used for MFIS structure
[28-30, 37-38].

Figure 11(a) shows the leakage current density versus electrical field (J-E) characteristics of
as-deposited BTV and BLTV thin films for MFIS structure. The leakage current density of
the as-deposited BLTV thin films were about one order of magnitude lower than those of the
non-doped lanthanum thin films. However, the lanthanum and vanadium doped BIT thin
films were lower than those of BIT thin films. We suggested that low leakage current density
attributed to substituting a bismuth ion with a lanthanum ion at A-site for lanthanum doped
BTV thin films. To discuss bismuth ion substituting by lanthanum ion effect, the leakage
current versus electrical field curves of BLTV thin films were fitted to Schottky emission and
Poole–Frankel transport models. The inset of Fig. 11(a) shows the JE characteristics for BIT,
BTV, and BLTV thin films in terms of J/E as vertical axis and E1/2 as horizontal axis. The fit‐
ting curves were straight in this figure and a JE curve of thin films was the Poole−Frankel
emission model. The high leakage current was attributed to the bismuth vacancies and oxy‐
gen vacancies of as-deposited BIT thin films [39−42]. Park et al. also suggested that the en‐
hanced stability of TiO6 octahedra against oxygen vacancies for fatigue resistance of
lanthanum doped BIT thin films [31].

In a previous study, the low threshold voltage of ferroelectric thin films was attributed by
bismuth and oxygen vacancy [9]. The threshold voltage for the lanthanum-doped BTV thin
films of MFIS structure was improved from 5 to 3 V. The memory functional effect and de‐
pletion delay of the MFIS structure was caused by remanent polarization of ferroelectric thin
films in CV curves. In this study, the memory window was increased from 15 to 18 V. The
large memory window of lanthanum-doped BTV thin films was also proved by p-E curves
in Fig. 11(b). As a result, the improvement in the capacitance of the BLTV thin films was at‐
tributed to the compensation of the oxygen vacancy of the BLSF structure. Additionally, the
440 Advances in Ferroelectrics

memory window of ferroelectric thin films was changed by the sweeping speed. The ferro‐
electric capacitance and threshold voltage of MFIS structure slightly decreases as the sweep‐
ing speed increases. That was influenced by the mobile ions and charge injection between
as-deposited ferroelectric thin films and metal electrode as the sweeping speed increased [9].

3.3. The Influence of Neodymium Doping on the Physical and Electrical Properties of
BTV (BNTV) Ferroelectric Thin Films

Figure 12(a) shows x-ray diffraction patterns of the as-deposited ferroelectric thin films for
different oxygen concentration on ITO substrate. From the XRD patterns, we found that the
ferroelectric thin films exhibited polycrystalline structure. In addition, the (117), (008), and
(220) peaks were observed in the XRD pattern. The intensity of the (117) peak of the ferro‐
electric thin films increases linearly as the oxygen concentration increases from 0 to 40%.
The intensity of the (117) peak of the as-deposited ferroelectric thin films decreases at oxy‐
gen concentration from 40 to 60%. As shown in Fig. 3, the (117) preferred phase and smallest
full-width-half-magnitude (FWHM) value were exhibited by the as-deposited ferroelectric
thin film with the 40% oxygen concentration. The polycrystalline structure of the as-deposit‐
ed (Bi3.25Nd0.75)(Ti2.9V0.1)O12 ferroelectric thin film was optimal at 40% oxygen concentration.

Figure 12. a) The x-ray diffraction patterns of the as-deposited (Bi3.25Nd0.75)(Ti2.9V0.1)O12 ferroelectric thin film for the
different oxygen concentration. (b) The surface morphology of the as-deposited (Bi3.25Nd0.75)(Ti2.9V0.1)O12 ferroelectric
thin film for 40% oxygen concentration.

Besides, the interface between an electrode and the as-deposited (Bi3.25Nd0.75)(Ti2.9V0.1)O12 thin
films was an important factor that seriously influences the physical and electrical properties
of the MIM capacitor structure. Therefore, the surface roughness of the as-deposited
(Bi3.25Nd0.75)(Ti2.9V0.1)O12 thin films for 40% oxygen concentration was absolutely determined
and calculated. Figure 12(b) shows the surface roughness of the as-deposited (Bi3.25Nd0.75)
(Ti2.9V0.1)O12 ferroelectric thin film from the AFM images. The roughness of the ferroelectric
thin film were 4.278nm. The surface roughness of the as-deposited ferroelectric thin films in‐
creases with the oxygen concentration. Therefore, we assume that the surface roughness of
the as-deposited ferroelectric thin films increases due to an increase in the crystallinity with
oxygen concentration.
 The Influence of Vanadium Doping on the Physical and Electrical Properties 441
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Figure 13. The surface morphology of the as-deposited (Bi3.25Nd0.75)(Ti2.9V0.1)O12 ferroelectric thin film for 40% oxygen
concentration. The surface micro-structure of the as-deposited (Bi3.25Nd0.75)(Ti2.9V0.1)O12 ferroelectric thin film for (a)
25% and (b) 40% oxygen concentration.

From the SEM images in Fig. 13, the surface morphology and grain size of the as-deposit‐
ed (Bi3.25Nd0.75)(Ti2.9V0.1)O12 thin films for 25 and 40% oxygen concentration were ob‐
served. The grain size of the as-deposited (Bi3.25Nd0.75)(Ti2.9V0.1)O12 thin films were about 110
nm and 50 nm, respectively. We deduced that grain size changed caused by the different
oxygen xoncentration.

Figure 14. a) The capacitance versus applied voltage (C-V) properties of the as-deposited (Bi3.25Nd0.75)(Ti2.9V0.1)O12 fer‐
roelectric thin film. (b) The polarization versus applied electrical field (p-E) properties of the as-deposited (Bi3.25Nd0.75)
(Ti2.9V0.1)O12 ferroelectric thin film.

Figure 14(a) shows the C-V characteristics measured with the MFM capacitor structure for
the as-deposited (Bi3.25Nd0.75)(Ti2.9V0.1)O12 thin films deposited under various oxygen concen‐
trations. The applied bias voltage is adjusted from -20 to 20V. The capacitance of ferroelec‐
tric thin films first increases with the increase of oxygen concentration and reaches the
maximum value in the 40 % oxygen atmosphere. Then the capacitance apparently decreases
in the further increase of oxygen to 60 %. This variation of capacitance has the similar results
with the XRD patterns and the AFM images. The polarization versus applied electrical field
(p-E) curves of the as-deposited (Bi3.25Nd0.75)(Ti2.9V0.1)O12 ferroelectric thin film at the frequen‐
cy of 1kHz were shown in fig. 14(b). From the p-E curves results, the remnant polarization of
ferroelectric thin films were 11 μC/cm2, as the coercive filed of 220 kV/cm. In addition, the
remnant polarization and coercive filed of ferroelectric thin films for 40% oxygen concentra‐
tion were about 10 μC/cm2 and 300 kV/cm. From the experimental measurement, this result
442 Advances in Ferroelectrics

was attributed to the suitable oxygen concentration sample as compared to that of the as-
deposited ferroelectric thin film. As the oxygen/argon mixtures were used as the depositing
atmosphere, the defects and oxygen vacancies in ferroelectric thin films were filled and com‐
pensated by oxygen gas, and the leakage current density were decreased. The low leakage
current density will reveal in the 40%-oxygen-deposited ferroelectric thin films. For that the
capacitance will be increased and the leakage current density will be decreased. As the ap‐
plied voltage of 15V was used, the leakage current density of ferroelectric thin films deposit‐
ed at 40% oxygen concentration is about 1×10-9A/cm2.

Figure 15. a) The leakage current density versus applied voltage (J-E) properties of the as-deposited (Bi3.25Nd0.75)
(Ti2.9V0.1)O12 ferroelectric thin film.(b) The retention and fatigue properties of the as-deposited ferroelectric thin film
corresponding hysteresis loop before and after fatigue test.

The retention and fatigue properties for the as-deposited (Bi3.25Nd0.75)(Ti2.9V0.1)O12 ferroelec‐
tric thin films were the time dependent change of the polarization state. After long time test‐
ing, the polarization loss of the as-deposited ferroelectric thin films was affected by oxygen
vacancies, defect, and space charges in the memory device test. Figure 15 shows the polari‐
zation versus electrical field (p-E) properties of the as-deposited (Bi3.25Nd0.75)(Ti2.9V0.1)O12 fer‐
roelectric thin films before and after the switching of 109 cycles. The remnant polarization
loss of ferroelectric thin films was about 9% of initial polarization value, respectively. The
remnant polarization of ferroelectric thin films was little changed after the test cycles. The
fatigue behavior and domain pinning were improved by neodymium and vanadium addi‐
tion in BIT thin films. To improve bismuth and oxygen vacancy, the high-valence cation
substituted for the A-site of (Bi3.25Nd0.75)(Ti2.9V0.1)O12 thin films were observed.

3.4. Bipolar Resistive Switching Properties of Transparent Vanadium Oxide (V2O5)

Resistive Random Access Memory

Figure 16(b) shows x-ray diffraction patterns of the as-deposited vanadium oxide thin films
for 60% oxygen concentration on ITO substrate prepared by different sintering temperature.
From the XRD patterns, we found that the vanadium oxide thin films exhibited polycrystal‐
line structure. In addition, the (110), (222), and (400) peaks were observed in the XRD pat‐
tern. The intensity of the (110) peak of the thin films increases linearly as the sintering
 The Influence of Vanadium Doping on the Physical and Electrical Properties 443
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temperature increases from 400 to 550 °C. The intensity of the (110) peak of the as-deposited
thin films decreases at sintering temperature from 550 to 600 oC. As shown in Fig. 16, the
(110) preferred phase and smallest full-width-half-magnitude (FWHM) value were exhibited
by the as-deposited vanadium oxide thin film with the sintering temperature of 550 °C. The
polycrystalline structure of the as-deposited vanadium oxide thin film was optimal at 550 °C
sintering temperature.

Figure 16. a) Metal-insulator-metal (MIM) structure using as-deposited vanadium oxide thin films. (b) The x-ray dif‐
fraction patterns of the as-deposited vanadium oxide thin films on ITO substrate for different sintering temperature.

The thickness of as-depoisted vandium oxide thin films for different sintering temperature
was determined by SEM morphology. As the oxygen concentration increases from 0 to 60%,
the thickness of as-deposited vandium oxide thin films linearly decreases. In addition, the
deposition rate of as-deposited vanadium oxide thin films with 60% oxygen concentration
was 2.62 nm/min. The decreases in the deposition rate and thickness of as-depoisted vanadi‐
um oxide thin films might be affected by the decrease in Ar/O2 ratio. The Ar/O2 ratio was
adjusted using argon gas to generate the plasma on the surface of the as-depoisted vanadi‐
um oxide ceramic target during sputtering. Figure 17 shows the surface morphology for the
as-deposited and 500 °C sintered vanadium oxide thin films. We found that the grain size of
500 °C sintered vanadium oxide thin films were larger than others. The better resistance
properties might be caused by this reason.
Figure 18 shows the current vsersus applied voltage (I-V) properties of vanadium oxide thin
films for the different sintering temperature. After the staring forming process, the device
reached a low resistance state (LRS) and high resistance state (HRS). By sweeping the bias to
negative over the reset voltage, a gradual decrease of current was presented to switch the cells
from LRS to HRS (reset process). Additionally, the cell turns back to LRS while applying a larg‐
er positive bias than the set voltage (set process). All of the vanadium oxide thin film were ex‐
hibit the bipolar behavior. The I-V properties of as-deposited vanadium oxide thin films of 60%
oxygen concentration was about 1×10-4A/cm2 when an applied electrical voltage of 0.1V. Dur‐
ing the rf sputtering deposition process, oxygen vacancies appear in the as-deposited vanadi‐
um oxide thin films. The defects and oxygen vacancies of as-deposited vanadium oxide thin
films were filled and compensated for to different extents at different oxygen concentrations.
In addition, the smallest leakage current density of as-deposited vanadium oxide thin films
444 Advances in Ferroelectrics

was obtained at an oxygen concentration of 40%. As shown in Fig. 18, the high leakage current
density and thin films of as-deposited vanadium oxide thin films for 60% oxygen concentra‐
tion were attributed to low argon sputtering gas concentration.

Figure 17. The surface morphology for (a) as-deposited (b) 500°C sintered vanadium oxide thin films.

Figure 18. a) Typical I-V characteristics of vanadium oxide thin films for the different oxygen concentration. (b) Typical
I-V characteristics of the as-deposited vanadium oxide thin films for different sintering temperature.

In addition, The transport current of the vanadium oxide thin films decreases linearly as
the sintering temperature increases from 450 to 500 °C. The transport current of the as-de‐
posited vanadium oxide thin films increases at sintering temperature from 500 to 550 °C.
We found the as-deposited vanadium oxide thin films prepared by 500 °C sintering temper‐
ature were exhibited the large the on/off ratio resistance properties. In addition, the switch‐
ing cycling was measured another type of reliability and retention characteristics were
observed. There was a slight flucation of resistance in the HRS and LRS states, and the sta‐
ble bipolar witching property was observed during 20 cycles. The results show remarka‐
ble reliability performance of the resistance random access memory devices for nonvolatile
memory applications.

4. Conclusion

In conclusion, BIT, BTV, BNTV, and BLTV thin films were prepared by rf magnetron sput‐
tering. We confirmed that all thin films on Pt/Ti/SiO2/Si substrate well crystallized by XRD
 The Influence of Vanadium Doping on the Physical and Electrical Properties 445
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analysis. The BNTV, BLTV, and BTV shows clear ferroelectricity form the p-E curves. The
remnant polarization properties of BLTV thin film decreased by 9%, while that of the BTV
decreased by 15% after the fatigue test with 109 switching cycles. Fatigue behavior in ferro‐
electric capacitors was attributed to oxygen and bismuth vacancies. The leakage current
density of as-deposited BLTV and BTV thin films were lower than those of BIT, which were
were attributed to the decrease of oxygen and ismuth vacancies after vanadium and lantha‐
num addition. The conduction mechanism of as-deposited BTV and BLTV thin films were
also proved these results in J-E curves. We indicated that small ions substitution for A and B
site of BLSF structure was effective decreased the oxygen and bismuth vacancies. Finally,
the low threshold voltage and memory window of BLTV thin films were improved from the
C-V curves measured. In addition, the metal oxide thin films such as, TiO2, Ta2O5, Al2O3, and
CuO were widely investigated and discussed for applications in nonvolatile resistive ran‐
dom access memory (RRAM) devices. The nonvolatile resistive random access memory
(RRAM) devices were well developed and studied because of their structural simplicity,
high density and low power, read / write speed (about 101 ~ 103ns), high operating cycles (>
1013) and other non-volatile advantages. Therefore, the electrical switching properties of the
vanadium oxide thin films for nonvolatile resistive random access memory (RRAM) device
were observed.

Acknowledgements

The authors will acknowledge to Prof. Ting-Chang Chang and Prof. Cheng-Fu Yang. Addi‐
tionally, this work will acknowledge the financial support of the National Science Council of
the Republic of China (NSC 99-2221-E-272-003) and (NSC 100-2221-E-272-002).

Author details

Kai-Huang Chen1, Chien-Min Cheng2, Sean Wu3, Chin-Hsiung Liao4 and Jen-Hwan Tsai4

1 Department of Electronics Engineering/Tung-Fang Design University/Taiwan,R.O.C., Tai‐

wan

2 Department of Electronic Engineering/Southern Taiwan University of Science and Tech‐

nology/Taiwan, R.O.C., Taiwan

3 Department of Physics/Military Academy/Kaohsiung / Taiwan, R.O.C., Taiwan

4 Department of Mathematics and Physics/Chinese Air Force Academy/Taiwan, R.O.C., Tai‐

wan
446 Advances in Ferroelectrics

References

[1] Shannigrahi, R., & Jang, H. M. (2001). Appl. Phys. Lett., 79, 1051.
[2] Hong, S. K., Suh, C. W., Lee, C. G., Lee, S. W., Hang, E. Y., & Kang, N. S. (2000). Appl.
Phys. Lett., 77-76.
[3] Xiong, S. B., & Sakai, S. (1999). Appl. Phys. Lett., 75.
[4] Kim, J. S., & Yoon, S. G. (2000). Vac. Soc. Technol., B, 18, 216.
[5] Wu, T. B., Wu, C. M., & Chen, M. L. (1996). Appl. Phys. Lett., 69, 2659.
[6] Chen, K. H., Chen, Y. C., Yang, C. F., & Chang, T. C. (2008). J. Phys. Chem. Solids, 69,
461.
[7] Yang, C. F., Chen, K. H., Chen, Y. C., & Chang, T. C. (2007). IEEE Trans. Ultrason. Fer‐
roelectr. Freq. Control, 54.
[8] Yang, C. F., Chen, K. H., Chen, Y. C., & Chang, T. C. (2008). Appl. Phys. A-Mater. Sci.
Process, 90.
[9] Chen, K. H., Chen, Y. C., Chen, Z. S., Yang, C. F., & Chang, T. C. (2007). Appl. Phys.
A-Mater. Sci. Process, 89, 533.
[10] Wu, S., Lin, Z. X., Lee, M. S., & Ro, R. (2007). Appl. Phys. Lett., 102, 084908.
[11] Lee, S., Song, E. B., Kim, S., Seo, D. H., Seo, S., Won, K. T., & Wang, K. L. (2012). Appl.
Phys. Lett., 100, 023109.
[12] Yang, Y., Jin, L., & Yang, X. D. (2012). Appl. Phys. Lett., 100, 031103.
[13] Scotta, J. F., Paz, C. A., & de Araujoa, B. M. (1994). J. Alloys, Compounds, 211 451.
[14] Araujo, C. A., Cuchiaro, J. D., Mc Millian, L. D., Scott, M. C., & Scott, J. F. (1995).
Nature (London), 374, 627.
[15] Park, B. H., Kang, B. S., Bu, S. D., Noh, T. W., Lee, J., & Jo, W. (1999). Nature (London),
401, 682.
[16] Leu, C. C., Yao, L. R., Hsu, C. P., & Hu, C. T. (2010). J. Electrochem. Soc., 157, 3, G85.
[17] Chen, K. H., Chen, Y. C., Yang, C. F., & Chang, T. C. (2008). J. Phys. Chem. Solids, 69.
[18] Yang, C. F., Chen, K. H., Chen, Y. C., & Chang, T. C. (2007). IEEE Trans. Ultrason. Fer‐
roelectr. Freq. Control, 54 1726.
[19] Yang, C. F., Chen, K. H., Chen, Y. C., & Chang, T. C. (2008). Appl. Phys. A, 90 329.
[20] Chen, K. H., Chen, Y. C., Chen, Z. S., Yang, C. F., & Chang, T. C. (2007). Appl. Phys. A,
89 533.
[21] Watanabe, T., Funakubo, H., Osada, M., Noguchi, Y., & Miyayama, M. (2002). Appl.
Phys. Lett., 80 1.
 The Influence of Vanadium Doping on the Physical and Electrical Properties 447
http://dx.doi.org/10.5772/52203

[22] Kim, S. S., Song, T. K., Kim, J. K., & Kim, J. (2002). J. Appl. Phys., 92 4.

[23] Noguchi, Y., & Miyayama, M. (2001). Appl. Phys. Lett., 78 13.

[24] Velu, G., Legrand, C., Tharaud, O., Chapoton, A., Remiens, D., & Horowitz, G.
(2001). Appl. Phys. Lett., 79 659.

[25] Chen, K. H., Yang, C. F., Chang, C. H., & Lin, Y. J. (2009). Jpn. J. Appl. Phys., 48
091401.

[26] Miao, J., Yuan, J., Wu, H., Yang, S. B., Xu, B., Cao, L. X., & Zhao, B. R. (2001). Appl.
Phys. Lett., 90 022903.

[27] Chen, K. H., Chen, Y. C., Chia, W. K., Chen, Z. S., Yang, C. F., & Chung, H. H. (2008).
Key Eng. Mater., 368-372.

[28] Wu, S. Y. (1974). IEEE Trans. Electron Devices, 21 499.

[29] Wu, S. Y. (1976). Ferroelectrics, 11 379.

[30] Sugibuchi, K., Kurogi, Y., & Endo, N. (1975). J. Appl. Phys. 46 2877. .

[31] Park, B. H., Kang, B. S., Bu, S. D., Noh, T. W., Lee, L., & Joe, W. (1999). Nature (Lon‐
don), 401 682.

[32] Noguchi, Y., Miwa, I., Goshima, Y., & Miyayama, M. (2000). Jpn. J. Appl. Phys, 39
L1259.

[33] Noguchi, Y., & Miyayama, M. (2001). Appl. Phys. Lett., 78 1903.

[34] Friessnegg, T., Aggarwal, S., Ramesh, R., Nielsen, B., Poindexter, E. H., & Keeble, D.
J. (2000). Appl. Phys. Lett., 77 127.

[35] Watanabe, T., Funakubo, H., Osada, M., Noguchi, Y., & Miyayama, M. (2002). Appl.
Phys. Lett., 80 1.

[36] Kim, S. S., Song, T. K., Kim, J. K., & Kim, J. (2002). J. Appl. Phys., 92, 4.

[37] Noguchi, Y., & Miyayama, M. (2001). Appl. Phys. Lett., 78 13.

[38] Rost, T. A., Lin, H., & Rabson, T. A. (1991). Appl. Phys. Lett., 59 3654.

[39] Rost, T. A., Lin, H., Rabson, T. A., Baumann, R. C., & Callahan, D. C. (1991). IEEE
Trans. Ultrason. Ferroelectr. Freq. Control, , 38

[40] Fleischer, S., Lai, P. T., & Cheng, Y. C. (1994). J. Appl. Phys., 73 8353.

[41] Mihara, T., & Watanabe, H. (1995). Part I, Jpn. J. Appl. Phys., 34 5664.

[42] Lin, Y. B., & Lee, J. Y. (2000). J. Appl. Phys., 87 1841.

 Provisional chapter
Chapter 20

Nanoscale Ferroelectric Films, Strips and Boxes

Nanoscale Ferroelectric Films, Strips and Boxes

Jeffrey F. Webb
Jeffrey F. Webb
Additional
Additionalinformation
informationis is
available at the
available endend
at the of the chapter
of the chapter

http://dx.doi.org/10.5772/52040

1. Introduction
A major characteristic of ferroelectric materials is that they posses a non-zero polarization
in the absence of any applied electric field provided that the temperature is below a certain
critical temperature[1]; in the literature this is often called a spontaneous polarization, or an
equilibrium polarization. Another important defining characteristic is that this polarization
can be reversed by applying an electric field. This is the basis of a useful application
of ferroelectrics in which binary information can be stored according to the polarization
direction which can be switched between two states by an electric field. For example, a
thin film of ferroelectric can be switched to different states at different regions by suitably
patterned electrodes, thus creating a ferroelectric random access memory[2].
With the increasing miniaturization of devices it becomes important to investigate size-effects
in ferroelectrics. Thin film geometries are of interest in which one spatial dimension is
confined, as well as strip geometries in which two-dimensions are confined, and, what here
we will call box geometry in which all three dimensions are confined. By confinement we
mean that surfaces of the ferroelectric that intersect on at least one line going through the
central region of the ferroelectric are sufficiently close to this region to make their presence
cause a non-negligible effect on the ferroelectric as a whole so that the behaviour is different
from what would be expected in a bulk region far from any surface. The geometries chosen
are typical of the sort that can be fabricated in micro or nanoelectronics and fit conveniently
into a Cartesian coordinate system.
The aim of this chapter is to show how the equilibrium polarization can be calculated in
general for a confined volume of ferroelectric and this is applied to the three aforementioned
geometries. In fact such calculations for thin films are well established[3–7]; here they are
included with the other geometries, which are not so well studied, for completeness, and
because they fit logical into the theoretical framework to be presented. A general problem
of a similar nature to the one of interest here, but applied to spheres and cylinders has been
considered by Morison’s et al.[8]. This work employed approximate analytical solutions to
the problem of calculating the polarization and avoided a full three-dimensional application
of the general theory.

©2012 Webb, licensee InTech. This is an open access chapter distributed under the terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
© 2012 F. Webb;
distribution, licensee InTech.
and reproduction in anyThis is an open
medium, access
provided thearticle distributed
original under the
work is properly terms of the Creative
cited.
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
450 Advances in Ferroelectrics
2 Advances in Ferroelectrics

T > TC T < TC

P❛r❛❡❧❡❝tr✐❝ ♣❤❛s❡ ❋❡rr♦❡❧❡❝tr✐❝ ♣❤❛s❡

Figure 1. A two-dimensional representation of how a crystal structure changes symmetry when passing between the
paraelectric (T > TC ) and ferroelectric (T < TC ) phases

2. Foundations of the Landau-Devonshire theory of ferroelectrics

2.1. Bulk ferroelectrics
Since Landau-Devonshire theory is the theoretical basis for the work in this chapter it will
be introduced here. Further details can be found elsewhere such as in Refs. [1, 9, 10]. In this
section we consider the case of a bulk ferroelectric; the effect of surfaces will be introduced
after that.
It is common to state that the starting point for Landau-Devonshire theory is the free
energy per unit volume of a bulk ferroelectric expressed as an expansion in powers of the
polarization P. The observed equilibrium polarization P0 is then given by the value of P
that minimizes the free energy. Here, however, following Strukov and Lenanyuk[10], we
outline how this expansion comes from a statistical thermodynamic treatment involving an
incomplete Gibbs potential, since this gives more insight into the theory. First a few more
details about the nature of ferroelectrics.
When a ferroelectric crystal is above the critical temperature TC there is no spontaneous
polarization; this is the paraelectric or high symmetry phase in which the crystal structure
is of higher symmetry than the ferroelectric phase below TC since the appearance of the
spontaneous polarization lowers the symmetry, as is evident from the two-dimensional
representation in Fig. 1. Thus we see that during the transition from the paraelectric to
ferroelectric state, a structural phase transition occurs. A consequence of this is that as the
temperature approaches TC the structure becomes easy to distort giving rise to anomalous
peaks in some of the properties such as the dielectric function ǫ, as illustrated in Fig. 2. In
fact, in the ferroelectric phase, a crystal may have different domains such that the polarization
in adjacent domains is not in the same direction[9], however it is possible to produce
single-domain crystals—by cooling through TC in the presence of an electric field in one
of the possible polarization directions for instance—and that is what we consider here.
 Nanoscale Ferroelectric Films, Strips and Boxes 451
Nanoscale Ferroelectric Films, Strips and Boxes 3
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T
TC
Figure 2. A peak in the dielectric function ǫ occurs as T → TC .

In the simplest case, then, a ferroelectric phase transition can be described by a single
parameter that in Fig. 1 would be describable by the displacement of the sublattice from
its central position. Since the paraelectric phase is of higher symmetry than the ferroelectric
phase we can consider it to be more orderly and so the parameter is sometimes referred to
as an order parameter. Actually the atoms are ions with charge and the corner-atom lattice
would have a charge opposite to that of the interior sub-lattice. From the macroscopic point
of view the corner atoms can be considered to produce a focus of charge at the center of
each rectangle of opposite sign to the atoms that are displaced during the phase transition
(see Fig. 1 where the centers of positive and negative charge are marked for the ferroelectric
phase). For this reason the order parameter is often taken to be the polarization, which
is the dipole moment per unit volume. For the time being, however, we will stay with
the displacement representation of the order parameter as this is more directly related to
the structural transition. If the displacement is denoted by η then it is clear that in the
ferroelectric phase η 6= 0 and in the paraelectric phase η = 0.
The description above implies that each center ion is displaced in the same direction and this
is the case for what are termed displacive ferroelectrics. There is another possibility, however,
in which the displacement is not the same for every unit cell. For example, in some cells the
displacement could be up while in others it could be down. Macroscopically ferroelectric and
paraelectric phases can still result but now the ferroelectric phase occurs when statistically
there are more displaced in one direction than in the other; and the paraelectric phase
corresponds to the number of atoms displaced upwards is statistically equal to the number
displaced downwards. In this case the ferroelectric is called an order-disorder ferroelectric.
In terms of the macroscopic crystal symmetry however displacive and order-disorder
ferroelectrics are equivalent and both can be described in general by Landau-Devonshire
theory. The crystal structure of order-disorder ferroelectrics tends to be more complicated
than for the displacive type[9, 10].
The basis of the Landau-Devonshire theory is that in the phase transition the ferroelectric
phase may be represented by a distorted symmetrical phase. As outlined above this is
a macroscopic view and the theory is phenomenological, as will be brought out further
below. It turns out that the symmetry elements lost by the crystal at the transition
temperature is sufficient information for a description of the anomalies of practically all
of the thermodynamic properties of the crystal[10].
452 Advances in Ferroelectrics
4 Advances in Ferroelectrics

To make further progress consider the crystal as a system of N interacting particles

with potential energy U (r1 , . . . , r N ). According to Gibbs[11, Chapter 8], the equilibrium
thermodynamic potential at pressure p and temperature T associated with the potential
energy of interaction of the particles is given by

Φ( p, T ) = −k B T ln Z, (1)

where k B is Boltzmann’s constant and

Z ∞
Z= exp [−U (r1 , . . . , r N )/(k B T )] ∏ dri . (2)
−∞ i

The expression for Z in Eq. (2) comes from the probability that the value of the radius vector
of the first particle lies between r1 and r1 + dr1 and similarly for the other vectors, being given
by

dw = C exp [−U (r1 , . . . , r N )/(k B T )] ∏ dri . (3)

i

Since integration of all of the variables must yield unity, C = 1/Z. The probability
distribution can therefore be written as

dw = exp [Φ( p, T ) − U (r1 , . . . , r N )] /(k B T ) ∏ dri .


(4)
i

A Gibbs thermodynamic potential for nonequilibrium states can also be formulated by using
a larger number of variables than only p and T. The new variables are introduced via a linear
transformation:

r1 , . . . , r N → ξ 1 , . . . , ξ 3N . (5)

We choose one of these variables to be η, which describes the nonequilibrium state of interest
as explained above, by setting ξ 1 = η. Now


dw = exp [Φ( p, T ) − U (η, ξ 2 . . . , ξ 3N )] /(k B T ) dηdξ 2 · · · ξ 3N , (6)

the probability that the variables will lie in the ranges η to η + dη, ξ 2 to ξ 2 + dξ 2 , and so on.
Focusing on the variable of interest η the probability of finding the system in a state in which
this variable is in the range η + dη is
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Z ∞ 
dw(η ) = dη exp [Φ( p, T ) − U (η, ξ 2 , . . . , ξ 3N )] /(k B T ) dξ 2 · · · ξ 3N . (7)
−∞

The thermodynamic potential is now also a function of η, and we write

Z ∞ 
Φ( p, T, η ) = −k B T ln exp [−U (η, ξ 2 , . . . , ξ 3N )] /(k B T ) dξ 2 · · · ξ 3N , (8)
−∞

and


dw(η ) = exp [Φ( p, T ) − Φ( p, T, η )] /(k B T ) dη. (9)

Here it can be seen that the value of η that minimizes Φ( p, T, η ) will maximize the
distribution function and so this value corresponds to the equilibrium value of η. If Φ( p, T, η )
is known, the usual equilibrium function Φ( p, T ) can be found, using Eq. (9), from

Z ∞ 
Φ( p, T ) = −k B T ln exp [−Φ(η )] /(k B T ) dη. (10)
−∞

Now, let the equilibrium value of η be η0 —which corresponds to the minimum value of
Φ( p, T, η )—and expand Φ( p, T, η ) in a series about the point η = η0 :

1
Φ( p, T, η ) = Φ( p, T, η0 ) + ∆Φ( p, T, η − η0 ) = Φ( p, T, η0 ) + A( p, T )(η − η0 )2 + · · · . (11)
2

Using Eq. (10), Φ( p, T ) can be written as

Z ∞ 
Φ( p, T ) = Φ( p, T, η0 ) − k B T ln exp [−∆Φ( p, T, η − η0 )] /(k B T ) dη. (12)
−∞

In Eq. (12) the first term is the minimum of the potential as a function of p, T and η, and
we are interested in the minimizing value η = η0 for given values of p and T. The second
term is the contribution to the thermodynamic potential of fluctuations in η with order of
magnitude given by the thermal energy per degree of freedom K B T/2. However since we are
dealing with a large number of particles in a macroscopic sample (∼ 1023 ) the fluctuations
are very small and the second term can be neglected to give

Φ( p, T ) = Φ( p, T, η0 ). (13)
454 Advances in Ferroelectrics
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Note that if the total number of degrees of freedom (left unintegrated as the single degree η
was) required to describe the system is comparable to N, then the neglect of the second term
is no longer valid and Eq. (10) must be used in place of Eq. (13). We will not be concerned
with such situations here, but very close to the transition temperature the Landau-Devonshire
theory breaks down and the fluctuations must be considered, which can be done with the
aid of Eq. (10), as discussed in Ref. [10].
In general thermodynamic functions which contain extra variables that remain unintegrated
as η was above, are nonequilibrium thermodynamic functions known as incomplete
functions. The general form is

Φ( p, T, η1 , η2 , . . . , , ηn ) = Φ0 ( p, T ) + Φ1 ( p, T, η1 , η2 , . . . , , ηn ). (14)

The equilibrium values of the ηi are found by minimizing Φ( p, T, η1 , η2 , . . . , , ηn ) according

to
∂Φ ∂Φ
= 0, . . . , = 0, (15)
∂η1 ∂ηn
which determine a set of minimizing values ηoi ( p, T ). Substituting these values into Eq. (14)
determines the equilibrium thermodynamic function

Φ( p, T ) = Φ0 ( p, T ) + Φ1 ( p, T, η01 , η02 , . . . , , η0n ). (16)

This does not take fluctuations of the η0i into account but the corresponding error will be
small provided that n ≪ 3N.
Although we are only considering a ferroelectric phase transition of the simplest type
describable by introducing a single extra variable η into the thermodynamic potential the
general form shows how to treat more complicated cases for which the polarization may
occur in more ways than along one line, as we will see later. Polarization in three-dimensionss
can be treated with three parameters, η1 to η3 .
Returning to a one-component case we now show how the form of the thermodynamic
potential can be worked out. As explained, in a ferroelectric phase transition we are dealing
with displacements of certain atoms or groups of atoms; the structure of the nonsymmetric
phase can be obtained from the structure of the symmetric phase by small displacements.
Although the same lowering of symmetry in a phase transition can occur with different types
of ordering implying that the choice of the order parameter is ambiguous, it turns out that
the character of the anomalies of the physical properties in the transitions can be elucidated
for any particular relationship between the order parameter and the displacements as long
at the appearance of the order parameter leads to a symmetry change corresponding to that
of the crystal’s[10, 12].
In view of this we can take the order parameter as the extra variable of the incomplete
thermodynamic potential. The phase transition can then be described at a given pressure
if Φ( p, T, η ) has a minimum at η = 0 in the symmetric phase (T > TC ), and at least two
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η η

T T
TC TC

(a) (b)

Figure 3. (a) Second order phase transition in which the order parameter decreases continuously to zero. (b) First order phase
transition in which the order parameter displays a discontinuity. There is a continuous decrease in η before, which means that
it is a first-order transition close to a second order transition. at T = TC .

minima1 at η 6= 0 in the nonsymmetric phase (T < TC ). The function Φ( p, T, η ) must be

consistent with this as T changes through the transition temperature so that it is determined
for both the symmetric and nonsymmetric phases. These requirements place restrictions on
the dependence of the potential Φ on η: Φ is a scalar function characterizing the physical
properties of ferroelectric crystals, and as such must be invariant under any symmetry
operations on the symmetric phase consistent with the crystal symmetry of this phase.
Before exploring further the form of Φ that describes the phase transition the difference
between first and second order phase changes will be discussed. In a second order transition
η decreases continuously to zero as the temperature is lowered through TC ; in a first order
transition, on the other hand, there is a discontinuous jump of η to zero at T = TC . Both
situations are illustrated in Fig. 3. The first order transition shown in this figure is in fact
close to a second order transition and so there is a continuous decrease in η before the
jump and the jump is not very large. Crystals can exhibit first or second order transitions
depending on the crystal structure[9, 10]. Either case can be treated by Landau-Devonshire
theory, as long as the first order case is close to a second order transition. Turning back
now to the development of an expression for Φ, we see that in the vicinity of a second order
transition it is permissible to deal only with small lattice distortions, that is, small η. Hence
the thermodynamic potential can be expanded into a series in η, with p and T treated as
parameters, and we obtain

1
Φ( p, T, η ) = Φ( p, T, 0) + Φ′ ( p, T, 0)η + Φ′ ( p, T, 0)η 2 + · · · . (17)
2

To represent a given crystal this expression must be invariant under symmetry operations
that correspond to the symmetry elements of the crystal. A ferroelectric phase transition
resulting in a spontaneous polarization occurs as long as the order parameter transforms as
a vector component. Only crystal symmetries for which this is true are ferroelectric and then
the order parameter can be considered to be equivalent to a component of the spontaneous
polarization (this point is discussed in more detail in Refs.[9, 10, 12]).
1
Part of the definition of a ferroelectric is that it has a reversible polarization in the nonsymmetric phase so that at
least two minimum are required; otherwise the reverse direction would not be an equilibrium state.
456 Advances in Ferroelectrics
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2/m 1 2 m 1̄
η=P P P −P −P
Table 1. Transformation of the order parameter

Φ − Φ0 Φ − Φ0

T > TC T < TC

− P0 P0
P P

Figure 4. The form of Φ − Φ0 that satisfies the basic requirements for a ferroelectric phase transition. When T > TC there is
single minimum at P = 0 and there is no spontaneous polarization; for T < TC a spontaneous polarization can exist at one of
the minima at P = ± P0 .

To make further progress we consider a definite example of a symmetry which allows the
order parameter to transform as a vector and so corresponds to a polarization having a
single component; to reflect this correspondence we also make the notation change η → P
where P is the polarization component.2 Consider a second-order phase transition such
that the change into the ferroelectric state at the critical temperature is accompanied by a
symmetry change from the group 2/m (symmetry elements: 1, 1̄, m, 2) to 2 (symmetry
elements: 1, 2). The ferroelectric triglycine sulphate shows this symmetry change during its
phase transition[13, 14]. During the transition to the nonsymmetric phase the crystal loses
the inversion center and the plane of symmetry, 1̄ and m. These disappearing symmetry
elements correspond to the symmetry operations that reverse the sign of the order parameter
η = P, as is shown in Table 1. Since Φ must be invariant under any transformations of the
symmetrical phase it is clear from this that it cannot include terms linear in P or odd powers
of P, since such terms would be changed by the operations m and 1̄.
Therefore the first η = P dependent term in Eq. (17) will be of the form A( p, T ) P2 .
For simplicity we now assume that the pressure is at some fixed value and discuss the
temperature dependence. The expression for Φ must reflect the fact that at T > TC there is
a minimum at P = 0 so that the equilibrium state (represented by the minimum) is one in
which P = 0, and when T < TC there will be two minima for which P 6= 0 so that the possible
equilibrium states occur at nonzero values of P. This is satisfied if A( T ) passes continuously
from A( T < TC ) < 0 to A( T > TC ) > 0 when T > TC , with A( T = TC ) = 0, provided that
the next allowable term B( T ) P4 (remembering that odd terms have the wrong symmetry)
is included with B( T ) > 0, as can be seen from Fig. 4. This results in a thermodynamic
potential of the form

Φ = Φ0 + A ( T ) P2 + B ( T ) P4 . (18)

2
The general case in which the polarization has three components would be covered by three order parameters and
the correspondence would be (η1 → P1 , η2 → P2 , η3 → P3 ), with P = ( P1 , P2 , P3 ).
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Generally the exact form of the temperature dependence may be difficult to find. However
near the phase transition temperature a series expansion in powers of T − TC (at a given
pressure) can be used to give

A( T ) = A( TC ) + A1 ( T − TC ) A2 ( T − TC )2 + · · · (19)
2
B( T ) = B( TC ) + B1 ( T − TC ) B2 ( T − TC ) + · · · . (20)

Taking into account the above mentioned properties: A( TC ) = 0 and B( TC ) > 0, the simplest
forms retaining the essential non-zero first terms gives

1
A( T ) = A1 ( T − TC ) = a( T − TC ) (21)
2
1
B( T ) = B( TC ) = b. (22)
4

The numerical factors are introduced for convenience, as will be clear shortly. We thus obtain,
for a given pressure,

1 1
Φ( T, P) = Φ0 ( T ) + a( T − TC ) P2 + bP4 . (23)
2 4

Usually it is sufficient to consider the energy due to the presence of the spontaneous
polarization per unit volume (we are dealing with a bulk sample assumed uniform of the
crystal volume) so that it is convenient to write, for a volume v of ferroelectric,

Φ( T, P) − Φ0 ( T ) 1 1
F= = α( T − TC ) P2 + βP4 , (24)
v 2 4

where α = a/v > 0, β = b/v > 0, and we refer to F as the Gibbs free energy density.
The equilibrium polarization P0 is now found by minimizing F from the conditions

∂F ∂2 F
= 0, and > 0.
∂P ∂P2

From this we find

(
0 for T > TC ,
P02 = (25)
− α( T −
β
TC )
for T < TC .

Here we see that it is necessary to differentiate to find P0 which explains why the numerical
coefficients 1/2 and 1/4 were introduced into the expansion of the thermodynamic potential.
The form of F in Eq. (24) is sufficient to describe a second order phase transition since P0 → 0
continuously as T → TC . For second order transitions in which there is a discontinuous jump,
Eq. (24) is insufficient. However a first-order transitions near to a second-order transition the
458 Advances in Ferroelectrics
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Figure 5. A component of polarization that is directed along a normal to the plane of the film when T < TC . The resulting
surface charges with opposite sides having signs of opposite charge, creates an electric field which in the opposite direction to
the polarization.

phase change can be described by adding a further term in P6 (a term in P5 , since it is an

odd power, does not fulfill the symmetry requirements) which results in an energy density
given by

1 1 1
F= α( T − TC ) P2 + βP4 + γP6 . (26)
2 4 6
But, whereas β > 0 for a second order transition, for F to exhibit a discontinuous jump it is
necessary to choose β < 0 with γ > 0. More on this can be found in Lines and Glass[9].
We have thus shown in some detail how it is that a relatively simple free energy expression
can account for the main characteristics of a ferroelectric, with the observed equilibrium
polarization found by minimizing the free energy. Other terms can be added to the free
energy to account for various external influences. For example an external electric field with
component E along the direction of polarization can be accounted by first substituting the
equilibrium polarization P0 into F and adding a term EP0 . The corresponding susceptibility
∂2 F
is then given by χ = ∂E 2.

Note that Landau-Devonshire theory is a phenomenological theory of the macroscopic

properties of the ferroelectric: the coefficients, α, β, etc., are not derivable from it; instead
they must be found from experiment, or, in some cases, can be found from first-principle
calculations[1].

2.2. Extension to thin films

Here a free-standing thin film is considered. If the equilibrium polarization below TC has a
component that is aligned with a normal to the plane of the film, then depolarization effects
due to the space charge that appears at the surfaces, as illustrated in Fig. 5, must be taken
into account. At first we avoid this complication by assuming a polarization that is in-plane.
Also to remain with a one dimensional treatment for now we assume that this this is along
the x direction of a Cartesian coordinate system and that the plane surfaces of the film are
normal to the z axis at z = 0 and z = L, where L is the thickness of the film. The effect of the
surfaces is such that the polarization near them may differ from the bulk value. For the case
just described this implies that P = P(z). It can be shown[1, 3, 15] that this can be accounted
for in the free energy by adding surface terms involving P2 integrated over the surfaces, and
a gradient term |dp/dz|. The free energy is now given by
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L
Z Z Z Z Z h
1D i
G= dxdy f ( P, dP/dz) dz + dx dy P2 (0) + P2 ( L ) , (27)
0 2 d
in which
 2
1 1 1 1 dP
f ( P, dP/dz) = AP2 + BP4 + CP6 + D , (28)
2 4 6 2 dz
the temperature dependence is in A through A = a( T − TC ), and the integrals over x and y
are factored out of the three dimensional integral over a volume of the film because P does
not vary in these directions.
RR Thus any surface area can be chosen to integrate over so that, if
this areas is S, then dxdy = S, and we can write a free energy per unit area as
" 2 #  2
P2 ( L )
Z L
P (0)
 
G 1 1 1 1 dP 1
F= = dz AP2 + BP4 + CP6 + D + D + . (29)
S 0 2 4 6 2 dz 2 d d

Here since the film is free standing with identical surface properties for both surfaces the
surface terms at z = 0 and z = L involve the same factor, 1/d, which simplifies the problem.
If the film was not free standing, with for example, one surface an interface with a substrate,
then this could be modeled by introducing different factors[6] so that the last term in square
brackets in Eq. (29) would be replaced by P(0)/d1 + P( L)/d2 .
The equilibrium polarization is still the P that minimizes F, but now the problem is to find
the function P(z) = P0 (z) that minimizes F rather than a finite set of values. So we are
dealing with the minimization of a functional and the classical methods from the calculus of
variations[16, Chapter 4] may be used, which cast the problem into the form of a differential
equation known as the Euler-Lagrange equation and the function that minimizes F is the
solution to this equation for a set of boundary conditions that also need to be specified. In
this case, as will be shown below the boundary conditions used are implicit in Eq. (29) and are
equivalent to allowing the polarization to be free at the film surfaces rather than fixed. More
details on the method for the general three dimensional case are given in Section 4. Here we
simply state that the classical methods lead to the following Euler-Lagrange equation and
boundary conditions for the equilibrium polarization in the film:

d2 P0
D − AP0 − BP03 − CP05 = 0. (30)
dz2

With boundary conditions

dP0 1
− P0 = 0, at z = 0, (31)
dz d

and

dP0 1
+ P0 = 0, at z = L. (32)
dz d
460 Advances in Ferroelectrics
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P0 (z) P0 (z)

d<0 d>0

z z
d d
Figure 6. The extrapolation length d for one of the film surfaces at z = 0. For d < 0 the polarization turns down as the surface
is approached; for d > 0 it turns up; this is also true for the surface at z = L (not shown). Here the extrapolated gradient line
crosses the z-axis at z = 0 + d; for the surface at z = L it would cross at z = L + d.

It can be seen from the boundary conditions that d can be interpreted as an extrapolation
length, as illustrated in Fig. 6. For d < 0 the polarization turns upwards as it approaches a
surface; for d > 0 it turns down as a surface is approached.
Now the task is to solve the differential equation—Eq. (30) which is nonlinear—subject to the
boundary conditions. For first order transitions in which C 6= 0 the equation must be solved
numerically[17, 18]. However, for the simpler case of second-order transitions (C = 0) even
though the equation is still nonlinear, an analytical solution can be found in terms of elliptic
functions[3, 19, 20] and is given by

 
z − L/2
P0 (z) = P1 sn K (λ) − ,λ , for d < 0, (33)
ζ

where sn is the Jacobian elliptic function with modulus λ = P1 /P2 , K (λ) is the complete
elliptic integral of the first kind (see Ref. [21] for more on elliptic functions and integrals),

s
A A2 4G
P12 =− − 2
− , (34)
B B B
s
A A2 4G
P22 = − + − , (35)
B B2 B
r
1 2D
ζ= , (36)
P2 B

and G is found by substituting it into the boundary conditions and solving the resulting
transcendental equations numerically.
A plot of the polarization profile according to Eq. (33) is given in Fig. 7 for parameter values
given in the figure caption. The polarization throughout the film decreases continuously to
zero as the temperature increases and approaches TC . So there are two states: a ferroelectric
state below TC for which there is a polarization everywhere in the film and a paraelectric
state above TC for which the polarization is zero everywhere.
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P0 (z/ζ 1 )/P0∞

0.4

0.3

0.2 z/ζ 0
0 0.25 0.5 0.75 1
Figure 7. Polarization in a thin film plotted from Eq. (33) and the boundary conditions in Eqs. (31) and (32). Dimensionless
variables and parameters used are: P0∞ = ( aTC /B)1/2 (the spontaneous polarization for a bulk ferroelectric), ζ 0 =
[2D/( aTC )]1/2 , ζ 1 = P0∞ /P2 (P2 is given by Eq. (35)), ∆T ′ = ( T − TC )/TC = −0.4, L′ = L/ζ 0 = 1, d′ = 4L′ ,
G ′ = 4GB/( a/TC )2 = 0.105 (found from the boundary conditions).

The case d > 0 is complicated by the appearance of a surface term between TC and a lower
temperature TC0 for which the regions near the film surfaces have a spontaneous polarization
but the polarization in the interior is still zero. Only below TC0 is there a nonzero polarization
in the interior of the film. The form of the solution, although still expressible in terms of an
elliptic function is somewhat different for the surface state, as is discussed elsewhere[3, 19, 20]
The above was for in-plane polarization which, as has been explained, avoids the need to
consider a depolarization field induced by the polarization. In general, however, there may
be an out-of-plane component that would give rise to a depolarization field. Theoretical
descriptions of the depolarization field have been considered by several authors[5, 7, 22, 23].
For the case in which there are no free charges at the surfaces it can be shown[5, 22] from
Maxwell’s equations that a term

1 h
i
P P − h Pi (37)
2ǫ0 ǫ∞

added to the energy density in Eq. (28) accounts for the effect of the depolarization field
provided that P is now taken to be directed along a normal to the plane of the the film (as it
is in Fig. 5). In Eq. (37) ǫ0 is the permittivity of free space and ǫ∞ is the background dielectric
constant of the film[5, 24], and
Z L
1
h Pi = P dz, (38)
L 0

which is the average value of P(z) in the film.

3. The free energy density appropriate for a three-dimensional treatment

of a ferroelectric crystal
The general form of the free energy density for the interior of a ferroelectric crystal in
three-dimensions can be written as series expansion in components of the polarization,
462 Advances in Ferroelectrics
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together with terms taking into account the influence of surfaces and depolarization fields.
The region occupied by the interior of the ferroelectric (the surface energy will appear later
as a surface energy density integrated over the surface), is taken to be the interior of a
rectangular box defined by

V = x | xi ∈ li− , li+ , i = 1, 2, 3 ,


(39)

so that the sides of the box are given by li = li+ − li− , i = 1, 2, 3. Extending the formalism in
the previous sections to three dimensions, the energy density can be written

f x, P, Px1 , Px2 , Px3 , hPi = f series x, P + f grad x, Px1 , Px2 , Px3 + f dep x, P, hPi (40)

The notation used for the arguments, which will be useful when applying calculus of
variations methods in the next section, is as follows: x = ( x1 , x2 , x3 ), for a position in the
crystal in Cartesian coordinates; P = ( P1 , P2 , P3 ), the polarization vector; Pi = Pi ( x1 , x2 ,
x3 ),
i = 1, 2, 3; Pxi = ∂P/∂xi , i = 1, 2, 3, and the averages vector is hPi = h P1 i, h P2 i, h P3 i in
which
Z l+
1 i
h Pi i = Pi dxi . (41)
li li−

The terms on the right of Eq. (40) are given next. The first of these terms f series is the series
expansion part of the free energy (due to the polarization, without a constant first term) in
terms of the components of the polarization. A general series expansion in these terms can
be written as
!
∞
1
f series x, P = ∑
i α1 >∑


A P
α1 ···αi α1 · · · Pαi . (42)
i =1 ···>α i

Here each αi runs from x1 to x3 and the notation α1 · · · αi indicates that all permutations
of Pα1 · · · Pαi of the ith term, which would otherwise appear as separate, have already been
summed: the inequalities insure that only one permutation is present for the ith term with
coefficient Aα1 ···αi . However in practice, depending on the crystal symmetry, terms which are
not separately invariant under the symmetry transformations of the symmetry group of the
crystal, will not appear.
The term f grad , a gradient term, is given by

"  #
1  ∂P 2  ∂P 2  ∂P 2
   
1 h

2 2 2
i
f grad x, Px1 , Px2 , Px3 = δ |∇P1 | + |∇P2 | + |∇P3 | = δ  + + .
2 2 ∂x1  ∂x2  ∂x3 
(43)
It is easy to show that 12 δ |∇P1 |2 + |∇P2 |2 + |∇P3 |2 is equal to the right hand side of
 

Eq. (43). Both forms are shown so that it can be seen that f grad involves gradient terms.
However the other form is sometimes convenient

to

work with. Note that in general there are
 ∂P 2  ∂P 2
   
other symmetry allowed terms such as  ∂x   ∂x 
1 2
. However usually such terms are ignored
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– a practice which will be followed here. Nonetheless, in the future it may be interesting to
study such terms to extended the formalism given here.
Finally f dep is the term due to the depolarization field for the general case in which the
polarization has components along x1 , x2 and x3 . It is given by

1 h


i
f dep x, P, hPi = P1 P1 − h P1 i + P2 P2 − h P2 i + P3 P3 − h P3 i . (44)
2ǫ0 ǫ∞

Having dealt with the energy density for the interior of the ferroelectric the remaining energy
density is the surface energy density at any point on the surface of the ferroelectric. This will
be proportional to P2 , where P = |P| and, as will be evident below, it is convenient to write
it as

δ
P2 (x)


f surf x, P = for x ∈ S, (45)
2d(x)

where S is the entire surface of the ferroelectric box given by

S = S x 1 = l − ∪ S x 1= l + ∪ S x 2 = l − ∪ S x 2 = l + ∪ S x 3 = l − ∪ S x 3 = l + (46)
1 1 2 2 3 3

where the sides of the box at xi = li∓ are given by

Sx j =l ∓ = x | xi = li∓ , xσ j (i) ∈ li− , li+ , j = 1, 2 ,

  
(47)
j

where we have introduced the cyclic operator σ which performs the operation x1 7→ x2 7→
x3 7→ x1 , so that

σ( xi ) = x j+1 (mod 3) ; (48)

also σ applied n times where n > 0 is denoted by σn , and the definition of the operator is
extended to when the xi are arguments of a function h such that



σ h ( x1 , . . . , x3 ) = h σ ( x1 ), . . . , σ ( x3 ) . (49)

It is easy to see that many of the terms in the free energy can be written in a shortened form
with this notation because successive terms can often be generated by cyclic permutations of
a starting term; later this operator notation will be useful when the free energy for the box is
inserted into the Euler-Lagrange equations in Section 5.
Showing the form of the free energy densities for the ferroelectric box helps pave a way for
dealing with the general problem of finding the minimum of the free energy density for an
arbitrary volume of ferroelectric, which will be discussed next.
464 Advances in Ferroelectrics
16 Advances in Ferroelectrics

4. The calculus of variations applied to the polarization of a ferroelectric

of arbitrary shape in three dimensions
The next step towards working out the equilibrium polarization for ferroelectric boxes and
strips—an extension of the theory for thin films—is to work out in general the free energy for
an arbitrary volume of ferroelectric. The minimization of this, as for the thin film, involves
the minimization of a functional, which involves the calculus of variations and will be dealt
with using classical methods.
It can be seen from the previous section that the general form of the free energy for a
ferroelectric in the region V in R3 bounded by the closed surface S is given by

Z
Z

G= f x, P, Px1 , Px2 , Px3 , hPi dV + f surf x, P dS. (50)
V S

Here G depends on whatever function P is, so the domain of G is a function space and the
equilibrium polarization distribution is that function P0 in the space which minimizes G.
At this point certain boundary conditions could be imposed on P according to the physical
situation. For a ferroelectric crystal no such conditions are imposed which implies that P is
free at the boundaries. However natural boundary conditions (that do not fix P) will emerge
from the minimization as we will see.
The minimization of the functional G in Eq. (50) will be carried out using a classical technique
due to Euler[16] which involves considering a variation around P0 = ( P01 , P02 , P03 ) in
function space. To this end we write

P(x) = P0 (x) + ǫη (x), (51)

in which ǫ is a variable parameter and η = (η1 , η2 , η3 ) is an arbitrary vector function. G can

now be expressed as

Z

G (ǫ) = f x, P0 + ǫη, P0x1 + ǫηx1 , P0x2 + ǫηx2 , P0x3 + ǫηx3 , hP0 + ǫη i , (52)
V

where
∂P0
P0xi = . (53)
∂xi
The key idea for finding the minimizing function P0 is that a necessary condition for its
existence is


dG 
= 0.
dǫ ǫ=0
 Nanoscale Ferroelectric Films, Strips and Boxes 465
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Applying this condition to Eq. (52), and using the chain rule when differentiating the
integrands, we find


dG 
Z       
= (∇P0 f ) · η + ∇P0x1 f · ηx1 + ∇P0x2 f · ηx2 + ∇P0x3 f · ηx3
dǫ ǫ=0
 V
  Z
+ ∇hP0 i f · hη i dV + (∇P0 f surf ) · η dS = 0, (54)
S

in which the notation

∂f ∂f ∂f
( ∇A f ) · B = B1 + B2 + B (55)
∂A1 ∂A2 ∂A3 3
has been introduced.
If all terms in the integrands in Eq. (54) could be written as a dot product with η, as is
the case for the first and last terms on the right of Eq. (54), then η would appear as a
single
R factorR in the volume and surface integrands. Eq. (54) could then be written in the form
V η · Λ 1 + S η · Λ2 , where Λ1 and Λ2 do not involve η. As shown below, the Euler-Lagrange
equations and boundary conditions will then follow by setting Λ1 = Λ2 = 0, which will
satisfy Eq. (54). Therefore we now proceed to express Eq. (54) in the η factored form.
To facilitate this we start by writing Eq. (54) as

dG 
Z  Z
= ( ∇ P0 f ) · η + I 1 + I 2 dV + (∇P0 f surf ) · η dS = 0, (56)
dǫ ǫ=0 V S

where
     
I 1 = ∇P0x1 f · ηx1 + ∇P0x2 f · ηx2 + ∇P0x3 f · ηx3 , (57)
 
I 2 = ∇hP0 i f · hη i. (58)

Now we want to find Λ1 and Λ2 such that I 1 = η · Λ1 and I 2 = η · Λ2 .

Starting with I 1 , by expanding the dot products and re-grouping the terms, it is easy to
show that it can be rewritten as

I 1 = (∇Po1 x f ) · (∇η1 ) + (∇Po2 x f ) · (∇η2 ) + (∇Po3 x f ) · (∇η3 ) , (59)

in which the following notation has been used:

 
∂A1 ∂A2 ∂A3 ∂A1 ∂A2 ∂A3
∇A = , , = x̂ + x̂ + x̂ , (60)
∂x1 ∂x2 ∂x3 ∂x1 1 ∂x2 2 ∂x3 3

the normal gradient operation, where x̂i , i = 1, 2, 3, are unit vectors along the corresponding
xi axes of a Cartesian coordinate system. Also,
466 Advances in Ferroelectrics
18 Advances in Ferroelectrics

 
∂ ∂ ∂
∇ Aix = , , , (61)
∂Aix1 ∂Aix2 ∂Aix3

with Aix j = ∂Ai /∂x j .

Now, we utilize the vector identity

(∇φ) · A ≡ ∇ · (φA) − φ (∇ · A) , (62)

together with the divergence theorem

Z I
∇ · A dV = A · (n̂ dS) , (63)
V S

where at each point on the surface S, n̂ = n̂ x|S is a unit normal vector directed outwards
(from the enclosed volume). Using Eqs. (62) and (63), it follows that

" # " #
Z Z 3 Z 3 n o
∑ ∇· ∑



I 1 dV = − η· ∇P0i x f x̂i dV + η· ∇P0i x f · n̂ x̂i dS. (64)
V V i =1 S i =1

Next the I 2 term is dealt with. But here is is better to look at it together with the integral
from the outset, by considering

!
3
∂f
Z Z   Z

V
I 2 dV =
V
∇hP0 i f · hη i dV =
V
∑ ∂h Pi i hη1 i dV. (65)
i =1

The reason for considering I 2 inside the integral is that, remembering that hηi i is
R l+
proportional to l −i ηi dxi , Eq. (65) can be written as
i

3  !
∂f
Z Z Z D E
V
I 2 dV =
V
∑ ηi ∂P0i
dV =
V
η · ∇hP0 i f dV, (66)
i =1

by changing
R R the
R order
R of integration. In doing this we have used the fact that dV ≡ dx1 dx2 dx3
and V ≡ x1 x2 x3 .
The goal of factoring out η involving a dot product has now been achieved and Eq. (54) can
be written, using Eqs. (64) and (66), as
 Nanoscale Ferroelectric Films, Strips and Boxes 467
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" #
Z 3 D E
∑ ∇·


η · ∇P0 f − ∇P0i x f x̂i + ∇hP0 i f dV
V i =1
" #
Z 3 n
o
+
S
η· ∑ ∇P0i x f · n̂ x̂i + ∇P0 f surf dS = 0. (67)
i =1

However, at first we consider a restricted function space such that η is zero on S; then the
surface integral in Eq. (67) vanishes resulting in

" #
Z 3 D E
∑ ∇·


η · ∇P0 f − ∇P0i x f x̂i + ∇hP0 i f dV = 0. (68)
V i =1

For this to be zero for any η in the restricted space, it follows from the lemma of du
Bois-Reymond[25], that

3 D E
∑ ∇·


∇ P0 f − ∇P0i x f x̂i + ∇hP0 i f = 0, (69)
i =1

which can be rewritten as

 
∂f
∂f
− ∇ · ∇P0ix f + = 0, i = 1, 2, 3. (70)
∂P0i ∂h P0i i

These form the Euler-Lagrange equations that we seek. It is clear that the lifting of the
restriction on η so that it is not necessarily zero on S, means that the Euler-Lagrange
equations still result from Eq. (67), provided the lemma of du Bois-Reymond is applied
to the surface integral term. This implies the boundary conditions

∂ f surf
(∇Pix f ) · n̂ + on S, i = 1, 2, 3. (71)
∂Pi

For any i the first term is a natural boundary condition arising from the minimization (not a
prescribed condition), and the second term is due to the surface energy.
Thus we have shown that the equilibrium polarization for a ferroelectric of arbitrary shape
in the region V is found by solving the Euler-Lagrange equations in Eq. (70), subject to the
boundary conditions in Eq. (71). This formulation can be applied to finding the polarization
in ferroelectrics with the geometries, box, strip and film, as will be shown in the next section
for the case of a ferroelectric exhibiting a symmetric phase of cubic symmetry.
468 Advances in Ferroelectrics
20 Advances in Ferroelectrics

Ba2+

O2 −

Ti4+

Figure 8. A structural unit for barium titanate, BaTiO3 .

5. The equilibrium Polarization in ferroelectric boxes, strips and films for

cubic symmetry
Cubic symmetry is chosen because it is the symmetry of the popular perovskite ferroelectrics
such as barium titanate (BaTiO3 ) and lead titanate (PbTiO3 ). A structural unit for barium
titanate is represented in Fig. 8
The interest is in nanoscale boxes, strips and films. The formalism itself could easily be
applied to thicker films, however for confinement in the nanoscale (in all three dimensions
for boxes, in two dimensions in strips and in one for films) it is expected that the influence
of the change in the polarization as it approaches a surface will have a more significant effect
that at lager scales where the bulk properties would be more dominant, and so is sometimes
referred to as a size effect.

5.1. Polarization for a ferroelectric nano-box

For a cubic crystal only those terms in f given by Eq. (40) that are invariant under the
symmetry 16 operations of the cubic symmetry group[26] are allowed.3 It can be shown[10,
12] that these are given by

3
1
i
f cubic x, P, Px1 , Px2 , Px3 , hPi = α1 ( T − TC ) P2 + ∑ 2i αi P2


i =2
2 2
1 1 
 1 
+ β 2 ∑ σi P12 P22 + β 3 ∑ σi P14 P22 + P32 + γ3 P12 P22 P32
2 i =0 2 i =0 2
3  2 3
1 ∂P  1
+ δ ∑  ∑


+ P P − h Pi i , (72)
2 i=1 ∂xi  2ǫ0 ǫ∞ i=1 i i

where the cyclic operator defined by Eqs. (48) and (49) is being used and, to lighten the
notation a little we make the replacement P0 → P ⇒ Poi → Pi , although the subscript that
distinguishes the equilibrium polarization from the general function space remains implied.

3
The operations are: 1, 1̄, 4, 4−1 , 4̄, 4̄−1 , 2′ , 2′′ , 2x , 2y , 2z , m1 , m2 , m3 , m4 , m5 .
 Nanoscale Ferroelectric Films, Strips and Boxes 469
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The Euler-Lagrange equations that need to be solved to find the equilibrium polarization in
the nano-box are then found from Eq. (70) with f = f cubic . The steps will not be shown here
but the cyclic operator can make the working easier and it is straightforward to show that
the required Euler-Lagrange equations are given by

3
j −1 2
∑ αj P2 ∑ σj Pj2


α1 ( T − TC ) Pi + Pi + β 2 Pi
j =2 j =1
 2 2 
1
+ β 3 Pi 2Pi2 ∑ σ j Pi2 + ∑ σ j Pj4 + δ∇2 Pi +



( P − h Pi i) , i = 1, 2, 3. (73)
j =1 j =2
ǫ0 ǫ ∞ i

The surface term is given by Eq. (45), but here we assume that d(x|S ) is constant over each
surface of the box. The boundary conditions in Eq. (71) can then be shown to reduce to

∂Pi 1
∓ + ∓ = 0 ∀x ∈ S xi = l ∓ i = 1, 2, 3. (74)
∂xi di j

For a free standing box it is reasonable to have di∓ = d ∀i = 1, 2, 3.

The solution of Eqs. (73) and (74) has not yet been obtained but progress is being made on
it and will be reported later. Eq. (73) is a nonlinear partial differential equation, and as such
it is unlikely that an analytical solution can be found. Instead, a numerical approach or an
approximate solution using trial functions with adjustable parameters could be employed.
The box geometry is likely to be amenable to a finite difference numerical solution. Dealing
with a simpler symmetry such as that discussed in the introduction would make the problem
less computationally intensive but still not amenable to an analytical solution, as will now be
discussed.
If Eq. (72) were reduced to a simpler form by putting α3 = β 2 = β 3 = γ3 = 0, neglecting
the depolarization terms, and arranging for the polarization to be aligned along only one
coordinate axis; the problem would then be something like a three-dimensional form of the
thin-film case discussed in Section 2.2. It might then be tempting to try a separation of
variables approach to solving the Euler-Lagrange equations with the hope that the solution
would be of the form P( x1 ) P( x2 ) P( x3 ) in which each factor is a solution of the form of the
thin film solution given in Section 2.2. However any attempt to do this would fail to produce
an exact solution to the three-dimensional problem due to the nonlinearity of a term cubic
in the polarization. However it might be useful to treat P( x1 ) P( x2 ) P( x3 ) as an approximate
function and introduce into it some variable parameters that could be optimized to find
the best approximation. This idea is currently being explored but as yet there are no final
conclusions.

5.2. Polarization for a ferroelectric nano-strip

The case of a strip in which confinement along two of the axes can be thought of as a special
case of the box in which one side, l1 say, approaches infinity such that P(x) = P( x1 , x2 , x3 ) →
470 Advances in Ferroelectrics
22 Advances in Ferroelectrics

P( x2 , x3 ), and is constant with respect to x3 since the boundaries in this direction have no
influence, which also implies that the depolarization terms only involve hPi = (h P2 i, h P3 i).
Now the relevant quantity is a free energy density per unit length, since for a section of the
strip between x1 = 0 and x1 = l1′ the free energy is

Z l′ Z Z l1′ Z
1

G= dx1 f x, P, Px2 , Px3 , hPi dA + dx1 f surf (x, P)dΓ, (75)
0 A 0 Γ

leading to an energy density

G
Z
Z
F= ′ = f x, P, Px2 , Px3 , hPi dA + f surf (x, P)dΓ, (76)
l1 A Γ
R
where Γ is a line integral around the path Γ that traces a rectangular cross section of the
R R l2+ R l3+
strip normal to x1 , A ≡ l − l − , and dA = dx2 dx3 .
2 3

For f = f cubic (Eq. (72)), the Euler-Lagrange equations are similar to Eq. (73) but P1 is
∂2 ∂2
constant, and so ∇2 = ∂x 2 + ∂x 2 , and the depolarization term for i = 1 reduces to zero.
2 3
Also the boundary conditions are given by Eq. (74), but with i = 2, 3. The solution is again
best approached by numerical or other approximate methods. Work on this is in progress.
The comments made in at the end of the previous section for the ferroelectric nano-box
with regard to simplifying it to a three dimensional form of the problem in Section 2.2 also
apply here: for the same reason it is not possible to express an exact solution of the form
P( x2 ) P( x3 ), where P has the form of the solution given in Section 2.2. Again it may be
possible to utilize such a solution as an approximate function. This needs to be investigated
further.

5.3. Polarization for a ferroelectric nano-film

For a film confined in the x3 direction, a similar argument to the one given for a nano-strip
yields P = P( x3 ), hPi = h P3 ix̂3 , and a free energy density

Z l+
G 3

F= ′ ′ = f x3 , P, Px3 , h P3 i dx3 . (77)
l1 l2 l3−

With f = f cubic given by Eq. (72), the Euler-Lagrange equations again take the form of
Eq. (73); now with P1 and P2 constant so that the depolarization terms reduce to zero for
∂2
i = 1, 2, and ∇2 → ∂x 2 . The boundary conditions are given by Eq. (74), with i = 3 and
3
∂
∂x3 → dxd3 . An analytical solution, even for this one-dimensional case is still not likely to
exist unless f is reduced to the simpler higher symmetry form for second order transitions
and in-plane polarization discussed in Section 2.2. However it is amenable to numerical
solution or other approximate methods. A similar thin film problem, but involving strain in
the ferroelectric as well, which we do no consider, has been solved numerically using a finite
difference method by Wang and Zhang[7].
 Nanoscale Ferroelectric Films, Strips and Boxes 471
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6. Conclusion
The foundations of Landau-Devonshire theory have been introduced and it has been used
to develop a general formulation for the calculation of the spontaneous polarization in
a ferroelectric nano-box which is confined to the nanoscale in all three dimensions, and
for which the influence of the surfaces is expected to be more pronounced than for large
scales. From the formalism for the box calculations it has been shown how to deal with a
nano-strip which is confined to the nanoscale in two dimensions and to a nano-film with
such confinement in only one dimension. The thin film case has been fairly well studied,
but much less work has been done on the other geometries, box and strip. Such work is
timely given the increasing use of nanoscale structures in electronic devices which include
ferroelectric materials, for example ferroelectric random access memories.
A particular example of how the formalism can applied to a ferroelectric crystal of cubic
symmetry has been given for all three geometries. Many ferroelectric materials have this
symmetry. However the general formalism presented is not restricted to this symmetry, any
symmetry can be handled through knowledge of which terms in the free energy needed to
be dropped, the criterion being that only terms invariant under the symmetry operations of
the symmetry group are allowed.
Future work will involve investigating the numerical or approximate function solutions to the
Euler-Lagrange equations which need to be solved in order to be able to plot the spontaneous
polarization. Such work is in progress and will be reported in due course.

Acknowledgements
The author would like to thank Manas Kumar Halder for useful and enlightening discussions
on several of the ideas presented in this chapter.

Author details
Jeffrey F. Webb
Faculty of Engineering, Computing and Science, Swinburne University of Technology,
Sarawak Campus, Kuching, Sarawak, Malaysia

References
[1] P. Chandra and P. B. Littlewood. A Landau primer for ferroelectrics. In K. Rabe, Ch. H.
Ahn, and J. M. Triscone, editors, Physics of Ferroelectrics, volume 105 of Topics in Applied
Physics, page 69. Springer, Heidelberg, 2007.

[2] J. F. Scott. The physics of ferroelectric ceramic thin films for memory applications.
Ferroelectr. Rev., 1:1, 1998.

[3] D. R. Tilley and B. Zeks. Landau theory of phase transtions in thick films. Solid State
Commun., 49:823, 1984.

[4] D. R. Tilley. Phase transitions in thin films. In N. Setter and E. L. Colla, editors,
Ferroelectric Ceramics, page 163. Birkhäuser Verlag, Berlin, 1993.
472 Advances in Ferroelectrics
24 Advances in Ferroelectrics

[5] D. R. Tilley. Finite-size effects on phase transitions in ferroelectrics. In Carlos Paz

de Araujo, J. F. Scott, and G. W. Taylor, editors, Ferroelectric Thin Films: Synthesis and
Basic Properties, Integrated Ferroelectric Devices and Technologies, page 11. Gordon and
Breach, Amsterdam, 1996.

[6] J. F. Webb. Theory of size effects in ferroelectric ceramic thin films on metal substrates.
J. Electroceram., 16:463, 2006.

[7] J. Wang and T. Y. Zhang. Influence of depolarization field on polarization states in

epitaxial ferroelectric thin films with nonequally biaxial misfit strains. Physical Review
B, 77:014104–1 to 014104–7, 2008.

[8] Anna N. Morozovska, Maya D. Glinchuk, and Eugene A. Eliseev. Phase transitions
induced by confinement of ferroic nanoparticles. Physical Review B, 76:014102–1 to
014102–13, 2007.

[9] M. E. Lines and A. M. Glass. Principles and Applications of Ferroelectrics and Related
Materials. Clarendon, Oxford, UK, 1977.

[10] B. A. Strukov and A. P. Lenanyuk. Ferroelectric Phenomena in Crystals. Springer, Berlin,

1998.

[11] R. C. Tolman. The Principles of Statistical Thermodynamics. Clarendon Press, Oxford, 1938.

[12] J. C. Toledano and P. Toledano. The Landau Theory of Phase Transitions. World Scientific,
Singapore, 1987.

[13] R. Blinc, S. Detoni, and M. Pintar. Nature of the ferroelectric transition in triglycine
sulfate. Physical Review Letters, 124:1036–1038, 1961.

[14] K. Itoh and T. Mitsui. Studies of the crystal structure of triglycine sulfate in connection
with its ferroelectric phase transition. Ferroelectrics, 5:235–251, 1973.

[15] M. G. Cottam, D. R. Tilley, and B. Zeks. Theory of surface modes in ferroelectrics. J.

Phys C, 17:1793–1823, 1984.

[16] R. Courant and D. Hilbert. Methods of Mathematical Physics, volume 1. Interscience, New
York, 1953.

[17] X. Gerbaux and A. Hadni. Static and dynamic properties of ferroelectric thin film memories.
PhD thesis, University of Colorado, 1990.

[18] E. K. Tan, J. Osman, and D. R. Tilley. First-order phase transitions in ferroelectric films.
Solid State Communications, 116:61–65, 2000.

[19] K. H. Chew, L. H. Ong, J. Osman, and D. R. Tilley. Theory of far-infrared reflection and
transmission by ferroelectric thin films. J. Opt. Soc. Am B, 18:1512, 2001.

[20] J. F. Webb. Harmonic generation in nanoscale ferroelectric films. In Mickaël Lallart,

editor, Ferroelectrics - Characterization and Modeling, chapter 26. Intech, Rijeka, Croatia,
2011.
 Nanoscale Ferroelectric Films, Strips and Boxes 473
Nanoscale Ferroelectric Films, Strips and Boxes 25
http://dx.doi.org/10.5772/52040

[21] M. Abramowitz and I. A. Stegun, editors. Handbook of Mathematical Functions. Dover,

New York, 1972.

[22] R. Kretschmer and K. Binder. Surface effects on phase transitions in ferroelectrics and
dipolar magnets. Phys. Rev. B, 20:1065–1076, 1979.

[23] M.D. Glinchuk, E.A. Eliseev, and V.A. Stephanovich. Ferroelectric thin film
properties—depolarization field and renormalization of a “bulk” free energy
coefficients. J. Appl. Phys., 93:1150–1159, 2003.

[24] D. L. Mills. Nonlinear Optics. Springer, Berlin, second edition, 1998.

[25] E. W. Honson. On the fundamental lemma of the calculus of variations and on some
related theorems. In Proceedings of the London Mathematical Society, volume s2-11, pages
17–28, 1913.

[26] J. Nye. Physical Properties of Crystals. Their Representation by Tensors and Matrices. Oxford
University Press, Oxford, 1964.
 Chapter 21

Emerging Applications of Ferroelectric Nanoparticles in

Materials Technologies, Biology and Medicine

Yuriy Garbovskiy, Olena Zribi and

Anatoliy Glushchenko

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52516

1. Introduction

Consider an insulating system with non-zero spontaneous polarization Ps (dielectric di‐

pole moment per unit volume). If an applied external electric field E that is greater than
the so-called coercive field Ec can reverse Ps then our system is a ferroelectric system.
Ferroelectricity has a long and exciting history described in [1,2]. In the beginning of its
historical development (the Rochelle salt period) ferroelectricity was considered an aca‐
demic curiosity with no practical applications. There was little theoretical interest due to
the quality of the ferroelectric materials (very fragile and water-soluble) existing at that
time. The discovery of ferroelectricity in robust ceramic materials (barium titanate) dur‐
ing World War II launched a new era of rapid progress in the field. The structural sim‐
plicity of barium titanate stimulated numerous theoretical works, while its physical
properties were utilized in many devices. Since that time, ferroelectric response has been
found in a wide range of materials, including inorganic, organic, and biological species.
According to [3] there are 72 families of ferroelectrics presented in Landolt–Börnstein‐
Vol.III/36 (LB III/36). Forty-nine of these families are inorganic crystals (19 families of ox‐
ides + 30 families of crystals other than oxides), and 23 families are organic crystals,
liquid crystals, and polymers.

The enormously broad range of materials exhibiting ferroelectricity and the variety of their
physical properties result in numerous applications of bulk ferroelectrics [4]. Table 1 shows
the connections between different physical effects exhibited by bulk ferroelectrics and their
applications.

© 2012 Garbovskiy et al.; licensee InTech. This is an open access article distributed under the terms of the
Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
476 Advances in Ferroelectrics

Recent advances in nanotechnologies, especially in nanoinstrumentation (for example,

scanning probe microscopy [5]) and materials nanofabrication [6], allowed the direct prob‐
ing of ferroelectricity at the nanoscale. The new and unexplored world of nanoscale ferro‐
electrics (nanoparticles of different shapes and sizes, nanofilms, nanopatterned structures,
etc.) raised fundamental questions and stimulated very active research in both academic
and industrial sectors [7]. As a result, a new era of nanoscale ferroelectrics was launched.
Novel effects, associated with reduced dimensions and found in nanoscaleferroelectrics,
highlighted exciting possibilities for new applications reviewed recently in [8]. Almost all
of the attention for the mentioned review [8] was devoted to the thin film nanoscale de‐
vice structures (which can be easily integrated with a Si chip) with focus on ultrafast
switching, electrocaloric coolers for computers, phase-array radar, three-dimensional
trenched capacitors for dynamic random access memories, room temperature magnetic
field detectors, and miniature X-ray and neutron sources. So far, we have not found a co‐
herent review summarizing the actual and possible applications of ferroelectric nanoparti‐
cles. Our book chapter is an attempt to describe and analyze the state of the field of
applications of ferroelectric nanoparticles with focus on materials technologies, medicine,
and biology.

Physical effect/property Applications

Ferroelectric hysteresis Nonvolatile computer information storage

High relative permittivities (several

Capacitors
thousands)

Direct piezoelectric effect Sensors (microphones, accelerometers, hydrophones, etc.)

Converse piezoelectric effect Actuators, ultrasonic generators, resonators, filters

Pyroelectric effect Uncooled infra-red detectors

Laser Q-switches, optical shutters and integrated optical (photonic)

Electro-optic effects
devices

Laser frequency doubling, optical mixing, including four-wave mixing and

Nonlinear optical effects
holographic information storage

Coupling between stress and birefringence Radar signal processing

Positive temperature coefficient of Electric-motor overload-protection devices and self-stabilizing ceramic

resistance (PTCR) heating elements

Table 1. Applications of bulk ferroelectrics

 Emerging Applications of Ferroelectric Nanoparticles in Materials Technologies, Biology and Medicine 477
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2. Methods of ferroelectric nanoparticles production: Nano-powders and

nano-colloids

The existing methods that produce ferroelectric nanoparticles are numerous and can be clas‐
sified as physical, chemical, and biological (Fig. 1). The primary goal of each method is to
control size, shape, morphology, and crystallinity of nanoparticles to produce a desirable ef‐
fect. This task represents a real challenge, and, as a result, there are no well-defined bounda‐
ries between physical, chemical, or biological methods. Moreover, in many cases, a
combination of at least two methods (for example, physical and chemical methods, i.e. a
physical-chemical approach) is required in order to fabricate good quality particles (small
sizes, narrow size distribution, ferroelectric phase).

Figure 1. Methods used to fabricate ferroelectric nanoparticles

2.1. Chemical methods

The most widely used chemical methods for the synthesis of ferroelectric nanoparticles are:
1) solid-state reaction; 2) sol-gel technique; 3) solvothermal method; 4) hydrothermal meth‐
od; and 5) molten salt method.
Table 2 shows selected examples of these methods applied to synthesis of ferroelectric nano‐
particles of BaTiO3. As can be seen from Table 2, the ultra-fine ferroelectric nanoparticles
(<10 nm) in almost all cases except [16] are synthesized in a cubic phase which is not ferro‐
electric. The tetragonal phase (with ferroelectric response) is possible for relatively large par‐
ticles (~50-70 nm). This fact can be critical for certain types of applications, and will be
discussed later.
478 Advances in Ferroelectrics

Relevant parameters (size,

Shape of morphology, crystallinity, Possible
Synthesis method;
nanoparticles; spontaneous polarization etc.); applications &
Raw materials
Ref. Measurement and comments
characterization methods

Uniform BaTiO3 nanotubes, a

cubic phase, average diameter =
10 nm and wall thickness = 3 nm
Wet chemical route at low
at room temperature; Promising
temperature (50°C);
Nanotubes; Powder X-ray diffraction (XRD), microwave-
H2TiO3 nanotubes; ethanol/water
[10] field-emission scanning electron absorbing
mixture with 25% ethanol by
microscopy (FE-SEM), materials
volume; Ba(OH)2·8H2O
transmission electron microscopy
(TEM), Raman spectroscopy, and
X-ray photoelectron spectroscopy

Sol-gel technique;
Barium titanium ethyl hexano-
isopropoxide, BaTi(O2CC7H15) Monodisperse
(OCH(CH3)2)5 ; a mixture of nanoparticles with diameters
Nanocrystals; Multilayer ceramic
diphenyl ether, (C5H5)2O; ranging from 6 to 12 nm, cubic
[11] capacitors
stabilizing agent oleic acid, phase;
CH3(CH2)7CHdCH(CH2)7- XRD,TEM
CO2H, at 140 °C, under argon or
nitrogen

Solid-state reaction as a function

of temperature (400–8000C),
time (1–24 hr);
Nanocrystalline TiO2, ultrafine
Dense polycrystalline
BaCO3 and submicrometer BaCO3 Nanoparticle size is 70 nm.
aggregates (~80 nm)
were intensively mixed in an Specific surface area up to Multilayer ceramic
of nanocrystals
aqueous suspension for 24 hr ~15m2/g, tetragonal phase; capacitors
(~30 nm);
using polyethylene jars and TG and DTA analysis, XRD, SEM
[12]
zirconia media. The polymer
(ammonium polyacrylate) was
required for the formation of a
monolayer on the particle surface

Molten salt method; 50 nm, cubic phase;

Polyhedral with
Hydroxide octahydrate XRD, Fourier transform infrared
hexagonal outline in Nanoparticles are
(Ba(OH)2·8H2O), titanium dioxide spectrometry, UV–Vis diffuse
shape; well dispersed
(TiO2), and the eutectic salts reflectance spectra, and field
[13]
(NaCl–KCl), 600-900 °C emission SEM
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Relevant parameters (size,

Shape of morphology, crystallinity, Possible
Synthesis method;
nanoparticles; spontaneous polarization etc.); applications &
Raw materials
Ref. Measurement and comments
characterization methods

Solvothermal method;
Single crystalline
Ba(CH3COO)2 and Ti(OC4H9)4 ; the 5-20 nm, cubic phase; Dense bulk
nanoparticles;
autoclave was maintained at XRD, TEM, SAED, FTIR nanocomposites
[14]
200 °C for 12 hr

Hydrothermal method; 15-50 nm,cubic or tetragonal

Nanoparticles; Dense bulk
(Ba,Sr)(OiPr)2, Ti(OiPr), EtOH, phase;
[15] nanocomposites
330–400 °C, 16-30 MPa XRD, TEM

125 nm, tetragonal phase,

remnant polarization Pr = 1.64
Combined wet-chemical and µC/cm2, the coercive field,
Nanopowders; Multilayer ceramic
rapid calcination process; Ec = 4.91 kV/cm; (cigar-like
[9] capacitor
BaCO3–TiO2 precursors loop);surface area 7.96 m2/g
XRD, TEM, TGA, SMPS,
SAED,dielectric spectroscopy

One-step solvothermal route;

Tetra-n-butyl titanate, Barium 5 nm, tetragonal phase;
Nanocrystals; Multilayer ceramic
hydroxide octahydrate, solvent XRD, TEM, HRTEM, Raman
[16] capacitor
(Diethylene glycol), surfactant spectroscopy
(Polyvinyl Pyrrolidone)

Table 2. Chemical methods

2.2. Physical methods

Dry and wet mechanical grindings are methods of choice for inexpensive nanoparticle prepa‐
ration. For technological applications, wet grinding is preferable because it allows more op‐
tions to control the size of the nanoparticles. During the last few years, substantial progress
was made in the field of ferroelectric nanoparticle preparation by means of wet mechanical
grinding [17]. Generally, three components are needed: raw material to grind (micron-sized
powders of BaTiO3); surfactant (which covers the particle surface and prevents their aggrega‐
tion and overheating during grinding; oleic acid is a good choice for BaTiO3); and fluid carrier
(both raw material and surfactant are mixed with fluid carrier; heptane is widely used to grind
BaTiO3). An extensive list of references, as well as recent achievements in the field, are dis‐
cussed in the review [18]. Table 3 shows how particle sizes depend upon grinding time [19].

As is seen from Table 3, wet mechanical grinding can produce 9 nm nanoparticles, and such
small particles are still in ferroelectric phase. It is important to remember that BaTiO3 nano‐
particles of the same sizes synthesized by the majority of chemical methods are not ferro‐
480 Advances in Ferroelectrics

electric – the method used to fabricate nanoparticles really does matter. The ability to
produce ferroelectric nanoparticles of very small sizes is a defining characteristic of this
physical method (see [18] for more references).

Grinding time, hrs 3 7 10 16 20 24

Average particle diameter, nm 26 14.9 11.6 9.5 9.2 9

Table 3. BaTiO3 particle sizes as a function of grinding time (liquid carrier – heptane; two-station PM200 planetary ball
mill from Retsch)

The net dipole moment of ferroelectric nanoparticles allows them to be harvested by using
an inhomogeneous electric field. The harvesting concept proposed in [20] is based on the
fact that dipoles experience a translational force only when exposed to a field gradient. For a
given linear field gradient and assuming a single ferroelectric domain, the net translational
force on a dipole scales proportionally with the particle size. The Brownian motion effects
also become progressively more pronounced at smaller particle sizes and so the required
field strength for successful separation scales nonlinearly as the particle size is reduced.

Both gas-phase and liquid-phase harvesting methods were proposed and tested successfully,
and single ferroelectric monodomain nanoparticles as small as 9 nm from mechanically
ground nanoparticles were selectively harvested [20]. In contrast to many reports on the lack
of ferroelectricity for nanoparticles below 10 nm (see Table 2), the harvested nanoparticles do
maintain ferroelectricity. The ferroelectric response of such tiny nanoparticles was attributed
to the existence of an induced surface strain as a result of the grinding process [20]. The lack of
a mechanically induced strain in similarly sized but chemically produced nanoparticles ac‐
counts for the absence of ferroelectricity in these materials. The concept of stress-induced fer‐
roelectricity was verified in further experiments, which are reviewed in [18]. It was found [21]
that the spontaneous polarization of the nanoparticles is four to five times larger than the
spontaneous polarization of the bulk raw materials. To obtain this result the following two
conditions must be satisfied: (1) a nonpolar solvent for the nanoparticle suspension and (2)
nonaggregated nanoparticles. Under these conditions, for 9 nm nanoparticles, the values of
100–120 μC/cm2 and 8.9 10-23C cm have been measured for the spontaneous polarization and
dipole moment, respectively. The aggregation of ferroelectric nanoparticles masks the ferro‐
electric response due to the partial compensation of the dipole moments of the individual par‐
ticles. Finally, we can conclude that recent advances in the production of uniform,
monodomain, highly ferroelectric nanoparticles indicate that this field has reached its maturi‐
ty. The particles can now be reliably prepared to certain specifications and characteristics [18].

2.3. Physical-chemical methods

In order to prepare ferroelectric nanoparticles with controllable sizes and shapes a combina‐
tion of chemical methods with external physical factors (for example, a chemical reaction in
the presence of electromagnetic fields or mechanical milling) is needed. Table 4 shows sever‐
al examples of these physical-chemical methods for the case of BaTiO3.
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As can be seen from Table 4, chemical reactions under the presence of an external driver
(microwave, ultrasonic, milling, heat, pressure) are able to produce very fine particles (~5-10
nm) with tetragonal structures.

Relevant parameters (size,

Shape of morphology, crystallinity, Possible
Synthesis method;
nanoparticles; spontaneous polarization etc.); applications &
Raw materials
Ref. Measurement and characterization comments
methods

Microwave (2.45 GHz, output

power ~ 800W) hydrothermal;
High-purity reagents
Cross section 70 ± 9 nm in [100]
barium nitrate (Sigma Aldrich,
projection; tetragonal structure; remnant
purity ≥99.99%), titanium
Truncated nanocubes; polarization is 15.5 µC/cm2; saturation Charge storage
isoproxide
[22] polarization is 19.3 µC/cm2; devices
(Sigma Aldrich, purity ≥97%),
XRD, high resolution TEM, impedance
nitric acid (ACS reagent 70%),
spectroscopy
ammonium hydroxide (Sigma
Aldrich), and glycine (Sigma-
Aldrich, purity ≥99%)

Sizes range from 50 to 75nm; transition

Oxygen
of BaTiO3 from cubic to a
atmosphere
Sol–gel-hydrothermal method pseudotetragonal phase with the
decreases sizes of
under an oxygen (partial pressure increase ofthe reaction temperature
Nearly spherical the nanoparticles
is ~60 bar); from 80 to 220 °C; remnant polarization
nanoparticles; (for example , at
TiCl4; HCl; BaCl2·2H2O; deionized Pr = 2.2 C/cm2; the coercive field,
[23] 200 °C sizes
water, stirring and N2 bubbling, Ec = 3.2 kV/cm (cigar-like loop);
decrease from
NaOH XRD, TEM, Raman and dielectric
72.54 nm to
spectroscopy; energy-dispersive X-ray
49.54 nm)
spectroscopy; AFM

Direct synthesis from solution

(DSS) – mechanochemical
synthesis;
Nanocrystals; 7 nm, tetragonal structure; Chemical reaction
Anhydrous Ba(OH)2 and
[24, 25] XRD, TEM, Raman spectroscopy during milling
tetrabutyl titanate [Ti (OC4H9)4]
Mechanical milling at the rate of
200 rpm, room temperature

Large aggregates of
5–10 nm small Sonochemical synthesis; 100 nm aggregates, cubic phase; Multilayer ceramic
nanocrystals; BaCl2 ; TiCl4; NaOH XRD, TEM, DLS, SAED capacitors
[26]
482 Advances in Ferroelectrics

Relevant parameters (size,

Shape of morphology, crystallinity, Possible
Synthesis method;
nanoparticles; spontaneous polarization etc.); applications &
Raw materials
Ref. Measurement and characterization comments
methods

RF-Plasma chemical vapor

Single nanocrystals; deposition (CVD); 12.2-15.4 nm; Multilayer ceramic
[27] iso-propoxide (Ti(OiPr)4, bis- XRD, TEM, SAED, EDX capacitors
dipivaloylmethanate (Ba(DPM)2

Electrospinning, sol-gel; 80-190 nm in diameter, 0.1 mm in Piezo, microwave

Nanofibers;
barium acetate, PVP, titanium length; material, sensors,
[28, 29, 30]
isopropoxide, ethanol, acetic acid XRD, TEM, SAED capacitors

Flame spray pyrolysis;

Nanopowders; 70 nm, tetragonal structure; Multilayer ceramic
barium carbonate and titanium
[31] XRD, TEM, SEM capacitors
tetra-iso-propoxide, citric acid

Table 4. Physical-chemical methods

Another interesting subject is the possible application of ceramic nanofibers produced by

the method of electrospinning. These possible applications include: nanofiber-based sup‐
ports for catalysts, nanofiber-based photocatalysts, nanofiber-based membrane for filtration,
nanofiber-based sensors, nanofiber-based photoelectrodes for photovoltaic cells, nanofiber-
based electrodes for lithium batteries, nanofiber-based electrode-supports for fuel cells, and
materials for implants [28, 29, 30].

2.4. Biological methods

The proper combination of chemical and physical methods (Table 4) allows the produc‐
tion of very small ferroelectric nanoparticles (5-10 nm). However, toxic chemicals and/or
high temperatures/pressures are needed in most cases. These requirements substantially
limit the possible biomedical applications of ferroelectric nanoparticles. Biological meth‐
ods were proposed as eco-friendly “green” alternatives to existing chemical and physical
methods. The biosynthesis of different types of nanoparticles was reviewed recently in a
few papers [32, 33, 34, 35], but biological methods that produce specifically ferroelectric
nanomaterials are not very numerous. For example, the first review [32] lists nearly a
hundred variations for the synthesis of nanoparticles by microorganisms, and only a few
of them produce ferroelectric nanoparticles. The biological methods applied to synthesize
the nanoparticles of the most widely known ferroelectric BaTiO3 are summarized in Table
5 (papers published before 2008 were discussed in [36]). The references listed in this table
show that most of the biological methods mentioned employ some chemical or physical
steps as well.
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Relevant parameters
(size, morphology,
Shape of nanoparticles; Synthesis method; crystallinity, spontaneous
Comments
Ref. Raw materials polarization etc.);
Measurement and
characterization methods

The peptides BT1 and BT2induce the 50-100 nm; tetragonal phase
Rapid room-
room-temperature precipitation remnant polarization
temperature
Aggregates (~500 nm) of of BaTiO3; Pr ~ 2-3 C/cm2; the coercive field,
synthesis of
nanocrystals(~ 50 nm); Aqueous precursor solution composed Ec = 5-6 kV/cm (cigar-like loop);
ferroelectric
[37] of barium acetate (Ba(OOCCH3)2) SEM, TEM, SAED and XRD
(tetragonal) BaTiO3
potassium bis(oxalato) oxotitanate(IV) analysis, dielectric
within 2 hr
(K2[TiO(C2O4)2]2H2O); pH 6.8 measurements

Lactobacillus - assisted biosynthesis;

Quasi-spherical BaCO3 and TiO2 solid state synthesis 20-80 nm, single-phase
Extracellular
nanoparticles; BaTiO3; Slush of micron-sized BaTiO3 tetragonal structure;
synthesis
[38] particles+ Lactic acid Bacillus XRD, TEM
spore tablets

(Fusarium oxysporum) fungus-assisted

Spherical nanoparticles; biosynthesis of BaTiO3 nanoparticles; 4-5 nm, tetragonal structure; Extracellular
[39] (CH3COO)2Ba and K2TiF6 + fungal XRD, DCS, TEM, SAED, XPS, SPM synthesis
micelles of Fusarium oxysporum

Spherical nanoparticles; Peptide nanorings used as templates; 6-12 nm, tetragonal structure;
4 days
[40] BaTi(O2CC7-H15)[OCH(CH3)2]5 AFM, TEM, XRD, EFM, Raman

(Saccharomyces cerevisiae) baker’s

yeast-assisted
8-21 nm, single-phase
Spherical nanoparticles; biosynthesis of BaTiO3 nanoparticles; Extracellular
hexagonal structure;
[41] BaCO3 and TiO2 solid state synthesis synthesis
XRD, TEM
BaTiO3, Slurry of large BaTiO3 + yeast
culture

Kinetically controlled vapor diffusion

Spherical nanoparticles; Single source, bimetallic alkoxide with 6-8 nm, cubic phase;
~250 g.
[42] the vapor diffusion of a hydrolytic XRD, TEM
catalyst (H2O)

Table 5. Biological methods

484 Advances in Ferroelectrics

One can note from Table 5 that these biological methods can be roughly grouped into two
categories: the synthesis of ferroelectric nanoparticles using a number of seed chemicals and
some type of biological or bio-inspired system, and the creation of nanoparticles using large
particles of ready ferroelectric material and some type of biological system. Most of the
methods that are currently available fall into the first category; the methods in the second
category have appeared only very recently.

The earliest discoveries of nanoparticle synthesis by microorganisms (fungus, Lactobacil‐

lus and yeast) involve metal, alloy, and metal oxide nanoparticles. With a lag of one to
two years, this research was followed by attempts at ferroelectric nanoparticle synthesis
by the same living systems [32]. Fungus (Fusarium oxysporum, commonly found in soil)
has been shown to synthesize extracellularly ferroelectric nanoparticles of barium tita‐
nate (4-5 nm of average size) [39, 43] at room temperature, producing small ferroelectric
nanoparticles on a scale that has been previously inaccessible. This method falls into the
first category, since fungus produces barium titanate from more than one seed chemical.
Lactobacillus (bacteria commonly used to curdle milk and produce buttermilk) has been
shown to synthesize ferroelectric nanoparticles (with sizes ranging from 20 to 80 nm)
from the slush of large barium titanate particles [38]. Baker’s yeast (Saccharomyces cerevi‐
siae) has also been attempted as a biosynthesis agent; the barium titanate nanoparticles
received were on average ~10nm [41]. Both the yeast- and lactobacillus-mediated produc‐
tion of barium titanate nanoparticles fall into the second category: they start with large
particles of ready barium titanate in water and produce small (under 100 nm) nanoparti‐
cles extracellularly.

Peptide nanorings provide another interesting biomimetic route to the template-mediated

synthesis of BaTiO3 and SrTiO3 nanoparticles [40]. Developed in 2006, it was the very first
method of obtaining ferroelectric barium titanate nanoparticles at room temperature (many
previous room-temperature methods had trouble growing barium titanate not in the cubic
phase).

In this category of biological methods, one has to mention bioinspired methods of dis‐
persing nanoparticles and producing stable colloids. Take for examplethe production of
stable nanoparticle suspensions using microbial-derived surfactants [44] where usual gar‐
den variety surfactants are replaced with bio-derived materials that are significantly
smaller in size and that help prevent aggregation of multiple nanoparticles during sol-
gel synthesis. This process relies on some physical/chemical steps, just like the majority
of other biological methods of ferroelectric nanoparticle production that have been devel‐
oped to date.

These bio-inspired methods show great promise because they produce relatively small fer‐
roelectric nanoparticles at room (or low) temperature compared to conventional physical
and chemical methods, many of which require lengthy processes, use of high temperatures,
harsh chemicals, etc.
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3. Applications of ferroelectric nanoparticles in materials technologies

3.1. Multilayered capacitors and nanocomposites

As was previously mentioned in the introduction, the era of applied ferroelectricity was
launched after the first reliable ferroelectric material – ceramic BaTiO3 – was discovered
[1]. The very high dielectric constants (~1000) of bulk ferroelectric materials were applied
in the manufacturing of discrete and multilayered ceramic capacitors. Advances in the
production of ferroelectric nanoparticles broadened this application to a large extent.
Currently, nanosized BaTiO3 powders are successfully used for manufacturing miniatur‐
ized and highly volume-efficient multilayer ceramic capacitors (MLCCs, for more details
see review [45]).

Typical MLCCs utilize pellets of nanopowders sintered at high temperatures, produc‐

ing structures with high rigidity that can impose certain limitations. Nanocomposites
made of flexible polymers and ferroelectric nanoparticles overcome the restrictions
caused by rigidity of sintered structures. Polymeric materials doped with ferroelectric
nanoparticles are of considerable interest as a solution for processable high permittivity
materials for various electronic applications: volume efficient multilayer capacitors, high-
energy-density capacitors, embedded capacitors, and gate insulators in organic field ef‐
fect transistors [46].

Both components (polymer and ferroelectric nanoparticle) of such nanocomposites are es‐
sential. The polymeric material brings flexibility and the ability to cover a large surface area,
while nanoparticles share high values of dielectric permittivity with the matrix-enhancing
effective dielectric permittivity of the composite. It’s not easy to achieve homogeneous dis‐
persion of ferroelectric nanoparticles in a polymeric matrix because of the high surface ener‐
gy of nanoparticles, which usually leads to aggregation and phase separation, resulting in
poor processability of the films and a high defect density. In order to make high-quality
nanocomposites (good solution processability, low leakage current, high permittivity, and
high dielectric strength), surface modification of nanoparticles is needed. The surface modi‐
fication of nanoparticles decreases attractive forces between them, thus preventing aggrega‐
tion. In addition, the proper design of a surface agent can increase interactions between the
nanoparticles and the polymeric matrix. As a result, a quite homogeneous distribution of the
nanoparticles in the polymeric matrix can be achieved. However, there are several obstacles
that prevent nanocomposites “polymer/ferroelectric nanoparticle” from mass commerciali‐
zation. The most common are poor temperature stability of dielectric constants and large di‐
electric losses. The proper design of both the nanoparticles (material size, shape, surface
modification) and the polymer matrix can overcome these problems. For example, Table 6
shows short descriptions of the relatively successful (in terms of material performance)
nanocomposites “polymer/BaTiO3”. All of them are optically transparent, have high dielec‐
tric permittivity (25-30), and moderate losses (loss tangent is in the range 0.01-0.05 for differ‐
ent materials).
486 Advances in Ferroelectrics

Dielectric Particle size

Composition (polymer/
Particle surface functionalization permitti-vity of &breakdown Ref.
nanoparticle)
nanocom-posite electric field

Barium titanate /
poly(vinylidene fluoride-co- Phosphonic acid surface-modified 30-50 nm
35 [46]
hexafluoro propylene), volume BaTiO3 nanoparticles >164 V/µm
concentration < 80%

Barium titanate/polyimide
Core-shell structure; polyamic acid (PAA) 70-100 nm
(BaTiO3/PI); volume 20 [47]
was used to cover particle 67 MV/m
concentration < 40%

Poly(vinylidene fluoride)/
Barium titanate (PVDF/ BaTiO3);
Surface hydroxylated BaTiO3 18-25 85-100 nm [48]
volume concentration
10%- 30%

Barium titanate/polyimide
BaTiO3 nanoparticles were prepared by 30-50 nm
(BaTiO3/PI); volume 30 [49]
the alkoxide route 50-80 nm
concentration < 50%

Barium titanate/poly(methyl BaTiO3 nanoparticles were modified

methacrylate) (BaTiO3/PMMA); with a silane coupling agent (3- 36 16-21 nm [50]
volume concentration 53% methacryloxypropyltrimethoxysilane)

Barium titanate/polyimide BaTiO3 nanoparticles are surface

(BaTiO3/PI); volume modified by phthalimide with the aid of 37 20 nm [51]
concentration 59% a silane coupling agent as a scaffold

Table 6. Nanocomposites of polymer/ferroelectric nanoparticles

3.2. Ferroelectric nanoparticles and liquid crystals: Display and non-display applications

It is an established fact that modern technologies require novel and highly advanced materi‐
als. During the last decade, nanochemistry has developed a dozen conceptually different
pathways of synthesis to satisfy the constantly growing demand for new materials [52].
However, chemical methods are elaborate, time consuming, and expensive. Although they
are generally accepted as universal, nanochemistry methods do not work perfectly in certain
cases. For example, it’s very difficult (but not impossible) to produce 5-10 nm ferroelectric
nanoparticles with tetragonal structures through chemical methods (see Table 2). In many
cases, the chemical methods used to produce novel materials can be efficiently supplement‐
ed or even replaced with non-synthetic ones. The addition of ferroelectric nanoparticles to
different materials (polymers; see Table 6, liquids, liquid crystals etc.) is a good example of a
non-synthetic method used to develop materials with improved properties. This subsection
will discuss how ferroelectric nanoparticles can modify properties of liquid crystals – mate‐
rials that found numerous applications in the display industry, photonics, optical process‐
ing, and the biotech industry.
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The concept of ferroelectric colloids in liquid crystals was created by Yu. Reznikov and co‐
authors [53] – liquid crystal material was doped with stabilized ferroelectric nanoparticles of
low concentration (~0.3 %). Ferroelectric nanoparticles share their intrinsic properties with
the liquid crystals matrix due to the alignment within the liquid crystal and interactions be‐
tween mesogenic molecules. The low concentration of nanoparticles and their stabilization
with surfactant (oleic acid) provided the stability of such systems. This classic paper report‐
ed on the main features of such colloids: (1) a lower threshold voltage by a factor of 1.7; (2)
an enhanced dielectric anisotropy by a factor of 2; (3) a linear electro-optical response (the
sensitivity to the sign of an applied electric field). It should be pointed out that pure nemat‐
ics are not sensitive to the sign of an electric field – this property is intrinsic to ferroelectric
liquid crystals rather than to nematics. The first experimental results stimulated a very ac‐
tive global interest in the field. More than 100 papers were published during the last decade,
and, in the last few years, several review papers summarized the most important results [18,
54, 55]. The review paper [54] published this year by the founder of this field is of special
interest since it comprehensively discusses the past, the present, and the future of the liquid
crystal colloids.

Ferroelectric nanoparticles embedded into a liquid crystal host strongly interact with the
surrounding mesogenic molecules, due to the strong permanent electric field of this particle.
These interactions can affect the basic physical parameters of liquid crystals: birefringence,
dielectric permittivity, elastic constants, viscosity, electrical and thermal conductivity, tem‐
peratures of phase transitions, etc. There are two basic mechanisms responsible for the ob‐
served effects: (1) the increase of the orientation coupling between mesogenic molecules;
and (2) the direct contribution of the permanent polarization of the particle [54]. Experimen‐
tal data suggests that the first scenario (the increase of the orientation coupling between
mesogenic molecules) is more likely to happen in the case of single component liquid crys‐
tals [54]. The second mechanism (associated with the direct contribution of the permanent
polarization of the ferroelectric nanoparticle to the physical properties of liquid crystals) is
the primary factor in the case of multi-component liquid crystal mixtures [54].

So far most of the reported experimental data describes the properties of multi-component
nematics: liquid crystals doped with ferroelectric nanoparticles. The electric field generated
by ferroelectric nanoparticles can cause micro- and/or nano-separation of such mixturesan‐
daffect the macroscopic properties of the liquid crystal colloid. As a result, in some cases, the
data found for single component liquid crystals (5CB) is different from the data obtained for
multi-component mixtures. Nevertheless, an analysis of the existing literature [18] shows
that most of the published experimental data report that ferroelectric nanoparticles embed‐
ded in liquid crystals at low concentrations: (1) enhance dielectric permittivity, dielectric
anisotropy, and optical birefringence; (2) lower the switching voltage Uth for the Freeder‐
icksz transition; (3) increase the orientational order parameter S and the isotropic–nematic
transition temperature TNI; and (4) reduce the switching times needed to reorient liquid crys‐
tals by an external electric field. It should be pointed out that in all of these cases, wet grind‐
ing was used to prepare the ferroelectric nanoparticles. Few papers claim results opposite to
the ones (1)-(4) listed above; however, nanoparticles used to make a liquid crystal colloid in
488 Advances in Ferroelectrics

this case were not ferroelectric [18]. The important conclusion to take from these findings is
that a strong ferroelectric response of ferroelectric nanoparticles is a key factor leading to all
“positive” effects (1)-(4).

The stability of liquid crystal colloids is the most challenging problem that prevents the tran‐
sition of liquid crystal colloids of ferroelectric nanoparticles from the academic sector to the
industrial domain. During the last few years, the general focus of the research has shifted
toward this problem, and the proper surface functionalization of nanoparticles is now being
considered as one of the most important factors affecting the stability of liquid crystal col‐
loids. The shape and size of nanoparticles are also of the utmost importance – it was found
that 10-20 nm ferroelectric nanoparticles affect the properties of a liquid crystal host much
morethan the same but larger nanoparticles(~100 nm).

In summary, ferroelectric nanoparticles can modify the intrinsic properties of liquid crystal
materials without time-consuming and expensive chemical synthesis. Experimental data on
the enhancement of electro-optical, optical, and nonlinear-optical responses of such materi‐
als shows the strong potential of ferroelectric nanoparticles for improving the ‘‘practical’’
properties of liquid crystals, especially for those materials where the method of chemical
synthesis has reached its limit. Such modified materials are very attractive and suitable for
use in switchable lenses, displays, and beam steering, as well as other light-controlling devi‐
ces (spatial light modulators, tunable filters etc.) [18].

4. Ferroelectric nanoparticles in biology

In the last decade, ferroelectric nanoparticle areas of application veered toward biology
and medicine. The first challenge to address when introducing nanoparticles to biological
and medical systems is how to make them stable in media that is bio-compatible, namely
in aqueous solutions. If the ferroelectric nanoparticles are not coated with a stabilizing
agent, the intrinsic properties of such nanoparticles very often lead to unwanted effects
such as aggregation and precipitation, as well as the leaching of some ions (leading to
change in particle properties) in aqueous solutions. There has been a tremendous amount
of effort in the last twenty years to create many species of ferroelectric nanoparticles with
different surface coatings [56and references within]. For example, such stabilizing agents
as polyacrylic acid, polymethacrylic acid, polyaspartic acid, (aminomethyl) phosphonic
acid and poly-l-lysine were tried on barium titanate nanoparticles. A large variety of pos‐
sible coatings yields different surface properties of said nanoparticles – different thick‐
ness and charge of the surface layer, different strength of stabilizing agent adhesion,
different resulting particle size – all of it leading to very different interactions with biolog‐
ical objects such as cells and cellular components. Such water-soluble ferroelectric nano‐
particles can be further functionalized with fluorescent markers or antibodies [57], and
they have been recently observed within a number of mammalian cells [58, 59, 60] in vi‐
tro. The majority of ferroelectric nanoparticles that have been successfully functionalized
are in the middle of nano size range (~100 nm or more), and the surface functionaliza‐
 Emerging Applications of Ferroelectric Nanoparticles in Materials Technologies, Biology and Medicine 489
http://dx.doi.org/10.5772/52516

tion very frequently adds a thick surface layer, resulting in particles that are a few hun‐
dred nanometers in size. This poses a challenge which a few researchers are attempting to
overcome through bio-inspired surfactants [44]. The surface functionalization of nanopar‐
ticles can be crucial for a desired effect in a biosystem – the response is often cell-specif‐
ic, and biocompatibilty has to be experimentally tested for each new combination of
nanoparticle and cell [61]. For example, a recent study [62] indicates that larger (over 200
nm) barium titanate nanoparticles have been successfully used with and without surface
modification and they cause no toxic response in endothelial cell cultures.
Current efforts in this area concentrate on carrying these findings through to the systems of
cells and tissue in vivo [63, 64]. Such biocompatible nanoparticles can be used in a variety of
ways: as imaging agents [58, 59, 60, 64, 65], biocompatible nanoprobes [62, 66, 67, 68], cell
proliferation agents [65], etc. Ferroelectric nanoparticles are currently being widely explored
for applications in the area of medical imaging, e.g. for enhancing contrast in second har‐
monic generating methods for imaging deep tissue in vitro and in vivo [64, 69] for such im‐
portant applications as screening for genetic diseases or cancer[70].

5. Ferroelectric nanoparticles applications in medicine and medical

engineering

As mentioned above, ferroelectric nanoparticles have become widely used in material sci‐
ence and engineering applications, but biological and medical applications of these fascinat‐
ing nanoparticles has only begun to be explored in the last decade. It has been recently
discovered that they can be used for cell imaging or the detection of malignancies in lung
cancer studies, or they can be functionalized to induce cell proliferation. Ferroelectric mate‐
rials have a non-centrosymmetric crystalline structure, and are thus capable of generating a
second harmonic of light [67]. This distinctive feature of ferroelectrics is the basis for a grow‐
ing number of applications of ferroelectric nanoparticles as imaging/diagnostic agents and
nanoprobes in optical imaging [64].
Optical imaging and detection methods are the most widespread among biological and
medical communities. For example, second harmonic generation imaging has been success‐
fully used for detection of osteogenesis imperfecta in biopsies of human skin [71] and lung can‐
cer [72]. To improve contrast, many of the imaging methods rely on imaging probes, such as
fluorescent markers or quantum dots [73]. This is the case for the SHG imaging technique:
the SHG signal from biological cell components is often weak, so novel nanoprobes have
been introduced to enhance contrast. SHG probes are photo-stable, and do not bleach or
blink unlike conventional fluorescent probes. By definition, second harmonic generating
nanoprobes (such as ferroelectric nanoparticles) are capable of converting two photons of
light into one photon of half the incident wavelength [74]. This second-harmonic light can be
detected using methods of nonlinear optical microscopy. Nonlinear optical properties of fer‐
roelectric nanomaterials can be used for optical phase conjugation [75] and nonlinear micro‐
scopy [62, 76] – these properties have allowed them to spread to the area of medical sensors.
490 Advances in Ferroelectrics

This also gives the ferroelectric SHG particle an edge in cell and tissue imaging in vivo. For
example, recent advances in this area include imaging a tail of a living mouse with the aid of
barium titanate nanoparticles [69].
The intrinsic large values of the dielectric permittivities of ferroelectric nanoparticles suggest
their use to enhance the dielectric contrast of materials, such as polymers [77 and references
within] and biological tissue [70]. These unique properties of ferroelectric nanoparticles lead
to their novel use as contrast-enhancing agents for microwave tomography, which is a meth‐
od of non-invasive assessment and diagnostics of soft tissues (such as detecting malignan‐
cies)[70].Recently, ferroelectric electro spun nanofibers also emerged in various biomedical
areas including medical prostheses, tissue engineering, wound dressing, and drug delivery
[28,29,30].
In conclusion, ferroelectric materials found a wide variety of biomedical applications in
the last decade – and the list is constantly growing [78]. The ferroelectric material (e.g. ba‐
rium titanate) used in medical implants has been known to accelerate osteogenesis [79],
and the same material in nanoparticle form works both as an SHG probe to detect Osteo‐
genesis Imperfecta [71] and, through microwave tomography, to detect lung cancer [70].
We expect more applications will become possible if other effects, such as piezoelectrici‐
ty, ferroelectric hysteresis or stress-birefringence coupling, are exploited with biology and
medicine in mind.

6. Conclusions

A review of recently published research papers allows us to conclude that the unique prop‐
erties of ferroelectric nanoparticles offer an enormous range of applications, especially in
material technologies, biology, and medicine. However, since such a conclusion has become
an academic cliché, we would like to make just a few realistic and optimistic comments on
the subject.
Discussing any application, we have to be more specific and distinguish between potential
applications and actual (i.e. mass commercialized) ones. So far, the “applied” field of ferro‐
electric nanoparticles is at the stage of high potential for commercialization rather than real
mass-commercialization. However, after the very first proof-of-concept research studies
were completed just recently, a serious shift toward real applications was initiated. The re‐
search community realized that the controllable preparation of nanoparticles (size, shape),
their proper surface functionalization, and the homogeneous dispersion into host material
(liquid crystals, polymers, biological species) are among the most critical steps on the way to
mass-commercialization. Many applications (especially bio-medical) require a large-scale
preparation of mono-dispersed, very fine (5-10 nm) ferroelectric nanoparticles in the tetrago‐
nal phase – and only recently has substantial progress been made in this direction (see sec‐
tion 2). However, such ultra-fine nanoparticles were mostly tested in material technologies
(ferroelectric liquid crystal colloids), while bio-medical methods utilized relatively large fer‐
roelectric nanoparticles (~50-100 nm) (sections 4-5). The bioconjugation of 5-10 nm ferroelec‐
 Emerging Applications of Ferroelectric Nanoparticles in Materials Technologies, Biology and Medicine 491
http://dx.doi.org/10.5772/52516

tric nanoparticles can extend the area of biomedical application even more, since these
nanoparticles can be used as both passive and active nanoprobes.
The applied science of ferroelectric nanoparticles is in the beginning of its development.
Many fundamental and applied problems still need to be solved before the potential appli‐
cations will be converted into actual ones. Nevertheless, despite the fact that the emerging
problems in applying nanoparticles in material technologies and biomedicine are still nu‐
merous [80], we can conclude that a good balance between purely academic and purely ap‐
plied foci of research is the key toward mass commercialization of ferroelectric nanoparticles
in all applied fields mentioned above.

Acknowledgements

The authors are very grateful to all coauthors of the papers related to the topic of ferroelec‐
tric nanoparticles. We acknowledge also the support of the UCCS Center for the Biofrontiers
Institute, University of Colorado at Colorado Springs. A great portion of the work described
in this review has been supported by the grants from the NSF #1102332 “Liquid Crystal Sig‐
nal Processing Devices for Microwave and Millimeter Wave Operation” and # 1010508
“STTR Phase 1: Design, Fabrication, and Characterization of Ferroelectric Nanoparticle Dop‐
ed Liquid Crystal / Polymer Composites.”

List of abbreviations

AFM atomic force microscopy

DCS differential scanning calorimetry
DLS dynamic light scattering
DTA differential thermal analysis
EDX energy dispersive X-rayspectroscopy
EFM electrostatic force microscopy
FE-SEM field-emission scanning electron microscopy
FTIR Fourier transform infrared spectroscopy
HRTEM high resolution transmission electron microscopy
MLCC multilayer ceramic capacitors
PAA polyamic acid
PTCR positive temperature coefficient of resistance
PMMA poly(methyl methacrylate)
492 Advances in Ferroelectrics

PVDF poly(vinylidene fluoride)

SAED selected area electron diffraction

SEM scanning electron microscopy

SHG probe second harmonic generating probe

SMPS scanning mobility particle size

SPM scanning probe microscopy

TEM transmission electron microscopy

TG or TGA thermo gravimetric analysis

XPSX-ray photoelectron spectroscopy

XRDX-ray diffraction

Author details

Yuriy Garbovskiy, Olena Zribi and Anatoliy Glushchenko

UCCS Center for the Biofrontiers Institute, Department of Physics, University of Colorado at
Colorado Springs, Colorado Springs, Colorado, USA

References

[1] Haertling, G.H. Ferroelectric ceramics: history and technology. Journal of the American
Ceramic Society82, 797-818 (1999).

[2] Cross, L.E. & Newnham, R.E. in High-Technology Ceramics—Past, Present,and Future
289–305 (American Ceramic Society, Westerville, OH, 1987).

[3] Mitsui, T. in Springer Handbook of Condensed Matter and Materials Data (ed. Warli‐
mont, W.M.a.H.) 903 – 938 (Springer, Berlin, 2006).

[4] Whatmore, R. in Springer Handbook of Electronic and Photonic Materials (ed. Cap‐
per, S.K.a.P.) 597 – 623 (Springer, Berlin, 2006).

[5] Kalinin, S.V. et al. Nanoscale Electromechanics of Ferroelectric and Biological Sys‐
tems: A New Dimension in Scanning Probe Microscopy. Annual Review of Materials
Research37, 189-238 (2007).

[6] Gruverman, A. & Kholkin, A. Nanoscale ferroelectrics: processing, characterization

and future trends. Reports on Progress in Physics69, 2443-74 (2006).
 Emerging Applications of Ferroelectric Nanoparticles in Materials Technologies, Biology and Medicine 493
http://dx.doi.org/10.5772/52516

[7] Ahn, C.H., Rabe, K.M. & Triscone, J.M. Ferroelectricity at the nanoscale: local polari‐
zation in oxide thin films and heterostructures. Science303, 488-91 (2004).
[8] Scott, J.F. Applications of modern ferroelectrics. Science315, 954-9 (2007).
[9] Sarkar, D. Synthesis and Properties of BaTiO3 Nanopowders. Journal of the American
Ceramic Society94, 106-110 (2011).
[10] Zhu, Y.-F., Zhang, L., Natsuki, T., Fu, Y.-Q. & Ni, Q.-Q. Facile Synthesis of BaTiO3
Nanotubes and Their Microwave Absorption Properties. ACS Applied Materials & In‐
terfaces4, 2101-2106 (2012).
[11] O'Brien, S., Brus, L. & Murray, C.B. Synthesis of Monodisperse Nanoparticles of Bari‐
um Titanate:  Toward a Generalized Strategy of Oxide Nanoparticle Synthesis. Jour‐
nal of the American Chemical Society123, 12085-12086 (2001).
[12] Buscaglia, M.T., Bassoli, M., Buscaglia, V. & Vormberg, R. Solid-State Synthesis of
Nanocrystalline BaTiO3: Reaction Kinetics and Powder Properties. Journal of the
American Ceramic Society91, 2862-2869 (2008).
[13] Zhang, Y., Wang, L. & Xue, D. Molten salt route of well dispersive barium titanate
nanoparticles. Powder Technology217, 629-633 (2012).
[14] Wei, X. et al. Synthesis of Highly Dispersed Barium Titanate Nanoparticles by a Nov‐
el Solvothermal Method. Journal of the American Ceramic Society91, 315-318 (2008).
[15] Hayashi, H. & Hakuta, Y. Hydrothermal Synthesis of Metal Oxide Nanoparticles in
Supercritical Water. Materials3, 3794-3817 (2010).
[16] Zhang, H. et al. Fabrication of Monodispersed 5-nm BaTiO3 Nanocrystals with Nar‐
row Size Distribution via One-Step Solvothermal Route. Journal of the American Ce‐
ramic Society94, 3220-3222 (2011).
[17] Atkuri, H. et al. Preparation of ferroelectric nanoparticles for their use in liquid crys‐
talline colloids. Journal of Optics A: Pure and Applied Optics11, 024006 (2009).
[18] Garbovskiy, Y. & Glushchenko, A. in Solid State Physics (ed. Camley, R.E.) 1 – 74
(2010).
[19] Cook, G. et al. Nanoparticle doped organic-inorganic hybridphotorefractives. Optics
Express16, 4015-4022 (2008).
[20] Cook, G. et al. Harvesting single ferroelectric domain stressed nanoparticles for opti‐
cal and ferroic applications. Journal of Applied Physics108, 064309-4 (2010).
[21] Basun, S.A., Cook, G., Reshetnyak, V.Y., Glushchenko, A.V. & Evans, D.R. Dipole
moment and spontaneous polarization of ferroelectric nanoparticles in a nonpolar
fluid suspension. Physical Review B84, 024105 (2011).
[22] Swaminathan, V. et al. Microwave synthesis of noncentrosymmetric BaTiO3 truncat‐
ed nanocubes for charge storage applications. ACS Appl Mater Interfaces2, 3037-42
(2010).
494 Advances in Ferroelectrics

[23] Fuentes, S. et al. Synthesis and characterization of BaTiO3 nanoparticles in oxygenat‐

mosphere. 505, 568–572 (2010).
[24] Qi, J.Q. et al. Direct synthesis of ultrafine tetragonal BaTiO3 nanoparticles at room
temperature. Nanoscale Research Letters6, 466 (2011).
[25] Kong, L.B., Zhang, T.S., Ma, J. & Boey, F. Progress in synthesis of ferroelectriccera‐
micmaterialsviahigh-energymechanochemicaltechnique. 53, 207–322 (2008).
[26] Dang, F. et al. Aneweffect of ultrasonication on the formation of BaTiO3 nanoparti‐
cles. 17, 310–314 (2010).
[27] Suzuki, K. & Kijima, K. Well-crystallized barium titanate nanoparticles prepared by
plasma chemical vapor deposition. 58, 1650–1654 (2004).
[28] Ramaseshan, R., Sundarrajan, S., Jose, R. & Ramakrishna, S. Nanostructured ceramics
by electrospinning. Journal of Applied Physics102, 111101-17 (2007).
[29] He, Y. et al. Humidity sensing properties of BaTiO3 nanofiber prepared via electro‐
spinning. Sensors and Actuators B: Chemical146, 98-102 (2010).
[30] Dai, Y., Liu, W., Formo, E., Sun, Y. & Xia, Y. Ceramic nanofibers fabricated by elec‐
trospinning and their applications in catalysis, environmental science, and energy
technology. Polymers for Advanced Technologies22, 326-338 (2011).
[31] Jung, D.S., Hong, S.K., Cho, J.S. & Kang, Y.C. Nano-sizedbariumtitanatepowders
with tetragonalcrystalstructureprepared by flamespraypyrolysis. 28, 109–115 (2008).
[32] Li, X., Xu, H., Chen, Z.-S. & Chen, G. Biosynthesis of Nanoparticles by Microorgan‐
isms and Their Applications. Journal of Nanomaterials2011 (2011).
[33] Chen, C.-L. & Rosi, N.L. Peptide-Based Methods for the Preparation of Nanostruc‐
tured Inorganic Materials. Angewandte Chemie International Edition49, 1924-1942
(2010).
[34] Briggs, B.D. & Knecht, M.R. Nanotechnology Meets Biology: Peptide-based Methods
for the Fabrication of Functional Materials. The Journal of Physical Chemistry Letters3,
405-418 (2012).
[35] Dhillon, G.S., Brar, S.K., Kaur, S. & Verma, M. Green approach for nanoparticle bio‐
synthesis by fungi: current trends and applications. Critical Reviews in Biotechnolo‐
gy32, 49-73 (2011).
[36] Beier, C.W., Cuevas, M.A. & Brutchey, R.L. Room-Temperature Synthetic Pathways
to Barium Titanate Nanocrystals. Small4, 2102-2106 (2008).
[37] Ahmad, G. et al. Rapid Bioenabled Formation of Ferroelectric BaTiO3 at Room Tem‐
perature from an Aqueous Salt Solution at Near Neutral pH. Journal of the American
Chemical Society130, 4-5 (2007).
[38] Jha, A.K. & Prasad, K. Ferroelectric BaTiO3 nanoparticles: Biosynthesis and character‐
ization. Colloids and Surfaces B: Biointerfaces75, 330-334 (2010).
 Emerging Applications of Ferroelectric Nanoparticles in Materials Technologies, Biology and Medicine 495
http://dx.doi.org/10.5772/52516

[39] Bansal, V., Poddar, P., Ahmad, A. & Sastry, M. Room-Temperature Biosynthesis of
Ferroelectric Barium Titanate Nanoparticles. Journal of the American Chemical Soci‐
ety128, 11958-11963 (2006).

[40] Nuraje, N. et al. Room Temperature Synthesis of Ferroelectric Barium Titanate Nano‐
particles Using Peptide Nanorings as Templates. Advanced Materials18, 807-811
(2006).

[41] Jha, A.K. & Prasad, K. Synthesis of BaTiO3 nanoparticles: A new sustainable green
approach. Integrated Ferroelectrics117, 49-54 (2010).

[42] Ould-Ely, T. et al. Large-scale engineered synthesis of BaTiO3 nanoparticles using

low-temperature bioinspired principles. Nature Protocols6, 97-104 (2011).

[43] Bansal, V., Bharde, A., Ramanathan, R. & Bhargava, S.K. Inorganic materials using
‘unusual’ microorganisms. Advances in Colloid and Interface Science.

[44] Kamiya, H. et al. Preparation of Highly Dispersed Ultrafine Barium Titanate Powder
by Using Microbial‐Derived Surfactant. Journal of the American Ceramic Society86,
2011-2018 (2012).

[45] Pithan, C., Hennings, D. & Waser, R. Progress in the Synthesis of Nanocrystalline Ba‐
TiO3 Powders for MLCC. International Journal of Applied Ceramic Technology2, 1-14
(2005).

[46] Kim, P. et al. High Energy Density Nanocomposites Based on Surface-Modified Ba‐
TiO3 and a Ferroelectric Polymer. ACS Nano3, 2581-2592 (2009).

[47] Dang, Z.-M. et al. Fabrication and Dielectric Characterization of Advanced BaTiO3/
Polyimide Nanocomposite Films with High Thermal Stability. Advanced Functional
Materials18, 1509-1517 (2008).

[48] Zhou, T. et al. Improving Dielectric Properties of BaTiO3/Ferroelectric Polymer Com‐

posites by Employing Surface Hydroxylated BaTiO3 Nanoparticles. ACS Applied Ma‐
terials & Interfaces3, 2184-2188 (2011).

[49] Fan, B.-H., Zha, J.-W., Wang, D.-R., Zhao, J. & Dang, Z.-M. Experimental study and
theoretical prediction of dielectric permittivity in BaTiO3/polyimide nanocomposite
films. Applied Physics Letters100, 092903-4 (2012).

[50] Nagao, D., Kinoshita, T., Watanabe, A. & Konno, M. Fabrication of highly refractive,
transparent BaTiO3/poly(methyl methacrylate) composite films with high permittivi‐
ties. Polymer International60, 1180-1184 (2011).

[51] Abe, K., Nagao, D., Watanabe, A. & Konno, M. Fabrication of highly refractive bari‐
um-titanate-incorporated polyimide nanocomposite films with high permittivity and
thermal stability. Polymer International, n/a-n/a (2012).

[52] Balzani, V. Nanochemistry: A Chemical Approach to Nanomaterials. Geoffrey A.

Ozin and André C. Arsenault. Small2, 678-679 (2006).
496 Advances in Ferroelectrics

[53] Reznikov, Y. et al. Ferroelectric nematic suspension. Applied Physics Letters82,

1917-1919 (2003).
[54] Reznikov, Y. in Liquid Crystals Beyond Displays: Chemistry, Physics, and Applica‐
tions (ed. Li, Q.) 403-426 (John Wiley & Sons, Inc., 2012).
[55] Liang, H.-H. & Lee, J.-Y. Enhanced Electro-Optical Properties of Liquid Crystals De‐
vices by Doping with Ferroelectric Nanoparticles. Ferroelectrics - Material Aspects,
193-210 (2011).
[56] Ciofani, G. et al. Preparation of stable dispersion of barium titanate nanoparticles:
Potential applications in biomedicine. Colloids and Surfaces B: Biointerfaces76, 535–543
(2010).
[57] Hsieh, C.-L., Grange, R., Pu, Y. & Psaltis, D. Bioconjugation of barium titanate nano‐
crystals with immunoglobulin G antibody for second harmonic radiation imaging
probes. Biomaterials31, 2272–2277 (2010).
[58] Hsieh, C.-L., Grange, R., Pu, Y. & Psaltis, D. (eds. Campagnola, P.J., Stelzer, E.H.K. &
von Bally, G.) 73670D-6 (SPIE, Munich, Germany, 2009).
[59] Hsieh, C.-L., Grange, R., Pu, Y. & Psaltis, D. Three-dimensional harmonic holograph‐
ic microcopy using nanoparticles as probes for cell imaging. Optics Express17,
2880-2891 (2009).
[60] Grange, R., Hsieh, C.L., Pu, Y. & Psaltis, D. in European Conference on Lasers and
Electro-Optics 2009 and the European Quantum Electronics Conference. CLEO Eu‐
rope - EQEC 2009. 1-1 (2009).
[61] Ciofani, G. et al. in Piezoelectric Nanomaterials for Biomedical Applications 213-238
(Springer Berlin Heidelberg, 2012).
[62] Yust, B.G., Razavi, N., Pedraza, F. & Sardar, D.K. (eds. Cartwright, A.N. & Nicolau,
D.V.) 82310H-6 (SPIE, San Francisco, California, USA, 2012).
[63] Zipfel, W.R. et al. Live tissue intrinsic emission microscopy using multiphoton-excit‐
ed native fluorescence and second harmonic generation. Proceedings of the National
Academy of Sciences100, 7075-7080 (2003).
[64] Pantazis, P., Maloney, J., Wu, D. & Fraser, S.E. Second harmonic generating (SHG)
nanoprobes for in vivo imaging. Proceedings of the National Academy of Sciences107,
14535-14540 (2010).
[65] Ciofani, G., Ricotti, L. & Mattoli, V. Preparation, characterization and in vitro testing
of poly(lactic-co-glycolic) acid/barium titanate nanoparticle composites for enhanced
cellular proliferation. Biomedical Microdevices13, 255-266 (2011).
[66] Pantazis, P., Pu, Y., Psaltis, D. & Fraser, S. (eds. Periasamy, A. & So, P.T.C.) 71831P-5
(SPIE, San Jose, CA, USA, 2009).
[67] Horiuchi, N. Imaging: Second-harmonic nanoprobes. Nature Photonics5, 7-7 (2011).
 Emerging Applications of Ferroelectric Nanoparticles in Materials Technologies, Biology and Medicine 497
http://dx.doi.org/10.5772/52516

[68] Hsieh, C.-L., Grange, R., Pu, Y. & Psaltis, D. (eds. Mohseni, H. & Razeghi, M.)
77590T-6 (SPIE, San Diego, California, USA, 2010).

[69] Hsieh, C.-L., Lanvin, T., Grange, R., Pu, Y. & Psaltis, D. in Conference on Lasers and
Electro-Optics (CLEO), 2011 1-2 (2011).

[70] Semenov, S., Pham, N. & Egot-Lemaire, S. in World Congress on Medical Physics
and Biomedical Engineering (eds. Dössel, O. & Schlegel, W.C.) 311-313 (Springer Ber‐
lin Heidelberg, Munich, Germany, 2009).

[71] Adur, J. et al. (eds. Periasamy, A., Konig, K. & So, P.T.C.) 82263P-7 (SPIE, San Fran‐
cisco, California, USA, 2012).

[72] Wang, C.-C. et al. Differentiation of normal and cancerous lung tissues by multipho‐
ton imaging. Journal of Biomedical Optics14, 044034-4 (2009).

[73] Chan, W.C.W. in Advances in Experimental Medicine and Biology 208 (Springer Sci‐
ence+Business Media, LLC, 2007).

[74] Dempsey, W.P., Fraser, S.E. & Pantazis, P. SHG nanoprobes: Advancing harmonic
imaging in biology. BioEssays34, 351-360 (2012).

[75] Yust, B.G., Sardar, D.K. & Tsin, A. (eds. Cartwright, A.N. & Nicolau, D.V.) 79080G-7
(SPIE, San Francisco, California, USA, 2011).

[76] Ganeev, R.A., Suzuki, M., Baba, M., Ichihara, M. & Kuroda, H. Low- and high-order
nonlinear optical properties of BaTiO3 and SrTiO3 nanoparticles. Journal of the Optical
Society of America B25, 325-333 (2008).

[77] Lai, K.T., Nair, B.G. & Semenov, S. Optical and microwave studies of ferroelectric
nanoparticles for application in biomedical imaging. Microwave and Optical Technolo‐
gy Letters54, 11-13 (2012).

[78] Ciofani, G. et al. 987-990 (KINTEX, Korea, 2010).

[79] Furuya, K., Morita, Y., Tanaka, K., Katayama, T. & Nakamachi, E. (eds. Martin-Pal‐
ma, R.J. & Lakhtakia, A.) 79750U-6 (SPIE, San Diego, California, USA, 2011).

[80] Florence, A.T. “Targeting” nanoparticles: The constraints of physical laws and physi‐
cal barriers. (2012).
 Chapter 22

Photorefractive Effect in Ferroelectric Liquid Crystals

Takeo Sasaki

Additional information is available at the end of the chapter

http://dx.doi.org/10.5772/52921

1. Introduction

Ferroelectric liquid crystals have been attracting great interest for their application in photo‐
refractive devices. The photorefractive effect is a phenomenon by which a change in refrac‐
tive index is induced by the interference of laser beams [1, 2]. Dynamic holograms are easily
realized by the photorefractive effect. Holograms generate three-dimensional images of ob‐
jects. They are produced by recording interference fringes generated by light reflected from
an object and a reference light (Figure 1). A hologram diffracts incident light to produce a
three-dimensional images of an object. 3D displays are expected to be widely used as next-
generation displays. However, current 3D displays are essentially stereograms. However,
holographic displays that can realize natural 3D images are anticipated.
The photorefractive effect has the potential to realize dynamic holograms by recording holo‐
grams as a change in the refractive index of the medium [1, 2]. The photorefractive effect
induces a change in the refractive index by a mechanism involving both photovoltaic and
electro-optic effects (Figure 2). When two laser beams interfere in an organic photorefractive
material, a charge generation occurs at the bright positions of the interference fringes. The
generated charges diffuse or drift within the material. Since the mobilities of positive and
negative charges are different in most organic materials, a charge separated state is formed.
The charge with the higher mobility diffuses over a longer distance than the charge with
lower mobility, such that while the low mobility charge stays in the bright areas, the high
mobility charge moves to the dark areas. The bright and dark positions of the interference
fringes are thus charged with opposite polarities and an internal electric field (space-charge
field) is generated in the area between the bright and dark positions. The refractive index of
this area between the bright and dark positions is changed through the electro-optic effect.
Thus, a refractive index grating (or hologram) is formed. One material class that exhibits
high photorefractivity is that of glassy photoconductive polymers doped with high concen‐
trations of D-π-A chromophores, in which donor and acceptor groups are attached to a π-

© 2012 Sasaki; licensee InTech. This is an open access article distributed under the terms of the Creative
Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
500 Advances in Ferroelectrics

conjugate system [3-5]. In order to obtain photorefractivity in polymer materials, a high

electric field of 10–50 V/μm is usually applied to a polymer film [6-8]. This electric field is
necessary to increase charge generation efficiency. Significantly, the photorefractive effect
permits two-beam coupling. It can be used to coherently amplify signal beams, and so has
the potential to be used in a wide range of optical technologies as a transistor in electric cir‐
cuits. With the aim of developing a 3D display, a multiplex hologram has been demonstrat‐
ed using a photorefractive polymer film [9,10]. Clear 3D images were recorded in the film.
However, the slow response (~100 ms) and the high electric field (30–50 V/μm) required to
activate the photorefractive effect in the polymer materials both need to be improved.

Figure 1. Hologram recording and image reconstruction. (a) A light reflected from an object is interfered with by a
reference light in a photo-sensitive material, such as a photopolymer. (b) The interference fringe is recorded in a pho‐
tosensitive material (hologram). (c) A readout beam is irradiated by the hologram. (d) The readout beam is diffracted
by the hologram and the object image is reconstructed.

Ferroelectric liquid crystals are expected to be used as high performance photorefractive ma‐
terials [11-13]. A photorefractive ferroelectric liquid crystal with a fast response of 5 ms has
been reported [14]. The photorefractive effect has been reported in surface-stabilized ferro‐
electric liquid crystals (SS-FLCs) doped with a photoconductive compound. Liquid crystals
are classified into several groups. The most well known are nematic liquid crystals and
smectic liquid crystals.
 Photorefractive Effect in Ferroelectric Liquid Crystals 501
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Figure 2. Schematic illustration of the mechanism of the photorefractive effect. (a) Two laser beams interfere in the
photorefractive material; (b) charge generation occurs at the light areas of the interference fringes; (c) electrons are
trapped at the trap sites in the light areas and holes migrate by diffusion or drift in the presence of an external electric
field and generate an internal electric field between the light and dark positions; (d) the refractive index of the corre‐
sponding area is altered by the internal electric field generated.

Nematic liquid crystals are used in LC displays. On the other hand, smectic liquid crystals
are very viscous and, hence, are not utilized in any practical applications. Ferroelectric liq‐
uid crystals (FLCs) belong to the class of smectic liquid crystals that have a layered structure
(Figure 3). The molecular structure of a typical FLC contains a chiral unit, a carbonyl group,
a central core - which is a rigid rod-like structure, such as biphenyl, phenylpyrimidine or
phenylbenzoate - and a flexible alkyl chain [15]. Thus, the dipole moment of an FLC mole‐
cule is perpendicular to the molecular long axis. FLCs exhibit a chiral smectic C phase
(SmC*) that possesses a helical structure. Compared to nematic LCs, FLCs are more crystal
than liquid and the preparation of fine FLC films requires several sophisticated techniques.
Obtaining a uniformly aligned, defect-free, surface-stabilized FLC (SS-FLC, Figure 3) using a
single FLC compound is very difficult, and mixtures of several LC compounds are usually
used to obtain fine SS-FLC films.
502 Advances in Ferroelectrics

FLC m olecule

Sm e c tic SS-FLC
Figure 3. Structures of the smectic phase and the surface stabilized smectic-C phase (SS-FLC).

The FLC mixtures are composed of the base LC - which is also a mixture of several LC com‐
pounds - and a chiral compound. The chiral compound introduces a helical structure into
the LC phase through supramolecular interactions. It should be mentioned here that in or‐
der to observe ferroelectricity in these materials, the ferroelectric liquid crystals must be
formed into thin films. The thickness of the film must be within a few micrometers. When an
FLC is sandwiched between glass plates to form a film a few micrometers thick, the helical
structure of the smectic C phase uncoils and a surface-stabilized state (SS-state) is formed in
which spontaneous polarization (Ps) appears. For display applications, the thickness of the
film is usually 2 μm. In such thin films, FLC molecules can align in only two directions. This
state is called a surface-stabilized state (SS-state). The alignment direction of the FLC mole‐
cules changes according to the direction of the spontaneous polarization (Figure 4). The di‐
rection of the spontaneous polarization is governed by the photoinduced internal electric
field, giving rise to a refractive index grating with properties dependent on the direction of
polarization.

electric field electric field

Electro-optical switching of FLC

Figure 4. Electro-optical switching in the surface-stabilized state of FLCs.

 Photorefractive Effect in Ferroelectric Liquid Crystals 503
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Figure 5 shows a schematic illustration of the mechanism of the photorefractive effect in

FLCs. When laser beams interfere in a mixture of an FLC and a photoconductive compound,
charge separation occurs between bright and dark positions and an internal electric field is
produced. The internal electric field alters the direction of spontaneous polarization in the
area between the bright and dark positions of the interference fringes, which induces a peri‐
odic change in the orientation of the FLC molecules. This is different from the processes that
occur in other photorefractive materials in that the molecular dipole rather than the bulk po‐
larization responds to the internal electric field. Since the switching of FLC molecules is due
to the response of bulk polarization, the switching is extremely fast.

Figure 5. Schematic illustration of the mechanism of the photorefractive effect in FLCs. (a) Two laser beams interfere
in the surface-stabilized state of the FLC/photoconductive compound mixture; (b) charge generation occurs at the
bright areas of the interference fringes; (c) electrons are trapped at the trap sites in the bright areas, holes migrate by
diffusion or drift in the presence of an external electric field to generate an internal electric field between the bright
and dark positions; (d) the orientation of the spontaneous polarization vector (i.e., the orientation of mesogens in the
FLCs) is altered by the internal electric field.

2. Characteristics of the photorefractive effect

Since a change in the refractive index via the photorefractive effect occurs in the areas be‐
tween the bright and dark positions of the interference fringe, the phase of the resulting in‐
dex grating is shifted from the interference fringe. This is characteristic of the
photorefractive effect that the phase of the refractive index grating is π/2-shifted from the
interference fringe. When the material is photochemically active and is not photorefractive,
504 Advances in Ferroelectrics

a photochemical reaction takes place at the bright areas and a refractive index grating with
the same phase as that of the interference fringe is formed (Figure 6(a)).

Asymm etric Energy Exchange

Figure 6. (a) Photochromic grating, and (b) photorefractive grating.

The interfering laser beams are diffracted by this grating; however, the apparent transmitted
intensities of the laser beams do not change because the diffraction is symmetric. Beam 1 is
diffracted in the direction of beam 2 and beam 2 is diffracted in the direction of beam 1.
However, if the material is photorefractive, the phase of the refractive index grating is shift‐
ed from that of the interference fringes, and this affects the propagation of the two beams.
Beam 1 is energetically coupled with beam 2 for the two laser beams. Consequently, the ap‐
parent transmitted intensity of beam 1 increases and that of beam 2 decreases (Figure 6(b)).
This phenomenon is termed ‘asymmetric energy exchange’ in the two-beam coupling ex‐
periment. The photorefractivity of a material is confirmed by the occurrence of this asym‐
metric energy exchange.

3. Measurement of photorefractivity

The photorefractive effect is evaluated by a two-beam coupling method and by a four-wave

mixing experiment. Figure 7(a) shows a schematic illustration of the experimental setup
used for the two-beam coupling method. A p-polarized beam from a laser is divided into
two beams by a beam splitter and the beams are interfered within the sample film. An elec‐
tric field is applied to the sample using a high voltage supply unit. This external electric
field is applied in order to increase the efficiency of charge generation in the film. The
change in the transmitted beam intensity is monitored. If a material is photorefractive, an
asymmetric energy exchange is observed. The magnitude of photorefractivity is evaluated
using a parameter called the gain coefficient, which is calculated from the change in the
transmitted intensity of the laser beams induced through the two-beam coupling [1]. In or‐
der to calculate the two-beam coupling gain coefficient, it must be determined whether the
 Photorefractive Effect in Ferroelectric Liquid Crystals 505
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diffraction condition is within the Bragg regime or within the Raman-Nath regime. These
diffraction conditions are distinguished by a dimensionless parameter Q.

Q = 2πlL/nΛ 2 (1)

(a) FLC sample (b) FLC sample

detectors
beam 1 beam 1
beam 2 beam 2
beam 3
beam 4

detector
Figure 7. Schematic illustrations of the experimental set-up for the (a) two-beam coupling, and (b) four-wave-mixing
techniques.

Q > 1 is defined as the Bragg regime of optical diffraction. In this regime, multiple scattering
is not permitted, and only one order of diffraction is produced. Conversely, Q < 1 is defined
as the Raman-Nath regime of optical diffraction. In this regime, many orders of diffraction
can be observed. Usually, Q > 10 is required to guarantee that the diffraction is entirely with‐
in the Bragg regime. When the diffraction is in the Bragg diffraction regime, the two-beam
coupling gain coefficient Γ (cm-1) is calculated according to the following equation:

Γ=
1
D
ln( gm
1 + m−g
) (2)

where D = L/cos(θ) is the interaction path for the signal beam (L=sample thickness, θ =prop‐
agation angle of the signal beam in the sample), g is the ratio of the intensities of the signal
beam behind the sample with and without a pump beam, and m is the ratio of the beam
intensities (pump/signal) in front of the sample.

A schematic illustration of the experimental setup used for the four-wave mixing experi‐
ment is shown in Figure 7(b). S-polarized writing beams are interfered in the sample film
and the diffraction of a p-polarized probe beam, counter-propagating to one of the writing
beams, is measured. The diffracted beam intensity is typically measured as a function of
time, applied (external) electric field and writing beam intensities, etc. The diffraction effi‐
ciency is defined as the ratio of the intensity of the diffracted beam and the intensity of the
probe beam that is transmitted when no grating is present in the sample due to the writing
beams. In probing the grating, it is important that beam 3 does not affect the grating or inter‐
act with the writing beams. This can be ensured by making the probe beam much weaker
than the writing beams and by having the probe beam polarized orthogonal to the writing
beams.
506 Advances in Ferroelectrics

4. Photorefractive effect of FLCs

4.1. Two-beam coupling experiments on FLCs

The photorefractive effect in an FLC was first reported by Wasielewsky et al. in 2000 [11].
Since then, details of photorefractivity in FLC materials have been further investigated by
Sasaki et al. and Golemme et al. [12-14]. The photorefractive effect in a mixture of an FLC
and a photoconductive compound was measured in a two-beam coupling experiment using
a 488 nm Ar+ laser. The structures of the photoconductive compounds used are shown in
Figure 8. A commercially available FLC, SCE8 (Clariant), was used. CDH was used as a pho‐
toconductive compound and TNF was used as a sensitizer. The concentrations of CDH and
TNF were 2 wt% and 0.1 wt% respectively. The samples were injected into a 10-μm-gap
glass cell equipped with 1 cm2 ITO electrodes and a polyimide alignment layer (Figure 9).

NO 2

N N NO 2
N O 2N

O
CDH TNF

ECz
Figure 8. Structures of the photoconductive compound CDH, ECz and the sensitizer TNF

Figure 9. Laser beam incidence condition and the structure of the LC cell.
 Photorefractive Effect in Ferroelectric Liquid Crystals 507
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Figure 10 shows a typical example of asymmetric energy exchange observed in the

FLC(SCE8)/CDH/TNF sample under an applied DC electric field of 0.1 V/μm [12]. The inter‐
ference of the divided beams in the sample resulted in the increased transmittance of one
beam and the decreased transmittance of the other. The change in the transmitted intensities
of the two beams is completely symmetric, as can be seen in Figure 10. This indicates that
the phase of the refractive index grating is shifted from that of the interference fringes. The
grating formation was within the Bragg diffraction regime and no higher-order diffraction
was observed under the conditions used.

The temperature dependence of the gain coefficient of SCE8 doped with 2 wt% CDH and 0.1
wt% TNF is shown in Figure 11(a). Asymmetric energy exchange was observed only at tem‐
peratures below 46°C. The spontaneous polarization of the identical sample is plotted as a
function of temperature in Figure 11(b).

Figure 10. A typical example of asymmetric energy exchange observed in an FLC (SCE8) mixed with 2 wt% CDH and
0.1 wt% TNF. An electric field of +0.3 V/μm was applied to the sample.
508 Advances in Ferroelectrics

(a) 20 (b) 6
S CE8 CDH2.0wt% S CE8 CDH 2.0wt%
5
15
4

10 3

2
5
1

0 0
25 30 35 40 45 50 55 60 65 25 30 35 40 45 50 55 60 65
Tem perature (°C) Tem perature (°C )

Figure 11. Temperature dependence of (a) the gain coefficient, and (b) the spontaneous polarization of an FLC (SCE8)
mixed with 2 wt% CDH and 0.1 wt% TNF. For two-beam coupling experiments, an electric field of 0.1 V/μm was ap‐
plied to the sample.

Similarly, the spontaneous polarization vanished when the temperature was raised above
46°C. Thus, asymmetric energy exchange was observed only in the temperature range in
which the sample exhibited ferroelectric properties; in other words, the SmC* phase. Since
the molecular dipole moment of the FLCs is small and the dipole moment is aligned perpen‐
dicular to the molecular axis, large changes in the orientation of the molecular axis cannot be
induced by an internal electric field in the SmA or N* phase of the FLCs. However, in the
SmC* phase, reorientation associated with spontaneous polarization occurs due to the inter‐
nal electric field. The spontaneous polarization also causes the orientation of FLC molecules
in the corresponding area to change accordingly. A maximum resolution of 0.8 μm was ob‐
tained in this sample.

4.2. Effect of the magnitude of the applied electric field

In polymeric photorefractive materials, the strength of the externally applied electric field is
a very important factor. The external electric field is necessary to increase the charge separa‐
tion efficiency sufficiently to induce a photorefractive effect. In other words, the photorefrac‐
tivity of the polymer is obtained only with the application of a few V/μm electric fields. The
thickness of the polymeric photorefractive material commonly reported is about 100 μm, so
the voltage necessary to induce the photorefractive effect is a few kV. On the other hand, the
photorefractive effect in FLCs can be induced by applying a very weak external electric
field. The maximum gain coefficient for the FLC (SCE8) sample was obtained using an elec‐
tric field strength of only 0.2–0.4 V/μm. The thickness of the FLC sample is typically 10 μm,
so that the voltage necessary to induce the photorefractive effect is only a few V. The de‐
pendence of the gain coefficient of a mixture of FLC (SCE8)/CDH/TNF on the strength of the
electric field is shown in Figure 12. The gain coefficient of SCE8 doped with 0.5–1 wt% CDH
increased with the strength of the external electric field. However, the gain coefficient of
 Photorefractive Effect in Ferroelectric Liquid Crystals 509
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SCE8 doped with 2 wt% CDH decreased when the external electric field exceeded 0.4 V/μm.
The same tendency was observed for M4851/050 as well. The formation of an orientational
grating is enhanced when the external electric field is increased from 0 to 0.2 V/μm as a re‐
sult of induced charge separation under a higher external electric field. However, when the
external electric field exceeded 0.2 V/μm, a number of zigzag defects appeared in the sur‐
face-stabilized state. These defects cause light scattering and result in a decrease in the gain
coefficient.

(a) 30 (b) 25
M 4851 /05 0
SCE8
25 1.0wt% 1.0wt%
20

20 2.0wt% 15
15
0.5wt% 10
10 0.5wt%
5
5

0 0
0 0.2 0.4 0.6 0 .8 1.0 1.2 0 0 .0 5 0.10 0 .1 5 0.20 0 .2 5 0.30 0 .3 5
Electric field (V/ mm ) Electric field (V/ mm )

Figure 12. Electric field dependence of the gain coefficient of SCE8 and M4851/050 mixed with several concentra‐
tions of CDH and 0.1 wt% TNF in a 10 μm-gap cell measured at 30 °C.

4.3. Refractive index grating formation time

The formation of a refractive index grating involves charge separation and reorientation.
The index grating formation time is affected by these two processes and both may be rate-
determining steps. The refractive index grating formation times in SCE8 and M4851/050
were determined based on the simplest single-carrier model of photorefractivity [1,2],
wherein the gain transient is exponential. The rising signal of the diffracted beam was fitted
using a single exponential function, shown in equation (3).

γ(t) – 1 = (γ– 1)[1 – exp(–t/τ)]2 (3)

Here, γ(t) represents the transmitted beam intensity at time t divided by the initial intensity
(γ(t) = I(t)/I0) and τ is the formation time. The grating formation time in SCE8/CDH/TNF is
plotted as a function of the strength of the external electric field in Figure 13(a). The grating
formation time decreased with increasing electric field strength due to the increased efficien‐
cy of charge generation. The formation time was shorter at higher temperatures, corre‐
sponding to a decrease in the viscosity of the FLC with increasing temperature. The
formation time for SCE8 was found to be 20 ms at 30°C. As shown in Figure 13(b), the for‐
510 Advances in Ferroelectrics

mation time for M4851/050 was found to be independent of the magnitude of the external
electric field, with a time of 80-90 ms for M4851/050 doped with 1 wt% CDH and 0.1 wt%
TNF. This is slower than for SCE8, although the spontaneous polarization of M4851/050 (-14
nC/cm2) is larger than that of SCE8 (-4.5 nC/cm2) and the response time of the electro-optical
switching (the flipping of spontaneous polarization) to an electric field (±10 V in a 2 μm cell)
is shorter for M4851/050. The slower formation of the refractive index grating in M4851/050
is likely due to the poor homogeneity of the SS-state and charge mobility.

(a) 20 0 (b) 2 00

SCE8 CDH2.0wt% M4851/050 CDH1.0wt%

15 0 30°C 1 50

1 00
49°C
10 0

42°C
50
37°C 50

0 0
0 0.2 0 .4 0.6 0.8 1 .0 1.2 1.4 1.6 0 0 .5 1 1.5 2 2 .5 3 3 .5
Electric field (V/ mm) Electric field (V/mm)

Figure 13. Electric field dependence of the index grating formation time. (a) SCE8 mixed with 2 wt% CDH and 0.1 wt
% TNF in the two-beam coupling experiment. , measured at 30 °C (T/TSmC*-SmA=0.95); , measured at 36 °C (T/TSmC*-
SmA=0.97). (b) M4851/050 mixed with 1 wt% CDH and 0.1 wt% TNF in a two-beam coupling experiment. , measured
at 42 °C (T/TSmC*-SmA=0.95); , measured at 49 °C (T/TSmC*-SmA=0.97).

4.4. Formation mechanism of the internal electric field in FLCs

Since the photorefractive effect is induced by the photoinduced internal electric field, the
mechanism of the formation of the space-charge field in the FLC medium is important. The
two-beam coupling gain coefficients of mixtures of FLC (SCE8) and photoconductive com‐
pounds under a DC field were investigated as a function of the concentration of TNF (elec‐
tron acceptor). The photoconductive compounds - CDH, ECz and TNF (Figure 8) - were
used in this examination. When an electron donor with a large molecular size (CDH) rela‐
tive to the TNF was used as the photoconductive compound, the gain coefficient was strong‐
ly affected by the concentration of TNF (Figure 14(a)). However, when ethylcarbazole (ECz)
- the molecular size of which is almost the same as that of TNF - was used, the gain coeffi‐
cient was less affected by the TNF concentration (Figure 14(b)).
 Photorefractive Effect in Ferroelectric Liquid Crystals 511
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40
(a) CD H (b ) E C z
35 0.5w t%
30 0.3w t%
0.1w t%
25
T N F con ce ntratio n
20
15
T N F con cen tra tion
10
5

0 0.2 0 .4 0.6 0.8 1.0

Electric field (V/ mm) Electric field (V/ mm )
Figure 14. Dependence of the TNF concentration on the gain coefficients of an FLC doped with photoconductive
dopants. (a) SCE8 doped with 2 wt% CDH, and (b) SCE8 doped with 2 wt% ECz. An electric field of ± 0.5 V/μm, 100 Hz
was applied.

These findings suggest that ionic conduction plays a major role in the formation of the
space-charge field. The mobility of the CDH cation is smaller than that of the TNF anion,
and this difference in mobility is thought to be the origin of the charge separation. In this
case, the magnitude of the internal electric field is dominated by the concentration of the
ionic species. On the other hand, the difference in the mobilities of ECz and TNF is small
and, thus, less effective charge separation is induced, indicating that the internal electric
field is independent of the concentration of ionic species.

4.5. Photorefractive effect in FLC mixtures containing photoconductive chiral compounds

4.5.1. Photoconductive chiral dopants

The photorefractive effect of FLC mixtures containing photoconductive chiral dopants has
been investigated [15]. The structures of the LC compounds, the electron acceptor trinitro‐
fluorenone (TNF) and the photoconductive chiral compounds are shown in Figure 15. The
mixing ratio of 8PP8 and 8PP10 was set to 1:1 because the 1:1 mixture exhibits the SmC
phase over the widest temperature range. Hereafter, the 1:1 mixture of 8PP8 and 8PP10 is
referred to as the base LC. The concentration of TNF was 0.1 wt%. Four photoconductive
chiral compounds with the terthiophene chromophore (3T-2MB, 3T-2OC, 3T-OXO, and 3T-
CF3) were synthesized. The base LC, TNF and a photoconductive chiral compound were
dissolved in dichloroethane and the solvent was evaporated. The mixture was then dried
in a vacuum at room temperature for one week. The samples were subsequently injected
into a 10-μm-gap glass cell equipped with 1-cm2 ITO electrodes and a polyimide align‐
ment layer for the measurements. The base LC, which is a 1:1 mixture of 8PP8 and 8PP10,
was mixed with the photoconductive chiral dopants and the electron acceptor (TNF). The
concentration of TNF was set to 0.1 wt%. The terthiophene chiral dopants showed high
512 Advances in Ferroelectrics

miscibility with the phenyl pyrimidine-type smectic LC. The chiral smectic C (SmC*)
phase appeared in all of the mixtures of the base LC and the chiral dopants. With the in‐
crease of the concentration of the chiral dopants, the temperature range of the SmC*
phase and the chiral nematic (N*) phase were reduced, whereas that of the smectic A
(SmA) phase was enhanced. The miscibility of the 3T-CF3 with the base LC was the low‐
est among the four chiral dopants. It was considered that the dipole moment of the tri‐
fluoromethyl substituted group is large, so that the 3T-CF3 molecules tend to aggregate.
All the samples exhibited absorption maxima at 394 nm. Absorption at 488 nm (wave‐
length of the laser used) was small. The absorption spectra were not changed when TNF
(1.0 × 10-5 mol/L) was added to the solution. The small absorption at the laser wavelength
is advantageous for minimizing the optical loss. The photocurrents in the mixtures of the
base LC, photoconductive chiral dopants and TNF were measured. As shown in Figure
16, the samples were good insulators in the dark. When a 488 nm laser irradiated the
samples, photocurrents were clearly observed. The magnitudes of the photocurrents were
slightly different in the four samples. The only difference in the molecular structures of
these compounds is the chiral substituent. Thus, the difference in the photocurrent cannot
be attributed to the difference in the molecular structure. It was considered that the misci‐
bility of the photoconductive chiral compounds to the LC and the homogeneity of the LC
phase affected the magnitude of the photocurrent.

N
C 8H17 OC 8 H 1 7 N O2
N
8P P8 O2N NO 2
N
C8 H17 OC 1 0 H 2 1 O
N TN F
8P P10
O O
C8H 17 S S C8H 17 S S
S O S O O
O
Me
3T-2M B 3T-O X O Me

O O C F3
C8H17 S S C8H 17 S S
S O C6H13 S O C6 H13

3T-2O C 3T-C F3
Figure 15. Structures of the smectic LCs (8PP8 and 8PP10), photoconductive chiral dopants (3T-2MB, 3T-2OC, 3T-OXO
and 3T-CF3) and the sensitizer TNF used in this work.
 Photorefractive Effect in Ferroelectric Liquid Crystals 513
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140 a) 140 b)
120 3 T-2 M B 4w t% 120 3T-2 O C 4 w t%
100 100
80 Ligh t curre nt 80
60 60
L ig ht cu rre n t
40 40
20 20
D a rk curre n t D a rk cu rre n t
0 0
0 0.2 0.4 0.6 0.8 1.0 1.2 0 0.2 0.4 0.6 0.8 1.0 1.2
E lectric fie ld (V / mm ) E le ctric fie ld (V / mm )

140 140
c) d)
120 120
3 T-C F 3 3w t% 3T-O XO 4 w t%
100 100
80 80
Ligh t curre nt
60 60
40 40
L ig ht cu rre n t
20 20
D ark cu rren t D ark cu rre nt
0 0
0 0.2 0.4 0.6 0.8 1.0 1.2 0 0.2 0.4 0.6 0.8 1.0 1.2
E lectric fie ld (V / mm ) E le ctric fie ld (V / mm )

Figure 16. Magnitudes of light-current and dark-current of mixtures of the base LC, photoconductive chiral com‐
pound and TNF measured in a 10-μm-gap LC cell as a function of the external electric field. An electric field of 0.1
V/μm was applied. A 488 nm Ar+ laser (10 mW/cm2, 1 mm diameter) was used as the irradiation source.

4.5.2. Two-beam coupling experiment on photoconductive FLC mixtures

The photorefractive effect was measured in a two-beam coupling experiment. A linearly po‐
larized beam from an Ar+ laser (488 nm, continuous wave) was divided into two by a beam
splitter, each of which was then interfered in the sample film. A p-polarized beam was used.
The laser intensity was 2.5 mW for each beam (1 mm diameter). The incident beam angles to
the glass plane were 30° and 50°. Each interval of the interference fringe was 1.87 μm. Figure
17 shows typical examples of the asymmetric energy exchange observed in a mixture of the
base LC, 3T-2MB and TNF at 30 ºC with the application of an electric field of 0.2–0.4 V/μm.
514 Advances in Ferroelectrics

Figure 17. Examples of the results of two-beam coupling experiments for mixtures of the base LC, 3T-2MB and TNF
measured at 30 °C.

The interference of the divided beams in the sample resulted in the increased transmittance of
one of the beams and the decreased transmittance of the other beam. These transmittance
characteristics were reversed when the polarity of the applied electric field was reversed.
Asymmetric energy exchange was only observed when an electric field was applied, indicat‐
ing that beam coupling was not caused by a thermal grating. With an increased concentration
of 3T-2MB, the magnitude of the gain coefficient also increased. In order to calculate the two-
beam coupling gain coefficient, the diffraction condition needs to be correctly identified.
 Photorefractive Effect in Ferroelectric Liquid Crystals 515
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12 0 80
3T-2M B 3T-O XO
1 00 a) 70 c)
8wt% 8wt%
60
80 4wt% 50
60
6wt%
40
2wt% 30
40
4wt%
20
20
10 2wt%
0 0
0 0.2 0 .4 0.6 0.8 1 1.2 0 0.2 0.4 0 .6 0 .8 1 1 .2
Electric field (V/ mm ) E lectric field (V / mm )
12 0 1 20
b) 3T-2O C 3T-C F3
1 00
d)
10 0

80 6w t% 80

60 60
2wt%

40 2wt% 40
4w t%
20 1w t% 20 1wt%
0 0
0 0.2 0 .4 0 .6 0 .8 1 1 .2 0 0 .2 0 .4 0.6 0.8 1 1 .2
Electric fie ld (V/ mm ) E lectric field (V / mm )
Figure 18. Electric field dependence of the gain coefficients of the mixtures of the base LC, photoconductive chiral
compounds and TNF. (a) 3T-2MB; (b) 3T-2OC; (c) 3T-OXO; (d) 3T-CF3.

The difference in the gain coefficients in mixtures of the base LC, photoconductive chiral
dopants (3T-2MB, 3T-2OC, 3T-OXO, and 3T-CF3) and TNF was investigated. All the sam‐
ples formed a finely aligned SS-state in 10-μm-gap cells with a LX-1400 polyimide alignment
layer and exhibited clear photorefractivity in the ferroelectric phase. The asymmetric energy
exchange was only observed in the temperature range in which the sample exhibits ferro‐
electric properties (SmC* phase). The gain coefficients of the samples are plotted as a func‐
tion of the magnitude of the external electric field in Figure 18. The gain coefficient increased
with the strength of the external electric field up to 0.2-0.6 V/μm and then decreased with
the strength of the external electric field. As the concentration of the photoconductive chiral
dopants increased, so did the gain coefficient. This may be due to the increased density of
charge carriers in the FLC medium and an increase in the magnitude of Ps. All the samples
exhibited relatively large photorefractivity. A gain coefficient higher than 100 cm-1 was ob‐
tained in the 3T-2OC (6 wt%) sample with the application of only 0.2 V/μm. This means that
a voltage of only 2 V is needed to obtain the gain coefficient of 100 cm-1 in a 10 μm FLC sam‐
516 Advances in Ferroelectrics

ple. In the FLCs reported previously, gain coefficients of only 50-60 cm-1 were obtained with
the application of a 1 V/μm electric field. A gain coefficient higher than 100 cm-1 was also
obtained in the 3T-2MB sample with an applied electric field of 0.5 V/μm. In order to obtain
photorefractivity in polymer materials, the application of a high electric field of 10-50 V/μm
to the polymer film is typically required. The small electric field necessary for the activation
of the photorefractive effect in FLCs is thus a great advantage for their use in photorefrac‐
tive devices. The miscibility of 3T-CF3 with the base LC was low and could be mixed with
the base LC at concentrations lower than 2 wt%. The grating formation time in the mixtures
of the base LC, photoconductive chiral dopants and TNF is plotted as a function of the
strength of the external electric field in Figure 19. The grating formation time decreased with
an increased electric field strength due to the increased efficiency of charge generation. The
shortest formation time was obtained as 5–8 ms with a 1 V/μm external electric field in all
chiral compounds. The 3T-CF3 sample exhibited the fastest response. This was because of
the larger polarity of the 3T-CF3.

50 70
a) 3T-2M B c) 3T-O XO
60
40 2wt%
50
30 2wt% 40 6wt%

20 30
4wt% 8wt%
20
10 8wt% 4wt%
10
0 0
0 0.2 0.4 0.6 0.8 1 1.2 0 0.2 0.4 0.6 0.8 1 1.2
Electric fie ld (V/ mm ) E lectric field (V /mm )
50 30
b) 3T-2OC d) 3T-CF3
40 25

20
1wt%
30
15
4wt%
20 2wt%
2wt% 10
10 6 wt%
5
1wt%
0 0
0 0 .2 0 .4 0.6 0.8 1 1.2 0 0.2 0.4 0.6 0.8 1 1.2
Electric field (V /mm ) Electric field (V/ mm )
Figure 19. Electric field dependence of the index grating formation times of mixtures of the base LC, photoconductive
chiral compounds and TNF measured at 30 °C. (a) 3T-2MB; (b) 3T-2OC; (c) 3T-OXO; (d) 3T-CF3.
 Photorefractive Effect in Ferroelectric Liquid Crystals 517
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4.5.3. Photorefractive effect in a ternary mixture of a SmC liquid crystal doped with the
photoconductive chiral compound

The photorefractive effect of the mixture shown in Figure 20 was investigated. The gain co‐
efficients of the samples were measured as a function of the applied electric field strength
(Figure 21(a)). The gain coefficient was calculated to be higher than 800 cm–1 in the 10 wt%
sample with the application of only 1 V/μm. This gain coefficient is eight times higher than
that of the FLCs described in the previous section. It was considered that a higher transpar‐
ency of the ternary LC mixture contributed to the high gain coefficient. The small electric
field required to activate the photorefractive effect in FLCs is a great advantage for photore‐
fractive devices. The response time decreased with an increased electric field strength due to
the increased charge separation efficiency (Figure 21(b)). The shortest formation time ob‐
tained was 8 ms for an external electric field of 1.5 V/μm. The large gain and fast response
are advantageous for realizing optical devices, such as real-time image amplifiers and accu‐
rate measurement devices.

base LC

7
photoconductive
chiral dopant
3T-2MB

sensitizer / electron trap

TNF
Figure 20. Photorefractive FLC mixture containing a ternary mixture of smectic LCs.
518 Advances in Ferroelectrics

Figure 21. (a) Electric field dependence of gain coefficients of mixtures of the base LC, 3T-2MB and TNF (0.1 wt%)
measured at 30 °C. The 3T-2MB concentration was within the range 2–10 wt%. (b) Refractive index grating formation
time (response time) of mixtures of the base LC, 3T-2MB and TNF (0.1 wt%) measured at 30 °C. The 3T-2MB concen‐
tration was within the range 2–10 wt%.

4.5.4. Formation of dynamic holograms in FLC mixtures

The formation of a dynamic hologram was demonstrated. A computer-generated animation

was displayed on a spatial light modulator (SLM). A 488 nm beam from a DPSS laser was
irradiated on the SLM and the reflected beam was incident on the FLC sample. A reference
beam interfered with the beam from the SLM in the FLC sample. The refractive index gra‐
ting formed was within the Raman–Nath regime, in which multiple scattering is allowed. A
633 nm beam from a He–Ne laser was irradiated on the FLC sample and the diffraction was
observed. A moving image of the animation on the computer monitor was observed in the
diffracted beam (Figure 22). No image retention was observed, which means that the holo‐
gram image (refractive index grating) formed in the FLC was rewritten sufficiently rapidly
to project the reproduction of a smooth holographic movie.
 Photorefractive Effect in Ferroelectric Liquid Crystals 519
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M irro r M irro r

SLM
l/2 PBS

D P S S la se r PBS L en s
(48 8 n m )
l/2
P B S : p o larizin g b e a m sp litter l/2
l/2 : h alf-w a ve p la te L e ns
Vo lta ge
su p ply
H e-N e la se r
(63 3 n m )

S a m p le

PC

Figure 22. Dynamic hologram formation experiment on an FLC sample. A computer-generated animation was dis‐
played on the SLM. The SLM modulated the object beam (488 nm), which was irradiated on the FLC sample and inter‐
fered with the reference beam. The readout beam (633 nm) was irradiated on the FLC and diffraction was observed.
520 Advances in Ferroelectrics

5. Photorefractive effect in FLCs with the application of an AC field

5.1. Formation of dynamic holograms based on the spatial modulation of the molecular
motion of FLCs

The formation of dynamic holograms based on the spatial modulation of the molecular mo‐
tion of ferroelectric liquid crystals (FLCs) was demonstrated [16, 17]. The switching move‐
ment of an FLC molecule is essentially a rotational motion along a conical surface. When an
alternating triangular-waveform voltage is applied, the FLC molecules uniformly go
through a consecutive rotational switching motion along a conical surface (Figure 23(a)). If a
photoconductive FLC material is used, this rotational motion can be modulated by illumi‐
nating the material with interfering laser beams, as shown in Figure 23. The internal electric
field vector is directed along the interference fringe wave vector and, in many cases, it dif‐
fers from the direction of the applied alternating electric field. Thus, the total electric field at
each moment on the FLC molecules is altered by the presence of the internal electric field.
The consecutive rotational motion of the FLC molecules in the areas between the light and
dark positions of the interference fringes is biased by the internal electric field. Consequent‐
ly, a grating based on the spatial difference in the rotational motion (or switching motion) of
the FLC molecules is created. This grating is different from those currently used for holo‐
grams, wherein changes in the static properties of a medium - such as absorbance, transpar‐
ency, film thickness and molecular orientation - are induced by photochemical reactions.
The formation of a motion-mode grating was examined using a SCE8/CDH/TNF mixture in a
10 μm-gap-cell. The formation of a holographic grating and the occurrence of a phase shift be‐
tween the formed grating and the interference fringes were examined in this experiment. An al‐
ternating triangular-waveform electric field (0 to ±1 V/μm, and 1 kHz to 3 MHz) was applied to
the sample. Under the effect of an alternating triangular-waveform electric field of ±0.5 V/μm -
100 kHz in the two-beam coupling experiment - the FLC molecules exhibited a consecutive
switching motion. This switching was confirmed using a polarizing microscope equipped with
a photodetector Figure 24. Figure 25(a) shows the transmitted intensities of the laser beams
through the FLC/CDH/TNF mixture upon the application of an alternating electric field as a
function of time. The interference of the divided beams in the sample resulted in the increased
transmittance of one of the beams and the decreased transmittance of the other. The incident
beam conditions were the same as those used in the DC experiment.
Although the transmitted intensity of the laser beam oscillates due to the switching motion
of the FLC molecules, the average intensities of the beams were symmetrically changed, as
shown in Figure 25. This indicates that a diffraction grating based on the spatial difference
in the rotational switching motion of FLC molecules was formed. The symmetric change in
the transmittance of the two beams proves that the phase of the motion-mode grating shift‐
ed from that of the interference fringe. No higher-order diffraction was observed under this
condition. The spacing of the grating was calculated to be 0.9 μm (1,100 lines/mm). Figure 26
shows the temperature dependence of the gain coefficient obtained under an AC electric
field. Asymmetric energy exchange was observed only at those temperatures at which the
FLC/CDH/TNF mixture exhibits a ferroelectric phase. This suggests that ferroelectricity or
the switching movement of SmC* is necessary for beam coupling under an AC electric field.
 Photorefractive Effect in Ferroelectric Liquid Crystals 521
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Figure 23. (a) Electro-optical switching of an FLC. (b) The rotational motion of FLC molecules under the application of
an alternating electric field. (c) Positive and negative charges appear at the light positions of the interference fringe.
(d) An internal electric field develops in the area between the light and dark positions of the interference fringes. The
rotational motion of the FLC molecules in the corresponding area is biased by the internal electric field.
522 Advances in Ferroelectrics

Figure 24. Switching behaviour of SCE8 mixed with 2 wt% CDH and 0.1 wt% TNF under a 100 Hz, ± 0.5 Vm/μm trian‐
gular wave electric field. (a) Transmittance of light through the FLC under a polarizing microscope. (b) Magnitude of
the applied electric field.
 Photorefractive Effect in Ferroelectric Liquid Crystals 523
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Figure 25. a) Typical example of the asymmetric energy exchange observed in two-beam coupling experiments. A trian‐
gular waveform AC electric field of ± 0.5 Vm/μm, 100 Hz was applied in this case. The sample angle α was 50° and the in‐
tersection angle ϕ was 20°. The shutter was opened at t = 0 s and closed at t = 2 s. (b) An example of the curve fit.

20

15

10

0
30 35 40 45

Figure 26. Gain coefficient of the two-beam coupling under an AC electric field as a function of temperature. An AC
electric field of ± 0.5 V/μm, 100 Hz was applied.
524 Advances in Ferroelectrics

Figure 27 shows the gain coefficient plotted as a function of the electric field strength. Asym‐
metric energy exchange was observed at electric field strengths higher than ±0.1 V/μm. Fur‐
thermore, no asymmetric energy exchange was observed without an external electric field.
This eliminates the possibility that beam coupling resulted from either a thermal grating or
from a photochemically-formed grating. The gain coefficient was independent of the exter‐
nal electric field strength for fields higher than ±0.1 V/μm. This behaviour differs from that
reported previously for the photorefractive effect of FLCs under an applied DC electric field,
wherein the gain coefficient decreased with the increasing strength of the external DC elec‐
tric field. The refractive index grating formation time was measured based on the simplest
single-carrier model for photorefractivity, whereby the gain transient is exponential. The
grating formation time τ was obtained from the fitted curve.

30

25

20

15

10

5
0
0 ±0.2 ±0.4 ±0.6 ±0.8 ±1.0 ±1.2 ±1.4

Figure 27. Gain coefficient of the two-beam coupling as a function of the applied AC electric field strength. The fre‐
quency of the field was 100 Hz.
 Photorefractive Effect in Ferroelectric Liquid Crystals 525
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100

80

60

40

20

0
0 ±0.2 ±0.4 ±0.6 ±0.8 ±1.0 ±1.2 ±1.4

Figure 28. Grating formation time as a function of the AC electric field strength. The frequency of the AC field was
100 Hz.

As seen in Figure 28, the grating formation time decreased with an increased applied electric
field strength as a result of the increased efficiency of charge generation. The grating forma‐
tion time was determined to be 30-40 ms in the present case.

5.2. Frequency dependence of the gain coefficient and the grating formation time

The gain coefficients are plotted as a function of the frequency of the applied external elec‐
tric field in Figure 29.

The gain coefficient was observed to increase with an increase in frequency within the range
of 1 Hz to 100 Hz. The FLC exhibited switching based on polarization reversal at a frequen‐
cy lower than 500 Hz. The gain coefficient reached a maximum at frequencies within the
range of 60 Hz to 500 Hz. However, the magnitude of the gain coefficient decreased as the
frequency was increased to higher than 500 Hz. This is thought to be because the FLC can‐
not perform a complete switching motion at frequencies higher than 500 Hz; therefore, the
FLC molecules showed vibrational motion. Moreover, at frequencies from 500 Hz to 2000
Hz, some of the FLC molecules go through a rotational switching motion, whereas others
undergo vibrational motion. When the frequency exceeded 2000 Hz, the magnitude of the
gain coefficient reaches a constant value, regardless of the frequency. Thus, the value of the
526 Advances in Ferroelectrics

gain coefficient at frequencies lower than 500 Hz can be attributed to the photorefractive ef‐
fect based on the complete switching of FLC molecules and, at frequencies higher than 2000
Hz, this represents the photorefractive effect based on the vibrational motion of FLC mole‐
cules caused by an alternating electric field. Figure 30 shows the frequency dependence of
the grating formation time.

10

0
0 1000 2000 3000 4000 5000
Frequency (Hz)

Figure 29. Gain coefficient as a function of the frequency of the applied electric field. The frequency was varied from
1 to 5000 Hz. The strength of the field was ± 0.5 V/μm.
 Photorefractive Effect in Ferroelectric Liquid Crystals 527
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80

70

60

50

40

30
20
0 1000 2000 3000 4000
Frequency (Hz)

Figure 30. Grating formation time as a function of the frequency of the applied electric field. The frequency was var‐
ied from 1 Hz to 4000 Hz. The strength of the field was ± 0.5 V/μm.

The grating formation time was shortened as the frequency increased. In addition, the fre‐
quency dependence of the formation time was not correlated with the dependence of the
gain coefficient. As the frequency of the applied electric field increased, the switching and
vibrational motion of the FLC molecules is thought to be accelerated and the affect on the
internal electric field becomes apparent. Asymmetric energy exchange in FLCs under a static
DC field is dominated by the direction of the DC field. The increase/decrease in the beam
intensity switches when the direction of the field is reversed. This originates from the direc‐
tion of charge separation. Thus, an internal electric field is thought to be difficult to form
under an AC electric field. However, asymmetric energy exchange was observed with good
reproducibility, suggesting that an internal electric field is formed even under an applied
AC electric field. In addition, no energy exchange was observed in any FLC lacking a photo‐
conductive dopant under an AC electric field (Figure 31). This observation indicates that
photoconductivity is necessary for two-beam coupling under an AC field.
528 Advances in Ferroelectrics

Figure 31. An example of the results of the two-beam coupling experiment under an AC electric field for SCE8 with‐
out a photoconductive dopant. An AC electric field of ± 0.5 V/μm, 100 Hz was applied. The shutter was opened at t =
0 s and closed at t = 2 s.

It is necessary to consider both hole transport by a hopping mechanism as well as ionic con‐
duction in order to explain the formation of the space-charge field under an AC field. In ad‐
dition, a number of experimental results support the large contribution of ionic conduction
to the FLC medium. In addition, the photorefractive effect in SCE8 doped with 2 wt% ECz
under an AC field was very small. If ionic conduction is the major contributor to the forma‐
tion of the space-charge field, the anisotropic mobility of ionic species in the LC medium
may affect the formation of the field. As shown in Figure 3, interference fringes are formed
across the smectic layer so that migration of ionic species occurs in the inter-layer direction.
The asymmetric structure of the surface stabilized state of the FLC may lead to the asym‐
metric mobility of cations and anions, which is thought to be one possible model explaining
the charge separation under an AC electric field. However, the mechanism of the formation
of the space-charge field under an AC field requires further investigation.

5.3. Two beam coupling experiment with the application of a biased AC field

An asymmetric energy exchange was observed upon the application of an AC field. This
grating was interpreted as being based on the spatial difference in the molecular motion of
the FLC molecules. The response time was on the order of a few tens of milliseconds and
was dominated by the formation of the internal electric field. The photorefractivity in FLCs
 Photorefractive Effect in Ferroelectric Liquid Crystals 529
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is accomplished through charge generation and diffusion. The application of an AC field to

an FLC results in a very stable photorefractive response. However, it is obvious that an AC
field is not advantageous for charge separation. Thus, the effect of a biased AC electric field
on the photorefractivity of SS-FLCs was investigated. Figure 32 shows the concept of apply‐
ing a biased AC field.

(a) (b)
E E

E p-p
Eb
0V 0V
Tim e Tim e

Figure 32. Concept of a biased AC field application. (a) Alternating electric field. (b) Biased alternating electric field.

A typical example of the two-beam coupling signal is observed with the application of a 2.0
Vp-pμm-1, 100 Hz square waveform electric field without a bias field (Eb = 0), as shown in
Figure 33(a). The transmitted intensities of the laser beams through the FLC/CDH/TNF mix‐
ture upon the application of an alternating electric field as a function of time is shown in the
figure. The interference of the divided beams in the sample resulted in the increased trans‐
mittance of one of the beams and the decreased transmittance of the other. Although the
transmitted intensity of the laser beam oscillates due to the switching motion of the FLC
molecules, the average intensities of the beams were symmetrically changed, as shown in
Figure 33(a). This indicates that a grating based on the spatial difference in the rotational
switching motion of FLC molecules was formed and acted as a diffraction grating.

Figure 33. FigAsymmetric energy exchange with a square waveform of 2.0 Vp-pμm-1, 100 Hz (a) without bias, and (b)
with a bias of 0.5 V μm-1. The intersection angle ϕ was 20° and the sample angle α was 50°.
530 Advances in Ferroelectrics

The asymmetric energy exchange between the signal and the pump beams proves the for‐
mation of a diffraction grating phase-shifted from the interference fringe. The grating is con‐
sidered to be based on the spatial difference in the rotational switching motion of FLC
molecules. When the biased electric field was set to Eb = 0.5 V μm-1, the two-beam coupling
signal was dramatically enhanced (Figure 33(b)). The gain coefficient increased from 10 cm-1
(Eb = 0) to 70 cm-1 (Eb = 0.5 V μm-1). Obviously, the biased field contributes to the formation
of the diffraction grating. The internal electric field is thought to be difficult to form under
an AC electric field. It has been reported that ionic conduction is the major contributor to the
formation of the space-charge field in the photorefractive effect of an FLC. The anisotropic
mobility of ionic species in an LC medium affects the formation of the field. In the experi‐
mental conditions reported, the interference fringe is formed across the smectic layer so that
migration of ionic species occurs in the inter-layer direction. The asymmetric structure of the
surface stabilized state of the FLC may lead to the asymmetric mobility of cations and
anions. It was considered that the charge separated state is more effectively formed under a
biased AC field.

6. Conclusion

The reorientational photorefractive effect based on the response of bulk polarization was
observed in dye-doped FLC samples. Photorefractivity was observed only in the ferroelec‐
tric phase of these samples and the refractive index formation time was found to be short‐
er than that of nematic LCs. The response time was in the order of ms and was
dominated by the formation of the internal electric field. These results indicate that the
mechanism responsible for refractive index grating formation in FLCs is different from
that for non-ferroelectric materials and that it is clearly related to the ferroelectric proper‐
ties of the material. The photorefractivity of FLCs was strongly affected by the properties
of the FLCs themselves. Besides, with properties such as spontaneous polarization, viscos‐
ity and phase transition temperature, the homogeneity of the SS-state was also found to
be a major factor. The gain coefficient, refractive index grating formation time (response
time) and stability of the two-beam coupling signal were all strongly affected by the ho‐
mogeneity of the SS-state. Therefore, a highly homogeneous SS-state is necessary to create
a photorefractive device. The techniques employed recently in the development of fine LC
display panels will be utilized in the future in the fabrication of photorefractive devices.

Acknowledgment

The authors would like to thank the Japan Science and Technology Agency (JST) S-innova‐
tion and the Canon Foundation for support.
 Photorefractive Effect in Ferroelectric Liquid Crystals 531
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Author details

Takeo Sasaki

Tokyo University of Science, Japan

References

[1] Yeh, P. Introduction to Photorefractive Nonlinear Optics; John Wiley: New York,
1993.

[2] Solymar, L.; Webb, J. D.; Grunnet-Jepsen, A. The Physics and Applications of Photo‐
refractive Materials; Oxford: New York, 1996.

[3] Moerner, W. E.; Silence, S. M. Chem. Rev. 1994, 94, 127-155.

[4] Meerholz, K.; Volodin, B. L.; Kippelen, B.; Peyghambarian, N. Nature 1994, 371,
497-500.

[5] Kippelen, B.; Marder, S. R.; Hendrickx, E.; Maldonado, J. L.; Guillemet, G.; Volodin,
B. L.; Steele, D. D.; Enami, Y.; Sandalphon; Yao, Y. J.; Wang, J. F.; Röckel, H.; Erskine,
L.; Peyghambarian, N. Science 1998, 279, 54-56.

[6] Kippelen, B.; Peyghambarian, N. Advances in Polymer Science, Polymers for Photon‐
ics Applications II, Springer, 2002, 87-156.

[7] Ostroverkhova, O.; Moerner, W. E. Chem. Rev., 2004, 104, 3267-3314.

[8] Sasaki, T. Polymer Journal, 2005, 37, 797-812.

[9] Tay, S.; Blanche, P. A.; Voorakaranam, R.; Tunc, A. V.; Lin, W.; Rokutanda, S.; Gu, T.;
Flores, D.; Wang, P.; Li, G.; Hilarie, P.; Thomas, J.; Norwood, R. A.; Yamamoto, M.;
Peyghambarian, N. Nature, 2008, 451, 694-698.

[10] Blanche, P. A.; Bablumian, A.; Voorakaranam, R.; Christenson, C.; Lin, W.; Gu, T.;
Flores, D.; Wang, P.; Hsieh, W. Y.; Kathaperumal, M.; Rachwal, B.; Siddiqui, O.; Tho‐
mas, J.; Norwood, R. A.; Yamamoto, M.; Peyghambarian, N. Nature, 2010, 468, 80-83.

[11] Wiederrecht, G. P., Yoon, B. A., Wasielewski, M. R. Adv. Materials 2000, 12,
1533-1536.

[12] Sasaki, T.; Katsuragi, A.; Mochizuki, O.; Nakazawa, Y. J. Phys. Chem. B, 2003, 107,
7659 -7665.

[13] Talarico, M.; Goelemme, A. Nature Mater., 2006, 5, 185-188.

[14] Sasaki, T; Miyazaki, D.; Akaike, K.; Ikegami, M.; Naka, Y. J. Mater. Chem., 2011, 21,
8678-8686.
532 Advances in Ferroelectrics

[15] Skarp, K.; Handschy, M. A. Mol. Cryst. Liq. Cryst. 1988, 165, 439-569.

[16] Sasaki, T.; Mochizuki, O.; Nakazawa, N.; Fukunaga, G.; Nakamura, T.; Noborio, K.
Appl. Phys. Lett., 2004, 85, 1329-1331.

[17] Sasaki, T.; Mochizuki, O.; Nakazawa, Y.; Noborio, K. J. Phys. Chem. B, 2004, 108,
17083-17088.