Piezoelectricity and ferroelectricity

Phenomena and properties

Prof.Mgr.Jiří Erhart, Ph.D.

Department of Physics FP TUL
 What is the phenomenon about?

• Metallic membrane with „something

strange“
• LEDs flash, why?

J.Erhart: Demonstrujeme piezoelektrický jev, Matematika, fyzika, informatika 20 (2010) 106-109

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 History

1880, 1881 - Pierre a Jacques Curie, discovery of piezoelectricity, tourmaline

and quartz
1917 – A.Langevin – ultrasound generation, sonar
1921 – ferroelectricity - J.Valasek: Piezoelectricity and allied phenomena in
Salt, Phys.Rev. 17 (1921) 475
1926 – W.Cady – frequency stabilization of oscillator circuit by the quartz
resonator
1944-1946 – USA, SSSR, Japonsko – BaTiO3 ferroelectric ceramics
1954 – B.Jaffe et al – PZT ceramics
60. léta – LiNbO3 and LiTaO3 single crystals
70.léta – ferroelectric polymer PVDF
80.léta – piezoelectric composites
90.léta – domain engineering in PZN-PT, PMN-PT single crystals
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 Predecessors of piezoelectricity

Pyroelectricity
tourmaline = lapis electricus
(Na,Ca)(Mg,Fe)3B3Al6Si6(O,OH,F)31

Franz Ulrich Theodor Aepinus Tourmaline crystal.

Carl Linnaeus
(1707 – 1778)
(1724 – 1802) – polar phenomenon

David Brewster – “pyroelectricity” 1824

pyros=oheň

David Brewster
(1781 – 1868)
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 Pyroelectricity

A.C.Becquerel William Thomson (Lord Kelvin)

first pyroelectricity measurement first pyroelectricity theory
1828 1878, 1893

∆PS = p ⋅ ∆θ

William Thomson,
Antoine César
Lord Kelvin
Becquerel
(1824 – 1907)
(1788 –1878)

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 Piezoelectricity discovery

Tourmaline crystal, 1880

8.4.1880
Société minéralogique de France
24.8.1880
Académie des Sciences

∆P = d ⋅ T

Paul-Jacques
Pierre Curie Curie
(1859 – 1906) (1856 – 1941)

Curie J, Curie P (1880) Développement, par pression, de l’électricité polaire dans les cristaux hémièdres à faces inclinées.
Comptes rendus de l’Académie des Sciences 91: 294; 383.
Curie J, Curie P (1881) Contractions et dilatations produites par des tensions électriques dans les cristaux hémièdres à faces
inclinées. Comptes rendus de l’Académie des Sciences 93: 1137-1140.

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 Phenomenon properties

• Linear phenomenon, charge is independent from crystal

length, it depends on the electrode area
• Phenomenon exists due to crystal anisotropy (polar axes),
amorphous materials are not piezoelectric
Curie’s principle
Symmetry elements of external field must be included in the
phenomenon symmetry.

Crystal under the influence of external field exhibits only symmetry elements
common to the symmetry of crystal itself and of the external field.

Example: mechanical pressure along [111] direction exerted on the cubic crystal with m3m
symmetry causes symmetry reduction of deformed crystal to 3m symmetry class

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 Piezoelectricity
Direct phenomenon mechanical pressure → electrical charge
Converse phenomenon electric field → mechanical deformation

It is limited to certain crystallographic symmetry classes (20 from 32 classes)

1, 2, m, 222, mm2, 4, 4, 422, 4mm, 4 2m,
3, 32, 3m, 6, 6, 622, 6mm, 6 2m, 4 3m, 23
Example: SiO2 (quartz) symmetry 32

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 Measurement technique

Direct phenomenon (Brothers Curie)

• Thompson’s electrometer
• Null method ∆Q=V∆C
(Daniel’s cell – 1.12V, 1836)

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 Measurement technique

Converse phenomenon (Brothers Curie)

• Holtz’s machine (induction electricity, HV)
• Strain measured by the direct effect,
optically

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 Piezoelectricity origin

Brothers Curie – molecular theory

Charges generated at the compression (a) and tension (b) of quartz crystal
basic unit

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 First theory and application of piezoelectricity

Tensor analysis developed for the crystal anisotropy description 1890

Woldemar Voigt: Lehrbuch der Kristallographie, Teubner Verlag 1910

First application – electrometer,

radioactivity study (Maria Skłodowska-Curie)

Woldemar Voigt
(1850 –1919)

Maria Skłodowska-
Curie’s electrometer
Curie
(1867 – 1934)

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 Coupled field phenomena
Heckmann’s
diagram

Piezoelectricity

Sλ = sλµ
E
Tµ + d iλ Ei Jonas Ferdinand
Gabriel Lippmann
Di = d iµTµ + ε ijT E j (1845 –1921)

Sλ = sλµ
D
Tµ + giλ Di
Ei = − giµTµ + β ijT D j

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 Ferroelectricity

Joseph Valasek, 1920, Rochelle Salt NaKC4H4O6.4H2O

Joseph Valasek
(1897-1993)

Hysteresis loop of Rochelle Salt – dry crystal, 0oC

Valasek J (1921) Piezoelectricity and allied phenomena in Rochelle salt. Phys. Rev. 17: 475-481

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 Electromechanical phenomena

Direct conversion between mechanical and

electrical energy
• Linear effects – Piezo- and Pyroelectricity
• Nonlinear effects - Ferroelectricity,
Electrostriction

Analogy in magnetic materials

• Piezomagnetic properties, magnetostriction, magnetoelectric effect, etc.

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 Crystallographic constraints
for piezoelectricity

Noncentrosymmetric classes (except of 432)

20 piezoelectric crystallographic classes

• Polar classes (10) – singular polar axis

1, 2, m, mm2, 4, 4mm, 3, 3m, 6, 6mm
• Polar-neutral classes (10) – multiple polar axes
222, 4, 422, 42m, 32, 6, 622, 6 m2, 43m, 23
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 Equations of state
Example: piezoelectricity

Sµ = E
sµνTν + d kµ E k S µ = sµν
D
Tν + g kµ Dk
Di = d iν Tν + ε Tik E k Ei = − g iν Tν + βTik Dk

Tµ = E
cµν S ν − ekµ E k Tµ = cµν
D
S ν − hkµ Dk
Di = eiν S ν + ε ikS E k Ei = −hiν S ν + β ikS Dk

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 Piezoelectric coefficients
Different coefficients due to the choice of independent variables

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 Material property anisotropy
d33 surface
PS[001]T

PbTiO3 – 4mm
Maximum
3+(d
d33l3 2 2
31+d15)l3(l1 +l2 )
l1=sin(θ)cos(φ), l2=sin(θ)sin(φ), l3=cos(θ)
83.7pC/N for θ = 0o, i.e. [001]C
d33= 83.7, d31= -27.2, d15= 60.2 [pC/N]
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 Material property anisotropy
d33 surface
PS[001]T

BaTiO3 – 4mm Maximum

d33l33+(d31+d15)l3(l12+l22) 224pC/N for θ = 51o
l1=sin(θ)cos(φ), l2=sin(θ)sin(φ), l3=cos(θ) 90pC/N for [001]C
d33= 90, d31= -33.4, d15= 564 [pC/N]
221pC/N for [111]C
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 Pyroelectricity

Direct effect
Temperature change → electric charge
Converse effect (electrocaloric effect)
Electric field → heat generation or absorption
Anisotropy

Example:
Lithium tetraborate Li2B4O7,
symmetry 4mm

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 Crystallographic constraints
for pyroelectricity
Polar symmetry classes (10) – singular polar axis
1, 2, m, mm2, 4, 4mm, 3, 3m, 6, 6mm

Pyroelectric polarization of material (dipole

moment) – polar axis direction

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 Electrostriction

• Nonlinear effect
Deformation proportional
to the square of
electric field

• No constraints on the material symmetry, effect

exists in all materials

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 Electrostriction

Nonlinear equations of state

Sij = d kij Ek + Qijkl Pk Pl

Without crystallographic limits!

All materials exhibit electrostrictive properties

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 Electrostriction in cubic materials

Electrostrictive coefficients Q11, Q12, Q44

 S1   Q11 Q12 Q12 0 0 0   P12 

     2 
 S 2   Q12 Q11 Q12 0 0 0   P2 
 S  Q  
Q12 Q11 0 0 0   P32 
 =
3 12 
 S4   0 0 0 Q44 0 0   P2 P3 
S     
 5  0 0 0 0 Q44 0   P1P3 
S   0 0 0 0 0 Q44   P1P2 
 6 

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 Ferroelectricity

Spontaneous dipole moments = pyroelectricity

with switchable polarization
Electric analogy of permanent magnets

Characteristic properties
• Ferroelectric domains and domain walls
• Hysteresis loop D-E (S-E)

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Hierarchy of electromechanical phenomena

SiO2, GaPO4, AlPO4, ...

Piezo-

Pyro- Li2B4O7, ...

BaTiO3, PbTiO3, PZT,

Ferro- KNbO3, TGS, KDP, ...

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 Ferroelectricity

Spontaneous existence of polarization (and

spontaneous strain at the same time)
- structural phase transition
Ferroelectric/ferroelastic domains
- orientation domain states
Domain walls
Hysteresis

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 BaTiO3 – paraelectric phase

Perovskite structure

A2+

B4+
O2-

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 BaTiO3 – ferroelectric phase

Several orientation states exist for the spontaneous polarization

m3 m

4mm mm2 3m

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 Domains, domain walls

Domain – space continuous region with the same

orientation of the spontaneous dipole moment
(polarization)
Domain walls – interfaces between domains
• Charged walls
• Neutral walls

Ferroelectric domains exist in ferroelectric phase

Phase transition – Curie temperature TC

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 D-E a S-E hysteresis loops

T. Liu, C. S. Lynch: Domain engineered relaxor ferroelectric single crystals

Continuum Mech. Thermodyn. 18 (2006) 119–135

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 Remanent polarization

PS, Pr, EC coercive field

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Mechanism of domain reorientation

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 Remanent deformation
Ferroelasticity in ferroelectric materials

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 Domains in BaTiO3 ceramics m3m → 4mm

Domain structure evolution during heating of BaTiO3 ceramics over the Curie
temperature
(a) Temperature gradient parallel to the domain walls
(b) Temperature gradient perpendicular to the domain walls
Sang-Beom Kim, Doh-Yeon Kim:J. Am. Ceram. Soc., 83 [6] 1495–98 (2000)

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 Domains in BaTiO3 ceramics m3m → 4mm

Etched surface of BaTiO3 ceramics

a) Herringbone and chessboard pattern
b) Band structure of DW’s, domains continuously cross the grain
boundaries
G.Arlt, P.Sasko: J.Appl.Phys. 51 (1980) 4956-4960

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 Ferroic phases

Structural phase transitions

Parent phase (e.g. paraelectric) → ferroic phase
Feroelectrics
Ferroelastics
LiNbO3 3 m → 3m
AgNbO3
KNbO3 m 3 m → mm2
NaNbO3 m 3 m → mmm
BaTiO3 m 3 m → 4mm Pb3(PO4)2 3 m → 2 / m
Pb5Ge3O11 6 → 3
KIO3 3m → m

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 Material property anomalies
Dielectric permittivity, spontaneous polarization, etc.

BaTiO3

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 Material property anomalies

Piezoelectric coefficient
LiTaO3

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 Landau-Ginzburg-Devonshire theory

Power expansion of thermodynamic potential

1 1 4
Φ (T ,η ) = Φ 0 + α (T − TC )η + βη
2
2 4
Equilibrium and stability 2
∂Φ ∂ Φ
= 0, 2 > 0
∂η ∂η
Equilibrium phase transition parameter value
∂Φ 0 T > TC
= α (T − TC )η0 + βη 03 = 0 
∂η η0 =   α (T − TC ) 1 2
 ±  − β
 T < TC
  

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 2nd order phase transition

Without hysteresis

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 1st order phase transition

Hysteresis

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 Curie – Weiss law

Dielectric permittivity temperature dependence

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 Spontaneous strain vs.
spontaneous polarization
Generally (for normal ferroelectrics)
S kl = Qijkl Pi Pj

Example for the ferroelectric species 4 / mmm → mxy

 S1   Q11 Q12 Q13 0 0 0   PS21 
     
 S 2   Q12 Q11 Q13 0 0 0   PS1 
2

 S  Q 0   2 
31 Q31 Q33 0 0
 PS 3 
 =
3

 S4   0 0 0 Q44 0 0   PS1PS 3 
S   0  
0 0 0 Q44 0   PS1PS 3 
 5  
S   0 0 0 0 0 Q66   P2 
 6   S1 
PS = ( PS1, PS1, PS 3 )
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 Experimental characterization
of spontaneous deformation
Lattice constants measured
by X-Ray diffraction

• In parent phase
(extrapolation down to
the ferroic phase)

• In ferroic phase
LB Tables III/16a

General formula for the components of strain tensor

J.L.Schlenker, G.V.Gibbs, M.B.Boisen, Jr.: Acta Cryst. A34 (1978) 52-54

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 Bi4Ti3O12

4 / mmm → mxy cmon

bmon
ctetr
btetr amon
atetr
8 ferroelectric DS
4 ferroelastic DS

Pa>>Pc

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 Bi4Ti3O12
Spontaneous deformation/polarization (components in the parent
phase coordinate system)
 S11 S12 S13 
  1 1 1 1
S (1) =  S12 S11 − S13  P I = ( Pa ,− Pa , Pc ) P II = (− Pa , Pa ,− Pc )
S 2 2 2 2
 13 − S13 S 33 
 S11 − S12 S13 
  1 1 1 1
S (2) =  − S12 S11 S13  P III = ( Pa , Pa , Pc ) P IV = (− Pa ,− Pa ,− Pc )
 S 2 2 2 2
 13 S13 S 33 
 S11 S12 − S13 
  1 1 1 1
S (3) =  S12 S11 S13  PV = (− Pa , Pa , Pc ) PVI = ( Pa ,− Pa ,− Pc )
− S 2 2 2 2
 13 S13 S 33 
 S11 − S12 − S13 
  1 1 1 1
S (4) =  − S12 S11 − S13  PVII = (− Pa ,− Pa , Pc ) PVIII = ( Pa , Pa ,− Pc )
− S 2 2 2 2
 13 − S13 S 33 

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 Domain wall orientation

(ds ) − (ds ) = ( S
( 2) 2 (1) 2 ( 2)
ij − S )dsi ds j = 0
(1)
ij

Example for Bi4Ti3O12

Domain state pair S(1) (P(1), P(2)) and S(2) (P(3),P(4))

S13
(ds1 − ds3 )ds2 = 0
S12
Two perpendicular domain walls
Charged wall (010) W-wall S13
Neutral wall (10K) S-wall K =−
S12

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 Domain wall orientations in Bi4Ti3O12

S(1) S(2) S(3) S(4)

P(1),P(2) P(3),P(4) P(5),P(6) P(7),P(8)
S(1) N/A (010) (1-10) (100)
P(1),P(2) (10-K) (001) (01K)
S(2) N/A (100) (110)
P(3),P(4) (01-K) (001)
S(3) N/A (010)
P(5),P(6) (10K)
S(4) N/A
P(7),P(8)
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 Domain wall types
W-walls
W∞ - arbitrary wall orientation
Wf – fixed crystallographic domain wall orientation
S-walls (“strange” walls, W’-walls)
S1 – PS direction
S2 – bijk and Qijkl
S3 – PS direction, bijk and Qijkl
S4 – PS direction and magnitude, bijk and Qijkl
S5 – PS magnitude, bijk and Qijkl
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 Permissible domain wall pairs
W∞ - arbitrary domain wall orientation
WfWf – fixed domain wall orientation
WfS – fixed and „strange“ walls
SS – pair of „strange“ walls
R – walls are not permissible

J.Fousek, V.Janovec: J.Appl.Phys. 40 (1969) 135

J.Sapriel: Phys.Rev. B12 (1975) 5128
J.Erhart: Phase Transitions 77 (2004) 989-1074

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 Antiferroelectricity

Dipole moments are partially compensated

Switching possible
at higher fields

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 Electromechanical coupling coefficient

Energy transfer efficiency between mechanical and

electrical energy via piezoelectric effect

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 Electromechanical coupling
2
d 33
2
k 33 = E T
s33 ε 33

W.Heywang, K.Lubitz, W.Wersing (edts.): Piezoelectricity, Springer Verlag 2008

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 Electromechanical coupling coefficients

Different modes
Transversal thickness-shear
2
d d152
2
k 31 = E 31T k =
2
s11ε 33 15
s55E ε 11T
thickness radial

2 2
e33 2 d
k t2 = k p2 = T E 31 E
D S
c33 ε 33 ε 33 ( s11 + s12 )

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 Dielectric losses

Permittivity – complex values

ε ''
ε = ε '− jε ' ' tan( δ ) =
ε'
Dissipated power = energy loss during 1s
2 2
C ' ' I C ' I
P = U ⋅ I = ZC I 2 = −j
ω (C ' +C ' ' )
2 2
ω (C '2 +C ' '2 )
C = (ε '− jε ' ') = C '− jC ' '
S
d
1 C ' '− jC '
ZC = =
jωC ω (C '2 +C ' '2 )

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 Mechanical losses

Elastic properties – complex compliance

s = s '− js ' '
Mechanical quality Qm

1
Qm =
2πf m Z C T keff
2

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 Young’s modulus and elastic coefficients

Examples for 4mm symmetry

Mechanical pressure Mechanical deformation
1 σ 11 σ 33
T11 = c11S11 + c12 S 22 + c13 S 33 S11 = T11 − T22 − T33
Y11 Y11 Y33
T22 = c12 S11 + c11S 22 + c13 S 33 1 σ σ
S 22 = T22 − 11 T11 − 33 T33
T33 = c13 S11 + c13 S 22 + c33 S 33 Y11 Y11 Y33
1 σ σ
S 33 = T33 − 11 T11 − 11 T11
Y33 Y11 Y11

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 Young’s modulus

Matrix form s11=1/Y11

c-1=s s33=1/Y33

2
2c13
Y33 = c33 −
c11 + c12
2
(c11 − c12 )[c33 (c11 + c12 ) − 2c13 ]
Y11 =
2
c11c33 − c13

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Thank you for your attention!

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