Sensors 2010, 10, 1935-1954; doi:10.

3390/s100301935
OPEN ACCESS

sensors
ISSN 1424-8220
www.mdpi.com/journal/sensors

Review

Advances in Lead-Free Piezoelectric Materials for Sensors and

Actuators
Elena Aksel and Jacob L. Jones *

Department of Materials Science and Engineering, University of Florida, 100 Rhines Hall, Gainesville,
FL 32611, USA; E-Mail: [email protected]

* Author to whom correspondence should be addressed; E-Mail: [email protected];

Tel.: +1-352-846-3788; Fax: +1-352-846-3355.

Received: 6 January 2010; in revised form: 3 February 2010 / Accepted: 12 February 2010 /
Published: 10 March 2010

Abstract: Piezoelectrics have widespread use in today’s sensor and actuator technologies.
However, most commercially available piezoelectric materials, e.g., Pb [ZrxTi1-x] O3
(PZT), are comprised of more than 60 weight percent lead (Pb). Due to its harmful effects,
there is a strong impetus to identify new lead-free replacement materials with comparable
properties to those of PZT. This review highlights recent developments in several lead-free
piezoelectric materials including BaTiO3, Na0.5Bi0.5TiO3, K0.5Bi0.5TiO3, Na0.5K0.5NbO3,
and their solid solutions. The factors that contribute to strong piezoelectric behavior are
described and a summary of the properties for the various systems is provided.

Keywords: ceramics; piezoelectrics; ferroelectrics; electromechanical

1. Introduction

Piezoelectric materials are commonly used in sensor and actuator technologies due to their unique
ability to couple electrical and mechanical displacements, i.e., to change electrical polarization in
response to an applied mechanical stress or mechanically strain in response to an applied electric
field [1]. Compared to other electromechanical transduction technologies, piezoelectric materials offer
a high pressure per density ratio for actuator devices, high environmental and chemical stability, and
capabilities of operating at high temperatures and frequencies. Applications of piezoelectric materials
range from buzzers to diesel engine fuel injectors, sonar, ultrasound, and nanopositioners in
scanning microscopes.
Sensors 2010, 10 1936

The most widely used piezoelectric ceramic is lead zirconate titanate (Pb [ZrxTi1-x] O3), or PZT.
One critical disadvantage of PZT is that it contains more than 60 percent lead (Pb) by weight. This
large lead content creates hazards during processing (lead volatilizes and is released into the
atmosphere), limits applications (e.g., in vitro), and is potentially environmentally toxic during
disposal. Over the past few years, regulatory agencies world-wide began putting strict restrictions on
the use of lead, with the exception of the electronics industry due to the lack of a suitable replacement
to PZT [23].
Suitable lead-free piezoelectric materials are still being developed as no single composition has
been proposed with properties that are comparable to that of PZT. This review highlights some of the
current advances in the development of lead-free piezoelectric materials with a focus on those
exhibiting the perovskite structure. The remaining sections of the manuscript are broken down as
follows. Sections 2 and 3 contain background information: the fundamentals of piezoelectricity are
briefly reviewed in Section 2 and the importance of morphotropic phase boundaries is described in
Section 3. Section 4 discusses developments in several different material systems that are based on one
particular composition, e.g., BaTiO3, Na0.5Bi0.5TiO3, etc. Section 5 introduces research advances in
solid solutions containing two of these compositions. Section 6 discusses the ternary solid solutions
that exhibit useful properties. Many of the material compositions and properties that are discussed in
each of the respective sections are also compiled in Table A.1 of Appendix A. A brief summary of the
paper is provided in Section 7.

2. Fundamentals of Piezoelectricity

The only crystallographic requirement for a material to exhibit piezoelectricity is that it must be
non-centrosymmetric. Examples of non-centrosymmetric structures that are used in piezoelectric
devices include aluminum nitride (AlN) and quartz. In many piezoelectric materials, a spontaneous
polarization also exists due to the separation of negative and positive charge centers in the
crystallographic unit cell. A characteristic example of a structure which exhibits a spontaneous
polarization is the perovskite structure, ABO3. As the perovskite structure is cooled from the high
temperature cubic phase (centrosymmetric), it can undergo several different phase transitions and
eventually transform to tetragonal, rhombohedral, orthorhombic, or monoclinic structures at various
phase transitions. The center atom (B) and the oxygen octahedron (O3) displace non-uniformly relative
to the corner atom (A), resulting in a non-centrosymmetric structure. The temperature at which the
structure transforms from the high-temperature cubic phase to the first structure exhibiting a
spontaneous polarization coincides with the Curie temperature. When cooling a material through the
Curie temperature, different regions of the material take on different crystallographic orientations of
the lower symmetry crystal structure. These different regions are referred to as domains and the
regions that separate different domains are referred to as domain walls.
Ferroelectricity is the ability of a material to change its direction of spontaneous polarization in
response to application of an electric field. The electric field required for this reorientation to occur is
known as the coercive field and typically involves the motion of a ferroelectric domain wall. There is
often a distribution of local coercive fields in a polycrystalline material since there may be
compositional variations across a grain or different stress states of different grains. The
Sensors 2010, 10 1937

macroscopically observed coercive field (Ec) is the electric field required to obtain zero macroscopic
polarization due to compensating positive and negative local polarization states.
Upon cooling from the high processing temperatures required for ceramic materials, polycrystalline
ceramics exhibit neither a net macroscopic spontaneous polarization nor piezoelectricity at the
macroscopic length scale. This is because the structure is constituted of an equal number of all possible
domain orientations, each with a spontaneous polarization oriented in different direction. Since the
material contains many domains all oriented in different directions, the local areas of spontaneous
polarization cancel each other and the material does not exhibit a net macroscopic polarization. For a
polycrystalline material to exhibit piezoelectricity at the macroscopic length scale it must go through a
poling process wherein an electric field is applied and the domains are aligned more closely parallel to
the electric field direction. After poling, the material will have a net macroscopic polarization parallel
to the direction of the poling field and will exhibit piezoelectricity at the macroscopic length scale.
The converse piezoelectric effect describes the strain generated in a piezoelectric material in
response to an applied electric field. This effect is written as:
Si = dijEj (1)
where Si is the electric field induced strain, Ej is the applied electric field and dij is the piezoelectric
coefficient. The piezoelectric coefficient is truly a third rank tensor, although is written in Equation (1)
in reduced matrix notation by representing the mechanical strain as a 1-dimensional matrix with
elements i = 1, 2…6. The converse piezoelectric effect is exploited in actuator devices.
For sensing applications, the direct piezoelectric effect describes a change in polarization due to an
applied stress and is written as:
Di = dijσj (2)
where Di is the dielectric displacement and σj is the applied stress.
In Equation (1) and (2), the coordinate axes are defined by the polarization of the sample and is
assigned to the 3-direction. When an electric field is applied parallel to the 3-direction and strain is
also measured in the 3-direction, the piezoelectric coefficient of relevance is the longitudinal
piezoelectric coefficient, d33:
S3 = d33E3 (3)
The piezoelectric coefficients described by the direct and converse piezoelectric effects are
mathematically equivalent. Therefore, the longitudinal piezoelectric coefficient described by the
converse piezoelectric effect (Equation (3)) is equivalent to the longitudinal piezoelectric coefficient
described by the direct piezoelectric effect:
D3 = d33σ3 (4)
Another important property of a piezoelectric material is permittivity, which is related to how much
electrical potential energy can be stored in a given volume of the material under the influence of an
electric field. This is often maximized near phase transitions and its distribution with temperature is
broad in relaxor ferroelectric materials. Often, the permittivity is reported relative to the permittivity of
free space (ε33T/ε0), also called the relative permittivity (εr) or often the dielectric constant. Finally, the
Sensors 2010, 10 1938

electromechanical coupling factor (kp) relates the electrical energy output to the total mechanical
energy input or vice versa [4].
The properties of a piezoelectric material can be improved with small addition of substitutional
impurities, or dopants, as previously exploited in designing the properties of PZT. Depending on the
type of dopant and its position in the unit cell, the structure and properties of a material will change in
different ways. In the case of PZT, for example, donor doping involves dopant ions which are more
positive in valance than the ions they are replacing and this leads to a “soft” ferroelectric material
behavior [5]. Some of the property changes associated with this type of doping are a decrease in the
coercive field, increased dielectric constant, and an increased electromechanical coupling factor [5].
On the other hand, acceptor doping in PZT involves a dopant ion which is less positive in valance than
the host ion and this leads to a “hard” ferroelectric material behavior [5]. Some of the characteristic
changes attributed to this type of doping are a moderately lowered electrical resistivity, higher
coercive field, and a relatively lower dielectric constant [5]. “Hard” PZT materials are also often more
difficult to pole and depole.

3. The Morphotropic Phase Boundary

The extremely high piezoelectric response of PZT is partially attributed to the presence of a
morphotropic phase boundary (MPB). The MPB describes the boundary that separates regions of
different symmetries and can be crossed through a change in composition [6]. In 1954, Jaffe et al.
found enhanced piezoelectric properties in a solid solution of lead zirconate (PZ) and lead titanate (PT)
at ~45 mol% PT [7]. They attributed these enhanced properties to the MPB between rhombohedral and
tetragonal PZT at that concentration (Figure 1).

Figure 1. Morphotropic phase boundary in PZT, reproduced from Jaffe et al. [8].
Sensors 2010, 10 1939

Recent experimental work by Noheda et al. has suggested that a monoclinic phase exists at
compositions very near the MPB [9], initiating a significant number of experimental and theoretical
works to either support or refute this claim. To date, there is still controversy in the field as to the
nature of the MPB in PZT. A few good reviews on this subject can be found in reference [10,11].
Nevertheless, the presence of an MPB is considered a necessary component of a lead-free replacement
material because of the enhancement in properties observed in compositions near MPBs.

4. One Component Systems

Useful lead-free materials are often binary or ternary solid solutions. Before discussing these more
complex material systems in Sections 5 and 6, this section introduces and discusses the respective end
member compositions.

4.1. Barium Titanate―BaTiO3 (BT)

Barium titanate was one of the first useful piezoelectric materials, developed in the 1940s
and 1950s [8,12,13]. Although this material does not have a very high piezoelectric constant, it has a
very high permittivity, making it a good material for capacitors [14]. BT is often used in solid solution
with other lead-free compounds to form an MPB which can enhance the piezoelectric and dielectric
properties. BT exhibits a relatively low Curie temperature, however, and therefore has not seen many
developments in recent years for applications in piezoelectric devices.
The low Curie temperature of BT results from the tetragonal to paraelectric cubic phase transition
at 120 °C [15]. BT undergoes several additional structural phase transitions upon decreasing
temperature, as illustrated in Figure 2 (top). Each of these temperature-dependent phase transitions is
referred to as a polymorphic phase transition (PPT), in contrast to the MPB which is
composition-dependent. More recent studies by Wada et al. on single crystal BT found that these
phase transitions can also be induced by applied electric field [16]. They found that the room
temperature structure can change from tetragonal to monoclinic under an applied electric field
amplitude of 10 kV/cm and then subsequently to rhombohedral at an amplitude of 30 kV/cm [16].
Recent developments in BT materials have reported extraordinary non-piezoelectric properties
including piezoresistivity [17], colossal permittivity up to ~106 in carefully prepared nanocrystalline
ceramics [18], and very large reversible strain up to ~0.8% due to defect-mediated domain
switching [19]. BT also continues to serve as a model system for more fundamental investigations,
as in reference [20,21].

4.2. Sodium Bismuth Titanate―Na0.5Bi0.5TiO3 (NBT)

This material system, like several other lead-free materials, was first reported in the 1960s by
Smolenskii et al. [22] but did not receive much attention until the recent surge in lead-free material
development in the past two decades. Some of the initial dielectric and optical property measurements
of NBT were reported in the 1990s by various sources [23-25]. Preliminary structural studies of NBT
did not provide a definitive structural understanding [26,27], but in 2002 Jones and Thomas found that
Sensors 2010, 10 1940

it expresses the rhombohedral R3c space group at room temperature and changes to tetragonal and
subsequently cubic during heating [28]. NBT is a promising material due to its high Curie temperature
of 325 °C, and a piezoelectric constant of 73 pC/N, similar to that of BT [29]. A schematic of the NBT
structure above its Curie temperature is shown in Figure 3.
Some of the main drawbacks of this material are that it has a high coercive field and high
conductivity. The issue of high conductivity was attributed to volatilization of Bi ions during
sintering [29]. To address this issue, Hiruma et al. found an increased resistivity with the addition of
excess bismuth [29]. NBT also exhibits a low depolarization temperature of 187 °C, far lower than its
Curie point, limiting its use at elevated temperatures [29]. Some literature attributes this depolarization
to the presence of an intermediate antiferroelectric phase [30,31], but other works claim that the
intermediate phase is not fully antiferroelectric [29], leaving this question unresolved.

Figure 2. Polymorphic phase transitions in barium titanate single crystals observed

through changes in the unit cell parameters [32], spontaneous polarization [33], and
dielectric constant [15], reproduced from the respective sources.
Sensors 2010, 10 1941

Figure 3. Schematic of the pseudo-cubic NBT perovskite structure. The structure

illustrated is locally ordered on the A-site (Bi, Na), although the extent of ordering is not
well known. The oxygen atoms are not shown for clarity and their positions are instead
represented by the oxygen octahedra.

Different dopants can be added to NBT to combat some of its drawbacks, such as to decrease
coercive field or increase the piezoelectric constant. When considering dopants for NBT, it is
important to recognize that it differs from PZT in several ways. While PZT has complex ions on the
B-site (Ti4+ and Zr4+), NBT has a mixture of Bi3+ and Na+ ions on the A-site. While PZT is therefore
mainly B-site active, substitution in NBT is more effective on the A-site [34]. Many different studies
have been done to test the impact of various dopants on NBT, some of which are tabulated in Table
A.1 [35-38]. For example, an exceptional change was observed by Xiao et al. with the use of Li+ and
K+ co-doping on the Na+ site [34,38]. Xiao et al. were able to increase the piezoelectric and coupling
coefficients of NBT to 146 pC/N and 36%, respectively, and reduce the coercive field
to 3.7 kV/mm while maintaining a high depolarization temperature to produce a lead-free middle
frequency filter which performed comparable to a Pb-based one [34,38].

4.3. Potassium Bismuth Titanate―K0.5Bi0.5TiO3 (KBT)

Similar to NBT, KBT was also first reported by Smolenskii et al. in the 1960s [22]. KBT is unique
from NBT, however, in that it is tetragonal at room temperature (whereas NBT is rhombohedral) and
does not depolarize until 270 °C [39] (NBT depolarizes at 187 °C). The polarization hysteresis
behavior of KBT measured at several temperatures is displayed in Figure 4, showing that a hysteresis
loop is observed even at temperatures as high as 260 °C [39]. As expected, the coercive field also
gradually decreases with an increase in temperature, as does the remnant polarization. One of the main
challenges of this system is that it is difficult to produce dense ceramics using ordinary firing methods.
This low density makes the materials difficult to fully pole. Density can be improved through the use
Sensors 2010, 10 1942

of sintering aids. For example, Hiruma et al. found that processing of KBT with excess bismuth oxide
improved the piezoelectric and ferroelectric properties of the material (e.g., d33 = 101 pC/N) because
Bi2O3 acts as a sintering aid and prevents the formation of micro-cracks [40].

Figure 4. Polarization of KBT measured at temperatures of (a) 100 °C, (b) 200 °C,
(c) 240 °C, and (d) 260 °C, reproduced from Hiruma et al. [39].

4.4. Sodium Potassium Niobate―K0.5Na0.5NbO3 (KNN)

KNN is unique from the bismuth-based NBT and KBT compositions in that it is a specific
composition (50/50) on a complete solid solution of NaNbO3 and KNbO3. This composition is at the
MPB between two orthorhombic phases where KNbO3 is ferroelectric (FE) and NaNbO3 is
antiferroelectric (AFE) [41,42], similar to the MPB observed in PZT. The structure of the material at
the 50/50 composition is orthorhombic [43]. The piezoelectric coefficient of KNN is higher than that
of undoped NBT or KBT [43], but not when processed through traditional processing methods [42].
Not only is the material difficult to sinter using ordinary conditions, but also the reactant powders
require special care [44]. Dense ceramics with a high piezoelectric constant of 148 pC/N were
achieved by Li et al. using advanced processing methods [43] compared to a piezoelectric constant of
90 pC/N for undoped KNN prepared using conventional methods [45].
The processing issues of KNN did not make it an attractive contender for a PZT replacement, but
the recent work of Saito et al. [3] promoted much research on this system. Saito et al. found that
extremely high piezoelectric properties can be achieved relative to typical actuator-grade PZT
compounds by combining the addition of several dopants with crystallographic texturing [3].
Following the publication of that paper, a great deal of literature on doping effects in KNN has been
published. With the addition of dopants such as lithium, tantalum, and antimony, high density samples
of KNN have been produced using traditional sintering. In some cases, the dopants are also used to
improve the piezoelectric properties by decreasing the orthorhombic to tetragonal PPT to room
temperature [44,46,47]. The aim of combining a material composition which contains the natural MPB
Sensors 2010, 10 1943

at the 50:50 Na:K ratio with a PPT that is lowered to room temperature through the use of dopants is
that the properties will be enhanced. Measurements of the dielectric constant with respect to
temperature in Figure 5 show a peak at the PPT from orthorhombic to tetragonal, analogous to the
behavior seen in BT in Figure 2. As certain dopants are added to decrease this temperature, the peak
shifts down and eventually vanishes [45]. This is beneficial because an increase in the dielectric
constant is correlated to an increase in the piezoelectric constant through the equation:
dij ~ 2QijεrεoPi (5)
where dij is the piezoelectric coefficient, Qij is the electrostriction coefficient, εr is the relative
permittivity, εo is the permittivity of free space, and Pi is the polarization [48].

Figure 5. Dielectric constant of [Lix (Na0.5K0.5)1-x]NbO3 measured as a function of

temperature for several Li concentrations, reproduced from Guo et al. [45].

4.5. Bismuth Ferrite―BiFeO3 (BFO)

Another intriguing system currently under study is bismuth ferrite. BFO is a unique lead-free
candidate in that it is both ferroelectric and ferromagnetic. The structure, which has a bulk
rhombohedral symmetry at room temperature, has spontaneous polarization mostly due to the bismuth
on its A-site and magnetization due to the iron on the B-site [49]. Contrary to the bulk rhombohedral
structure, BFO thin films have a monoclinic crystal structure [50]. A schematic of the structure,
reproduced from Chu et al. in Figure 6, illustrates the spontaneous polarization direction as well as the
planes of antiferromagnetic ordering [51]. Due to the co-existence of ferroelectricity and
anti-ferromagnetism in this structure, a magnetic field can be used to change the orientation of the
ferroelectric domains or, vice versa, an electric field can be used to change the ferromagnetic
orientation [51].
Sensors 2010, 10 1944

Figure 6. Schematic of the crystal structure of BFO, showing the direction of spontaneous
polarization (Ps) as well as the antiferromagnetic ordering (displayed in the grey plane),
reproduced from Chu et al. [51].

In thin film studies, Wang et al. found that BFO has promising properties, with a remnant
polarization of 50–60 µC/cm2 and a piezoelectric coefficient of 70 pm/V [50]. Fujino et al. attempted
to further improve on these properties through doping with samarium and found an MPB at 14 mol%
Sm between FE rhombohedral and AFE pseudo-orthorhombic structures [52]. This composition led to
a decrease in the coercive field as well as an increase in the piezoelectric constant (110 pm/V) [52].
Developments in BFO have also extended to single crystals, where an extremely large spontaneous
polarization of 100 µC/cm2 in the [001] direction was reported for highly pure single crystals [53].
Although recent work with BFO has shown great potential for its use, there are still many unanswered
questions about its behavior, such as the lack in understanding of the BFO phase diagram and
switching processes [49].

5. Binary Systems

For some of the lead-free systems described above, the piezoelectric properties are enhanced
through the use of dopants. As mentioned previously, however, another useful method for the
enhancement of properties is the selection of a composition near an MPB in a solid solution. This
section discusses the structure and properties of several lead-free binary solid solution material
compositions.

5.1. NBT-KBT

A solid solution of NBT – KBT forms an MPB between rhombohedral (NBT-rich) and tetragonal
(KBT-rich) structures in the region of 16–22 mol% KBT [54,55]. Compositions near the MPB show an
improvement in certain properties such as the piezoelectric constant, dielectric constant, and the
coupling factor, many of which are summarized in Table A.1 [54]. Figure 7 shows an example of the
change seen in the coupling factor as a function of composition in the NBT-KBT solid solution.
Since this solid solution contains several elements that volatilize easily, such as K, Na, and Bi, the
sintering conditions used play a large role in the final piezoelectric properties achieved in these
materials [55]. For example, Zhang et al. found that with a change of only 40 °C in the sintering
Sensors 2010, 10 1945

temperature of an NBT-KBT solid solution at the MPB, the piezoelectric constant increased from 155
to 192 pC/N [55].

Figure 7. Electromechanical coupling factor of [Bi0.5(Na1-xKx)0.5] TiO3 as a function of

KBT concentration (x), reproduced from Sasaki et al. [54].

5.2. NBT-KNN

In the case of a combination of NBT with KNN, several different MPBs have been reported. In an
NBT-rich system, Kounga et al. reported an MPB at 6–7 mol% KNN between a rhombohedral FE
phase (NBT-rich) and a tetragonal AFE phase [56]. Although the addition of KNN made the material
more antiferroelectric in its behavior, it also led to a much higher unipolar strain [56]. On the contrary,
with a KNN rich solution, an MPB was reported at 2–3% NBT between ferroelectric orthorhombic and
tetragonal phases [57]. This composition leads to a high piezoelectric constant of 195 pC/N and
electromechanical coupling factor of 43% [57].

5.3. NBT-BT

BT has also been combined in a solid solution with NBT, in which case an MPB is found
at 6–7 mol% BT between the NBT-rich rhombohedral and BT-rich tetragonal phases [58]. At this
composition, the system exhibits improved properties relative to NBT, such as the piezoelectric
constant (d33 = 125 pC/N), coupling factor (kp = 20%), and dielectric constant (εr = 580). NBT-BT
compositions near the MPB also exhibit high bending strength (e.g., 200 MPa), which is 2–3 times that
of PZT based materials [58]. One of the drawbacks of this system is the temperature dependence of the
properties. As shown below in Figure 8, the MPB in NBT-BT is not linear with temperature, but rather
has a curved shape [58]. It can be observed that the FE to AFE transition temperature decreases as the
concentration of BT increases [58]. The behavior seen in the phase diagram was confirmed in more
recent work by Hiruma et al. through electrical measurements, such as the temperature dependence of
the dielectric constant and loss tangent, of various compositions of NBT-BT [59]. Daniels et al. found
that compositions near the MPB exhibit electric field induced phase transitions from rhombohedral to
tetragonal [60], similar to the electric-field-induced phase transitions mentioned earlier for BT. This
behavior results in a strong orientation of the ferroelectric and ferroelastic domain orientations relative
to the electric field direction in the material [60].
Sensors 2010, 10 1946

Figure 8. Phase diagram of NBT-BT showing the MPB between the ferroelectric
rhomboheral phase and the ferroelectric tetragonal phase, reproduced from
Takenaka et al. [58].

5.4. NBT-BFO

NBT was also combined with BFO by Nagata et al., showing an increase in the Curie temperature
(Tc = 340 °C) and the electromechanical coupling factor (kp = 33.6%) [61] compared to undoped NBT
(Tc = 325 °C, kp = 16.8%) [29]. However, in this case, the structure remains a single rhombohedral
phase with no MPB [61]. A change from the NBT system is observed at high temperatures of 200 °C,
where the binary solution does not show the FE to AFE transition found in NBT [61].

5.5. KBT-BT

As mentioned previously, a major drawback of KBT is the difficulty in synthesizing dense ceramics
using conventional processing methods. When KBT is in a solid solution with BT, the density of the
material is improved [62]. With the addition of 10 mol% BT, dense textured materials were formed
using ordinary sintering methods [62]. The properties for this system (e.g., d33 = 85 pC/N) [62] were
comparable to those reported for KBT obtained through more advanced processing methods
(d33 = 70 pC/N) [39].

5.6. KNN-BT

The addition of BT to KNN also aids in the densification of KNN-based materials, and Ahn et al.
found improved piezoelectric properties for this system by comparing different sintering conditions
of 0.95KNN-0.05BT [63]. Guo et al. reported an MPB in this system at ~6 mol % BT and another
transition to a cubic phase at 20 mol % BT [64]. KNN-BT systems were also prepared with Li doping,
the results of which showed that higher piezoelectric coefficients were found at MPB compositions
which were tetragonal-rich [65]. Table A.1 lists the properties of two KNN-BT systems, 0.95 KNN-0.05 BT
and Li doped 0.90 KNN-0.10 BT, and both cases yield a piezoelectric constant above 200 pC/N [63,65].
Sensors 2010, 10 1947

6. Ternary Systems

As the binary systems described above still have many drawbacks and are not capable of replacing
PZT in all of its applications, new lead-free compositions have become even more complex through
the use of ternary solid solutions. Since the various end members described in Section 4 exhibit the
perovskite structure, their combination is mostly expected to form solid solutions. Ternary systems
also allow for more degrees of freedom in identifying compositions with enhanced properties.
Several reports have been published by Zhang et al. for the NBT-BT-KNN ternary system [66,67].
The MPB in this system is between FE and AFE phases, where compositions such
as 0.94 NBT-0.05 BT-0.01 KNN, 0.93 NBT-0.05 BT-0.02 KNN, 0.92 NBT-0.05 BT-0.03 KNN,
and 0.93 NBT-0.06 BT-0.01 KNN show FE behavior, while 0.92 NBT-0.06 BT-0.02 KNN, 0.91
NBT-0.06 BT-0.03 KNN, 0.92 NBT-0.07 BT-0.01 KNN, 0.91 NBT-0.07 BT-0.02 KNN, and 0.90
NBT-0.07 BT-0.03 KNN show AFE behavior [66]. The ternary solid solution of 0.92 NBT-0.06
BT-0.02 KNN had the largest strain ever reported for a polycrystalline lead-free ceramic, ~0.45% [66].
Further temperature dependent studies of the material found that this large strain comes from an
electric-field-induced phase transition from FE to AFE rather than piezoelectric lattice distortion [67].
Temperature dependent strain and polarization loops of the MPB composition show that at higher
temperatures the polarization loops begin to express AFE behavior as the strain loops display
unusually large strain, shown in Figure 9 [67].

Figure 9. Polarization (a) and strain (b) loops of 0.93 NBT-0.05 BT-0.02 KNN ceramics at
several temperatures, reproduced from Zhang et al. [67].

Studies of another ternary mixture, NBT-KBT-BT, at MPB compositions show that there is a
trade-off between piezoelectric properties and depolarization temperature [68,69]. Generally, materials
with higher piezoelectric properties exhibit lower depolarization temperatures. Wang et al. attempted
to break this trend by finding the optimal amount of KBT to increase properties without the reduced
depolarization temperature [70]. They found that the addition of ~5 mol% KBT to a 0.95NBT-0.05BT
mixture enhanced the piezoelectric coefficient (d33 = 148 pC/N) without having a strong impact on the
depolarization temperature [70]. Recently a solid solution of NBT-KBT-KNN was examined by Yao et al.
and an MPB was found for (Bi1/2Na1/2)1−x (Bi1/2K1/2)x TiO3 – 0.03 (Na0.5K0.5) NbO3 at x = 0.20 – 0.24 [71].
Sensors 2010, 10 1948

At a composition of x = 0.22, improved piezoelectric properties are found with a relatively high Curie
temperature (d33 = 167 pC/N, Tc = 340 °C), showing a high potential for these compositions [71].

7. Summary

Over the past few years there have been many developments in the field of lead-free piezoelectric
materials. Several material systems have been explored, some of which show properties comparable to
PZT. However, there is still no single system that is as versatile in its applications as PZT. BT is
historically significant and will continue to be a fundamental system of investigation, but it does not
have properties comparable to PZT and is especially limited by its low Curie temperature
of 120 °C. NBT has a higher Curie temperature, but lacks high enough piezoelectric properties and
depolarizes below 200 °C. While KBT and KNN do not depolarize below their Curie points, they are
difficult to process into dense ceramics using conventional sintering methods. The addition of dopants
to KBT and KNN systems allows for easier processing of the materials. BFO is a unique material that
has both ferroelectric and ferromagnetic properties. Recent developments show improvement in the
piezoelectric properties for BFO thin films and single crystals.
Solid solutions containing MPBs such as KNN-BT and NBT-BT-KNN show promise, particularly
when coupled with substitutional doping or positioning of the PPT temperature. Ultimately, more
complex solid solutions and doping schemes will have to be explored because these provide an
increasing number of degrees of freedom for identifying extraordinary properties. The materials
reviewed in this paper form a foundation for the search for improved lead-free materials and show
great potential for the future.

Acknowledgements

This work was supported by the U.S. National Science Foundation (NSF) under award number
DMR-0746902. J.L.J. acknowledges support from the U.S. Department of the Army under
W911NF-09-1-0435.

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Sensors 2010, 10 1953

Appendix A

Table A. 1. Summary some relevant properties of various lead-free materials.

Material d33 ε33T/ε0 kp Pr Ec Tc Reference
(pC/N) (meas. freq) (%) (µC/cm2) (kV/mm) (oC)
BaTiO3 single crystal 85.6 168 - - - - [14]
BaTiO3 ceramic 191 1,680 - - - - [14]
BaTiO3 single crystal - - - - - [16]
Parallel to [001] 125
Parallel to [111] 203
At high field - 295
Bi0.5Na0.5TiO3 72.9 343 (1 MHz) 16.8 - - 325 [29]
1%Mn:NBT <001> oriented single 130 - - - - - [35]
crystal
[(Na0.5Bi0.5)1-1.5xV0.5xLax] TiO3 x = 88 - 15.4 - - - [36]
0.01
[Na0.5Bi0.5-xLax] TiO3 x = 0.01 68 - 13.8 - - - [36]
(Bi0.5Na0.5)(1−1.5x)LaxTiO3 91 550 (1 kHz) 13 - - 345 [37]
x = 0.0172
[Bi0.5(Na1-x-yKxLiy)0.5] TiO3 164- 1,190 36.3- 38.8-40.2 2.47- - [38]
x = 0.15, y = 0.075 231 41.0 3.73
[Bi0.5(Na1-x-yKxLiy)0.5] TiO3 146 - 36 38.9 3.7 - [34]
x = 0.15, y = 0.075
Bi0.5K0.5TiO3 69.8 517 (1 MHz) - 22.2 5.25 437 [39]
KBT + 0.6wt% Bi2O3 101 764 (1 MHz) - 27.6 5.30 391 [40]
Na0.5K0.5NbO3 148 559 (100 kHz) 38.9 - - 395 [43]
Na0.5K0.5NbO3 70 400 25 - - - [42]
(Na0.5K0.5)1-x (LiSb)xNb1-xO3 286 1,372 51 - - 385 [46]
x = 0.052
[Lix(Na0.5K0.5)1-x] NbO3 235 - 42 - - 460 [45]
x = 0.06
(Na0.5-x/2,K0.5-x/2,Lix)NbO3 (7%Li) 240 950 (1 kHz) 45 - - 460 [44]

(Na0.5-x/2,K0.5-x/2,Lix) (Nb1-yTay) O3 190 920 (1 kHz) 46 - - 310 [44]

x = 3,y = 20
(K0.44Na0.52Li0.04) 300 - - - - 253 [3]
(Nb0.84Ta0.10Sb0.06) O3
(K0.44Na0.52Li0.04) 416 1,570 61 - - 253 [3]
(Nb0.84Ta0.10Sb0.06) O3 textured (1 kHz)
0.95 (Na0.5K0.5) NbO3-0.05LiTaO3 200 570 36 9 1.25 - [47]
(10 kHz)
BiFeO3 15 – 60 ~30 (GHz) - - - - [49]
BiFeO3 thin film 70 - - 50 – 60 - - [50]
BiFeO3 single crystal - - - 100 1.2 870 [53]
BiFeO3 ceramic 50 – 60 - - 40 - - [72]
Bi0.86Sm0.14FeO3 thin film 110 - - 70 - - [52]
Sensors 2010, 10 1954

Material d33 ε33T/ε0 kp Pr Ec Tc Reference

(pC/N) (meas. freq) (%) (µC/cm2) (kV/mm) (oC)
[Bi0.5(Na1-xKx)0.5] TiO3 - (100 kHz) - - - [54]
x = 0.16 635 31.4
x = 0.20 1,030 27.0
[Bi0.5(Na1-xKx)0.5] TiO3 192 1,007 32.5 19.5 - - [55]
x = 0.22
0.94Bi0.5Na0.5TiO3– ~94 - ~26 37 3.6 - [56]
0.06K0.5Na0.5NbO3
0.97(Na0.5K0.5) NbO3– 195 - 43 - - 375 [57]
0.03(Bi0.5Na0.5) TiO3
0.995(Bi1/2Na1/2) TiO3– - 530–700 - 33.6 6 340 [61]
0.005BiFeO3 (1 MHz)
(Bi1/2Na1/2)0.94Ba0.06TiO3 125 580 (10 kHz) - 20 - 288 [58]
(0.9)(Bi1/2K1/2) TiO3–0.1BaTiO3 84.5 560 (1 kHz) - - - - [62]
electric field applied parallel to
tape stacking direction
0.90 (K0.48Na0.48Li0.04) NbO3– 206 ~530 ~38 - - ~38 [65]
0.10BaTiO3 0
0.95 (Na0.5K0.5) NbO3–0.05BaTiO3 225 1,058 36 - - - [63]
0.92NBT-0.06BT-0.02KNN 30 2,320 - 16 1.3 - [66]
576* (10 kHz)
0.93NBT-0.05BT-0.02KNN 98 2,060 - 32 3.1 - [66]
276* (10 kHz)
(0.90)(Bi1/2Na1/2)TiO3– 148 700 (1 kHz) 34 35.9 - - [70]
0.05(Bi1/2K1/2) TiO3–0.05BaTiO3
0.852(Bi1/2Na1/2) TiO3– 191 1,141 33 - - 301 [69]
0.028BaTiO3–0.12(Bi1/2K1/2) TiO3 (1 kHz)
0.88NBT–0.08KBT–0.02BT 181 - - - - 300 [68]
(MPB)
0.78NBT–0.146KBT–0.074BT 128 - - - - 300 [68]
(tetragonal)
(Bi1/2Na1/2)0.78 (Bi1/2K1/2)0.22TiO3– 167 - 35.5 27.6 2.79 340 [71]
0.03(Na0.5K0.5) NbO3
*Values are measured under large driving signals.

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