Lead-Free Piezoelectrics Current Status and Perspe

Review
JOURNAL OF ADVANCED DIELECTRICS

Vol. 3, No. 2 (2013) 1330002 (22 pages)
© World Scientific Publishing Company
DOI: 10.1142/S2010135X13300028
Lead-free piezoelectrics: Current status and perspectives

Indrani Coondoo*, Neeraj Panwar and Andrei Kholkin
Department of Materials and Ceramic Engineering & CICECO,
University of Aveiro, 3810-193 Aveiro, Portugal
*indrani.coondoo@ua.pt
*
indrani coondoo@yahoo.com
Received 26 April 2013; Revised 29 May 2013; Accepted 4 June 2013; Published 2 August 2013
In the last few years, there has been tremendous effort to develop lead-free ferroelectric ceramics with high piezoelectric properties
by various doping and alloying routes. Several material systems have been explored, however, no prominent alternative to the
versatile lead zirconate titanate (PZT) system has been found yet. Despite the achieved improvement in piezoelectric properties,
there are problems in the synthesis, processing and poling of the sintered ceramics. Various processing techniques including
microwave, hydrothermal, solgel, Pechini and spark plasma sintering have been used to overcome the drawbacks related to
synthesis issues. In this paper, an attempt is made to review recent developments on lead-free piezo materials emphasizing their
preparation, structureproperty relations, and consequent physical properties. In this context, both compositional and structural
J. Adv. Dielect. 2013.03. Downloaded from www.worldscientific.com
engineering approaches to achieve acceptable piezoelectric properties in lead-free materials are discussed. Piezoelectric properties
of the most promising lead-free compositions/families including titanates, alkaline niobates and bismuth perovskites and their solid
solutions, along with non-perovskites such as bismuth layer-structured ferroelectrics are reviewed in detail. A brief coverage of the
by 23.94.27.117 on 06/13/14. For personal use only.
recent developments in the area of piezoelectric energy harvesting is also encompassed.

Keywords: Lead-free piezoelectrics; energy harvesting.
1. Introduction remain in the range 0.11 kHz.1 Therefore, much of

Piezoelectricity is a long studied phenomenon in crystal the recent research into power harvesting is focused on the
physics, discovered by Curie brothers in 1880. A piezo- methods of accumulating enough energy to power the
electric crystal when subjected to mechanical stress polarizes intended electronics. One of the solutions is to use a material
electrically in proportion to the applied stress and conversely, that possesses a strong piezoelectric effect where favorably
on application of electric field, the crystal changes its shape low voltages should be enough for large deformations. It is
(strains) depending upon the field level. Piezoelectric cer- well established that the piezoelectric coupling coefficients
amics have multifaceted applications in devices: various are very large in ferroelectrics where polarization can be
types of sensors (e.g., to measure acceleration, temperature, switched by the electric field. The best known ferroelectric
gas, pressure, etc.), piezoelectric actuators for nanoposition- compositions showing the highest piezoelectric effect are Pb
ing and fuel injection, transducers for ultrasonic medical (Zrx Ti1x ÞO3 (PZT)-based ceramics, which with a specific
imaging, structure health monitoring, microphones and buz- design enabled to achieve a strain of the order of 0.2%.2
zers, piezoelectric ignition devices, sonars, piezoelectric loud Compositionally, PZT ceramics lie near a morphotropic
speakers, resonators and filters, and many others. Recently, phase boundary (MPB) separating tetragonal and rhombo-
energy saving technologies such as biomechanical, piezo- hedral phases, at x ¼ 0:48 PbTiO3, shown in Fig. 1.3 The
electric and pyroelectric energy harvesting are attracting a most useful piezoelectric materials display a transition region
broad interest. Among these, most promising technique is in their composition phase diagrams, known as a morpho-
mechanical energy harvesting that utilizes the ability to tropic phase boundary. At MPB, the crystal structure changes
convert mechanical strain energy into electrical energy and abruptly and the electromechanical properties are maximal as
vice versa by piezoelectric components. While significant a result of enhanced polarizability, arising from the coupling
headway has been made in the field of power harvesting, the between the equivalent energy states. This allows most
amount of energy produced in most cases is still not sufficient favorable domain reorientation during the poling process.
to power an electrical device. In practice, piezoelectric gen- The common ferroelectric materials used for MPB appli-
erators remain of limited use to very low power domain, cations are usually PbZr1x Tix O3 (PZT) and lead magnesium
usually in the milliwatt range or below. This is mainly due to niobatelead titanate (1xÞ PbMg1=3 Nb2=3 O3xPbTiO3,
the insufficient mechanical properties of piezoelectric ma- abbreviated as PMNPT. For example, for the composition
terials: they accept very large stresses but their strains are of 52% lead zirconate and 48% lead titanate (MPB for PZT),
very small. Also, high mechanical frequencies of the order of the piezoelectric properties of the ceramic are particularly
hundreds of kilohertz are necessary to effectively use these advantageous (Fig. 1). The ceramics possess a coercive
materials, however, ambient mechanical vibrations usually field of about 1 kV/mm and a remanent polarization of
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I. Coondoo, N. Panwar & A. Kholkin J. Adv. Dielect. 3, 1330002 (2013)
2. Lead-Free Piezoelectric Materials

2.1. Bismuth layer structured ferroelectrics (BLSF )
The crystal structure of BLSF compositions, first described
by Aurivillus,40 is characterized by pseudo-perovskite layers
(An1 Bn O3nþ1 Þ 2 stacked between (Bi2O2 Þ 2þ sheets.41 A is a
mono-, divalent or trivalent cation and B is a quadric-, penta-
or hexavalent metal; n represents the number of perovskite
layers. The family of bismuth layer-structured ferroelectrics is
very attractive from the viewpoint of their applications
because BLSF are characterized by low dielectric constant
("), high Curie temperature (Tc ), and owing to the layered
structure, the compositions exhibit a very high anisotropy of
properties, for example a pronounced anisotropy in the
electromechanical coupling factors.31,4246 The piezoelectric
Fig. 1. Phase diagram of PZT. Source: Copyright 2009, Reprinted coefficient is the highest in the ab-plane. Thus, BLSF cer-
with permission from Springer. amics seem to be excellent candidates for lead-free piezo-
electric applications as high-temperature piezoelectric
sensors, filters and ceramic resonators with large figures of

about 35 C/cm2. A large signal piezoelectric coefficient
merit (e.g., high mechanical quality factor, Qm , and low
779 pm/V derived from strain versus electric field curve,
temperature coefficient of resonance frequency). Moreover,

has been reported for doped PZT.4 On the other hand, the
the piezoelectric properties can be effectively controled by
environmental concerns are strongly driving the need to
the processing conditions and dopant concentration. There-
replace lead-based piezoelectric materials like PZT which
fore, a better understanding of different processes that affect
contains more than 60% of a toxic element, i.e., lead (Pb).
piezoelectric properties in this group of compositions is of a
Undoubtedly, the last decade has witnessed enormous effort
towards development of lead-free piezoelectric ceramics and wide interest.
a large increase of publications has followed up537 (Fig. 2). Bismuth titanate, Bi4Ti3O12 (BIT), is a well-known BLSF
In particular, a tremendous number of articles have appeared material that exhibit high anisotropy with spontaneous
since 2006. Bulk piezoelectricity has been reported in many polarizations reported to be 50 and 4 C/cm2 along the a- and
families of lead-free ceramic materials including perovskites, c-axes, respectively.47 These properties prompted a wide
tungsten bronze and bismuth layer-structured ferroelectrics as research of their respective piezoelectric properties. However,
well as various grain-oriented nonferroelectric materials.38 studies suggest that the platelet shape of the BIT single
The present article provides an overview of the current crystals and the low-resistivity and large coercive field in BIT
developments in several lead-free piezoelectric materials ceramics, hinder reliable procurement of piezoelectric prop-
including BaTiO3, Na0:5 Bi0:5 TiO3, K0:5 Bi0:5 TiO3, Na0:5 K0:5 erties.4853 To overcome these drawbacks, researchers have
NbO3, and their solid solutions and highlights a brief survey attempted doping BIT with donor ions (e.g., Nb 5þ , Ta 5þ ,
on the specific application of piezoelectric ceramics i.e., Sb 5þ , V 5þ Þ to increase the resistivity.54 The resistivity (Þ
energy harvesting. values were indeed increased from 10 10 10 11 cm for BIT
(x ¼ 0) to about 10 13 10 14 cm in Nb- and V-doped BIT
ceramics.25 Not only a dramatic increase in the resistivity was
observed, but Nb-doped BIT[Bi4Ti3x Nbx O12 (BITN-xÞ] and
V-doped BIT [Bi4Ti3x VxO12 (BITV-xÞ] also show high
Tc 650 C. Thus, the donor-doped BIT could be polarized,
and exhibit d33 between 18 and 20 pC/N accompanied by
good stability with time and temperature.55 The k33 value of
the grain-oriented BITN-0.08 ceramic has a value of 0.39 and
maintains this property up to 350 C. Further, in case of grain-
oriented Nd and V co-substituted BIT (BNTV with Nb ¼
0:01 and V ¼ 0:75), the ceramics have excellent piezoelectric
properties, e.g., Qm 2230, Qemax ¼ 37.38 These properties
are comparable to those of hard PZT ceramics for resonator
applications. Table 1 compares the obtained values for the
respective ceramic material.38
In another report,56 BIT doped with a small amount of
Fig. 2. Publications on lead-free piezoceramics.39 niobium, Bi4Ti2:95 Nb0:04 O12 , exhibited properties that were
1330002-2
Table 1. Piezoelectric properties of ordinarily fired (OF)- and hot forged increase the transition point Tc , there has not been much of a
(HF)-BNTV (0.01, 0.75) ceramics. success. For instance, (Ba0:92 Ca0:08 Þ(Ti0:95 Zr0:05 ÞO3 has
Mechanical quality Electrical quality
high piezoelectric coefficient d33 ¼ 365 pC/N and high planar
factor, Qm factor, Qemax electromechanical factor kp ¼ 48:5%; nevertheless, the Tc is
even lower, down to 110 C. Recently, Liu and Ren69
OF HF OF HF reported a new lead-free system, Ba(Zr0:2 Ti0:8 )O3x
(Ba0:7 Ca0:3 )TiO3 (BZTxBCT), characterized by a phase
BIT-V 1500 — 12.8 —
BIT-Nd — —
boundary between rhombohedral (BZT side) and tetragonal
6640 7.8
BNTV (0.01, 0.75) 4200 2230 50.9 36.9 (BCT side) phases. The d33 as high as 600 pC/N was obtained
Hard PZT 2440 — 28.0 — in the optimized composition.6971 Yet another Pb-free
pseudo-binary system has been designed, Ba(Sn0:12 Ti0:88 )
O3x(Ba0:7 Ca0:3 )O3 (BTSxBCT), characterized by a phase
similar to those of PZT ceramics. The piezoelectric d33 boundary starting from a tricritical triple point of a para-
coefficient was nonlinear and showed frequency dependence, electric cubic phase, ferroelectric rhombohedral, and tetra-
while the charge density exhibited a large hysteresis with gonal phases. The optimal composition BTS30BCT
respect to the driving pressure. exhibited a high piezoelectric coefficient d33 530 pC/N at
room temperature.72 However, the transition temperature is
still low. Structural engineering approaches by several groups

2.2. Perovskites have also led to significantly improved piezoelectric response
Most of the commercially important ferroelectric materials in BT. Microwave sintered BT ceramics prepared from
have a perovskite-type crystal structure, having the generic nanoscale particles resulted in a high d33 value of 350
composition ABO3, where ion A is 12 fold coordinated with pC/N.7375 Hydrothermally synthesized BaTiO3 powders
respect to oxygen and ion B is octahedrally coordinated to followed with optimized sintering process resulted in fine
oxygen. The perovskite type structure is tolerant to variations grains (size of about 12 m) and d33 460 pC/N.76,77
in composition and distortions due to its ability to adapt a Moreover, a d33 value of 788 pC/N was reported in [110]
mismatch between the equilibrium AO and BO bond grain oriented BT ceramics with submicron domain size.78
lengths, allowing the existence of a large number and variety These findings clearly demonstrate that structural engineering
of stoichiometric compounds. The perovskite structure can could be a key concept in achieving large piezoelectric res-
undergo many different distortions of the unit cell: (a) along ponse in lead-free piezoceramics. BT is often used in solid
the cubic [100] direction (b) along the [110] direction solution with other lead-free compounds to form an MPB
(c) along the [111] direction or (d) along arbitrary [hk0] or which can enhance the piezoelectric and dielectric properties.
[hkl].57 These distortions, namely, tetragonal, orthorhombic, For instance, in the solid solution 0.80BT0.20(K0:5 Bi0:5 )
rhombohedral and monoclinic, give rise to changes in the TiO3 TC reaches a value around 240 C, but the relative per-
crystal symmetry, and one or more cations shift from high- mittivity is lower than in pure BT.38,79 Such solid-solution
symmetry positions in the lattice, thus producing a ferro- systems are discussed in the following sections.
electric or an antiferroelectric behavior. These compositions
Sodium bismuth titanate — (Bi1/2Na1/2)TiO3 — (BNT ):
show relatively high piezoelectric constant (d33 ), and are
First reported in the 1960s by Smolenskii et al.,80 BNT
suitable for actuator and high power applications. The most
gained much attention due to the recent surge in lead-free
studied perovskite-based lead-free piezo-ceramics are
material development in the past two decades. It is a
BaTiO3 (BT), Bi0:5 Na0:5 TiO3 (BNT) and K0:5 Na0:5 NbO3
perovskite-type ferroelectric at room temperature and exhibits
(KNN).5,6,8,1012,1625,31,34,35,5860
relaxor ferroelectric behavior. A diffused phase transform-
Barium Titanate (BaTiO3BT): Barium titanate, devel- ation in the temperature range 200 C320 C is observed in
oped in the 1940s and 1950s was the first oxide with per- BNT corresponding to a transition from the rhombohedral to
ovskite-type structure exhibiting ferroelectric behavior.6163 It tetragonal symmetry.8183 At room temperature, BNT is
has a relatively high electromechanical coupling factor (k33 Þ strongly ferroelectric with a relatively large remnant polar-
and has been partially used for piezoelectric applications such ization, Pr ¼ 38 C/cm2 and a high coercive field, Ec ¼
as sonar although its main use was for capacitor applications 73 kV/cm.84 However, because of its large coercive field and
owing to its very high permittivity (10410 6 Þ.6466 The d33 of relatively large conductivity, pure BNT is hard to pole
pure BT fabricated by conventional solid-state processing is resulting in a limited piezoelectric performance. In addition,
approximately 190 pC/N.67 However, BT exhibits a relatively BNT ceramics require high sintering temperature (> 1200 C)
low Curie temperature, Tc ð120 C)68 constraining the to obtain a dense body resulting in significant loss of bismuth.
working temperature range and limiting their use in piezo- Various authors have studied BNT-based solid solutions and
electric applications. While a lot of efforts were devoted to the effect of different dopants on BNT to combat these
simultaneously improve the piezoelectric properties and to drawbacks. For example, Li þ and K þ co-doped BNT showed
1330002-3
an exceptional change. Xiao et al. were able to increase the

piezoelectric and coupling coefficients of BNT to 146 pC/N
and 36%, respectively, and reduce the coercive field to
Temperature ( °C )
37 kV/cm while maintaining a high depolarization tempera-
ture to produce a lead-free middle frequency filter with
performance comparable to Pb-based counterpart.21,85
Herabut and Safari86 studied the effect of La in BNT
[(Bi0:5 Na0:5 Þð11:5xÞ Lax TiO3] and concluded that the d33 value
increases to 92 pC/N for optimal composition with 6 mole%
lanthanum oxide. Li et al.87 prepared lead-free bismuth sodium
titanatesodium niobate (BNTNN), [(Na0:5ð1xÞ Bi0:5ð1xÞ Þ
(Tið1xÞ Nbx ÞO3] ceramics. They found that the dielectric permit- Bi1/2Na1/2TiO 3 BaTiO3 mol%
tivity was increased with NaNbO3 content, however d33
increases from 64 to 88 pC/N for 2 mol% of NaNbO3 and then Fig. 4. Phase diagram of Bi0:5 Na0:5 TiO3BaTiO3 (BNTBT).31
gradually decreases. They attributed this behavior to the sim- Source: Copyright 1991, The Japan Society of Applied Physics.
ultaneous effect of soft (Nb 5þ Þ at B-site and hard (Na þ Þ
additive at the A-site. Effect of Bi2O3 Sc2O3 in BNT-based properties was observed.91 In particular, a strong piezo-
solid solution ð1 xÞ(Bi0:5 Na0:5 ÞTiO3x(Bi2O3 Sc2O3 Þ0:5 was
electricity is expected in the BNT-based solid solutions with a

also investigated from the view point of a new group of lead-free MPB because BNT has a rhombohedral symmetry at room
piezoelectric ceramics.88 Figure 3 shows the phase relations temperature. Takenaka et al.31 designed the solid solution
between (Bi0:5 Na0:5 ÞTiO3, KNbO3, and (Bi2O3 Sc2O3 Þ0:5 on system, (1xÞBNTxBT and reported that MPB exists at
pseudo-three-component-system. The effects of modified x ¼ 0:060.07 for BNBT system between the BNT-rich
Bi 3þ ions were studied in the pseudo-ternary system a rhombohedral and BT-rich tetragonal phases with a TC of
(Bi1=2 Na1=2 ÞTiO3bKNbO3c(Bi2O3 Sc2O3 Þ0:5 that revealed 288 C. The system at MPB exhibits improved properties
an increase in the coercive field Ec with increase in Bi content compared to BNT with enhanced d33 ¼ 125 pC/N (in pure
(a decrease when the amount of Bi ions is decreased, making BNT, d33 ¼ 64 pC/N)), d31 ¼ 40 pC/N, k33 ¼ 0:55, and
poling easier and k33 higher).89 Shuvaeva et al. studied the local k31 ¼ 0:19. BNTBT compositions near the MPB also
structure of lead-free potassium substituted lead-free relaxor exhibit high bending strength (e.g., 200 MPa), which is 23
ferroelectric (KxNa1x)0.5Bi0.5TiO3 by x-ray absorption fine times of that of the PZT-based materials.31 However, one of
structure (XAFS) tachnique.90 It was found that the local en- the major drawbacks of this MPB system is the temperature
vironment of Bi is much more distorted than that determined dependence of the properties. The MPB in BNTBT (Fig. 4)
from conventional diffraction experiments. is not linear with temperature, but rather has a curved shape.31
Ichinose and Udagawa reported that the piezoelectric Hiruma et al.92 through various electrical measurements,
property of (Bi0:5 Na0:5 Þ0:87 (Sr0:5 Ca0:5 Þ0:13 TiO3 system is such as the temperature dependence of the dielectric constant
close to MPB composition from the view point of lead-free and loss tangent, of various compositions of BNTBT,
piezoelectric materials. With 1 wt.% addition of MnO, an confirmed the behavior encompassed by the phase diagram.
improvement in the electromechanical and mechanical Electric field induced phase transitions from rhombohedral to
tetragonal in the MPB composition (similar to the electric
field-induced phase transitions for BT), resulting in a strong
orientation of the ferroelectric and ferroelastic domain
orientations relative to the electric field direction, was
established by Daniels et al.93 In the case of textured
(Bi0:5 Na0:5 )0.94(Ba0:06 TiO3 Þ ceramics prepared by tem-
plate grain growth, the d33 reached 200 pC/N which is 1.6
times higher than the polycrystal.94
The influence of nonstoichiometry and doping on piezo-
electric properties and structure of BNTBT-based solid
solutions near the MPB were studied by Chu et al.95 Their
preliminary research indicated that, similar to PZT-based
ceramics, high-valence cations can be seen as a soft additive
and low-valence cations as hard additive to the base com-
position. Nb 5þ (soft additive) led to the enhancement of
piezoelectric constant (d33 149 pC/N), dielectric constant,
Fig. 3. Phase relation between BNT, KNbO3, and (Bi2O3 Sc2O3 Þ0:5 .89 dielectric loss, etc. while Co 3þ (hard additive) caused com-
Source: Copyright 1998, The Japan Society of Applied Physics. positional inhomogeneity resulting in the multiphase
1330002-4
character over a relatively wide temperature range. Zhou

et al.96 studied the effect of Mn in the BNTBT system:
(Na0:5 Bi0:5 Þ0:92 Ba0:08 TiO3 þ x mol% Mn (BNBTMn). The
piezoelectric constants d33 and kt increased up to x ¼ 0:56,
taking the maximum value of 160 pC/N and 58.5%, while the
values decreased slightly with x > 0:56. They argued that
with Mn lower than 0.56 mol%, the increase in piezoelectric
properties was partly due to the decrease of tetragonality of
BNBT while excess of Mn ions accumulates in the grain
boundaries, resulting in the pinning effect of domains.
Fig. 5. Phase diagram of Bi0:5 K0:5 TiO3BaTiO3.38
Yttrium modified (Bi0:5 Na0:5 Þ0:94 Ba0:06 TiO3 piezoelectric Source: Copyright 2008, The Japan Society of Applied Physics.
ceramics showed optimum piezoelectric properties with
d33 ¼ 137 pC/N and the electromechanical coupling factor
BKT with BT, BNT, etc. Both BaTiO3 and (Bi0:5 K0:5 )TiO3
kp ¼ 0:30.97
are well-known lead-free piezoelectric materials with the
Ba(Ti,Zr)O3 (BZT) system has a good piezoelectric con-
tetragonal symmetry having TC 120 and 370 C, respect-
stant equal to 236 pC/N at room temperature.98 Hence, a
ively. The binary system BTBKT has been investigated in
binary system of BNTBZT was studied and the properties
order to obtain a compound with enhanced piezoelectric
at the MPB were investigated. Dense BNTBZT ceramics

properties and higher TC than pure BaTiO3. Phase diagram
(5.695.82 g/cm 3 Þ were obtained by the perovskite route in
of the BKTBT solid solution,38 is shown in Fig. 5. In
which BNT and BZT were prepared separately. For
the ð1 xÞBTxBKT composition range, Tc increases with
BNTBZT binary system, a high piezoelectric constant,

increasing amount of x.25,38 In compositions above x ¼
d33 ¼ 147 pC/N was obtained at the composition near MPB.
60 mol% BKT, a second transition from tetragonal to an in-
Piezoelectric properties of a new system, ð1 x yÞ
termediate pseudocubic phase is observed at around 300 C
Bi0:5 Na0:5 TiO3xBaTiO3yBi0:5 Ag0:5 TiO3 lead-free cer-
and remains nearly independent of BKT content. The ob-
amics demonstrated that a MPB between rhombohedral and
served values of the d33 coefficient did not change signifi-
tetragonal phases of BNTBTBAT ceramics is formed for
cantly with composition and were in the range 6070 pC/N.
x ¼ 0:060.08.99 Near the MPB, the ceramics with x ¼ 0:06
Compositions with x > 60 mol% BKT showed good thermal
and y ¼ 0:050.06 possess optimum electrical properties:
stability of the coupling coefficient and are considered
Pr 42:5 C/cm2, Ec 32 kV/cm, d33 172 pC/N, kp
attractive for piezoelectric applications even with their low
32:6%, and kt 52:6%. The temperature dependences of
d33 70 pC/N. The highest d33 100 pC/N was obtained for
kp and PE hysteresis loops revealed that the depolarization
x ¼ 5 mol% BKT with the addition of Mn, however, this
temperature (Td ) of BNTBTBAT-0.06/y ceramics
composition has a relatively low Tc of 168 C.
decreased with increasing y.
Piezoelectric coefficient, d33 , for randomly oriented
Bismuth potassium titanate (Bi0.5K0.5)TiO3 — BKT: BKT, BKTBT were relatively small for the practical use in
another common lead-free ferroelectric ceramic material, was actuators. Thus, structural engineering methods, to enhance
originally fabricated by Popper et al.100 in 1957 and its ferro- their piezoelectric properties were tried and textured samples
electricity was confirmed later by Buhrer.101 BKT is unique by Reactive Template Grain Growth (RTGG) were then
from BNT, in that it is tetragonal at room temperature fabricated. Structural engineering in BKTBT led to a sig-
(whereas BNT is rhombohedral) and does not depolarize until nificantly improved d33 value of 121 pC/N, for x ¼ 10 mol%
270 C.102 However, one of the main challenges of this system BKT textured using the template grain growth tech-
is that it is difficult to produce dense ceramics using ordinary nique.104,105 The piezoelectric properties of the textured and
firing methods causing difficulty in poling. Density was nontextured BKTBT10, 20 and 30 are summarized in
improved using sintering aids, e.g., Hiruma et al. found that Table 2.
the processing of BKT with excess bismuth oxide helps The solid solution of BNTBKT was synthesized by
improving the piezoelectric and ferroelectric properties of the Elkechai et al. in 1996106 and an increase in piezoelectric
material (e.g., d33 ¼ 101 pC/N) because Bi2O3 prevented the properties was observed in the MPB region, shown in Fig. 6.
formation of micro-cracks.103 Alternatively, high densities A solid solution of BNTBKT forms a MPB between
(97% of the theoretical one) can also be achieved by hot rhombohedral (BNT-rich) and tetragonal (BKT-rich) struc-
pressing methods yielding piezoelectric d33 70 pC/N.102 tures in the region of 1622 mol% BKT.107 The existence of
Hot pressed BKT attests a pronounced increase of TC to an MPB in the compositional range 1620 mol% BKT was
410 C435 C whereas the temperature of the second phase validated by Sasaki et al.108 based on structural studies. Since
transition was also increased (315 C340 C). this solid solution contains several elements that volatilize
A considerable amount of work was also devoted to the easily, such as K, Na, and Bi, the sintering conditions used
dielectric and piezoelectric properties of solid solutions of plays an important role in the final piezoelectric properties
1330002-5
Table 2. Piezoelectric properties of BKTBT10, 20 and 30 prepared by ordinary

firing (OF) and RTGG methods. k33 s E33 d33 d 33 are electromechanical coupling factor,
elastic constant, piezoelectric strain constant and dynamic d33, respectively.104,105
BKTBT10 BKTBT20 BKTBT30
OF RTGG OF RTGG OF RTGG
k33 0.35 0.37 0.36 0.33 0.38 0.38

s E33 (pm 2 /N) 8.2 10.5 8.2 10.1 7.8 13.0
d33 (pC/N) 73.4 84.5 69.3 70.7 67.6 83.3

d 33 (pm/V) 103 168 116 143 103 134
achieved in these materials.107 For example, Zhang et al. composition (Bi1x Na0:8 K0:2 Lax Þ0:5 TiO3 have also been
found that with a change of only 40 C in the sintering tem- studied.115 Moderate substitution of La 3þ for Bi 3þ in BNKT
perature of the BNTBKT solid solution at the MPB, the ceramics enhanced the piezoelectric properties. Composition
piezoelectric constant increased from 155 to 192 pC/N.107 with x ¼ 0:005 showed the highest piezoelectric perform-
More recent studies30,109111 confirmed high piezoelectric ance and strong ferroelectricity with d33 ¼ 155 pC/N;
kp ¼ 29:5% and kt ¼ 47:3%; Qm ¼ 110; Pr ¼ 20:2 C/cm2;
properties (d33 in the range 140192 pC/N) of the MPB

composition. Tc (280 C300 C) of the MPB composition and Ec ¼ 27:2 kV/cm.
was higher than that of pure BNT, however, the depolariz- The effects of co-doping with Ta- and Li-ions on ferro-
ation temperature Td decreased to 140 C at the MPB. electric and electric field-induced strain properties of Bi1=2
Zhang et al. investigated the microstructure and electrical (Na0:82 K0:18 Þ1=2 TiO3 (BNKT) ceramics were investigated.116
properties of Bi-compensated BNTBKT ceramics sintered Li substitution at Na-sites resulted in a ferroelectric-nonpolar
at 1110 C1170 C.107,113 Enhancement in grain growth, phase transition and a large accompanying normalized strain
densification, and improvement of piezoelectric and ferro- ðSmax /Emax Þ ¼ 727 pm/V was observed near the phase
electric properties was observed with increasing sintering boundary, with 2.5 mol% Li and 2.5 mol% Ta doped on A-
temperature. However, sintering temperature > 1170 C was and B-sites, respectively.
detrimental to the piezoelectric properties. An MPB-like Depolarization temperature and piezoelectric properties of
phase transition from tetragonal to rhombohedral symmetry lead-free (Bi1=2 Na1=2 ÞTiO3(Bi1=2 Li1=2 ÞTiO3(Bi1=2 K1=2 Þ
was observed in BNKT20 and BNKT22 specimens. Owing TiO3 piezoelectric ceramics were reported by Hiruma et al.117
to the MPB-like behavior, enhanced electrical properties Ceramics of compositions x(Bi1=2 Na1=2 ÞTiO3y(Bi1=2 Li1=2 Þ
were obtained for the BNKT22 samples with d33 , Pr , and kp TiO3z(Bi1=2 K1=2 ÞTiO3 [x þ y þ z ¼ 1] (abbreviated as
were 192 pC/N, 19.5 C/cm2, and 35%, respectively. Yoo BNLKT100y100zÞ ceramics were investigated. A MPB
et al. investigated the variations of Sr substitution in Bi0:5 between rhombohedral and tetragonal phases at z ¼
(Na0:84 K0:16 Þ0:5 TiO3 system114 and concluded that a MPB 0:180.20 was observed. The piezoelectric constant d33
could be obtained with the 46 mol% Sr addition. A high increased with increasing y; however, Td decreased above
piezoelectric constant, d33 185 pC/N, was reported. La 3þ y ¼ 0:06. The d33 and Td values of BNLKT4-20 and
modified BNKT piezoelectric ceramics with the BNLKT8-20 were 176 pC/N and 171 C, and 190 pC/N and
115 C, respectively.
Electric field-induced strain (EFIS) of lead-free Bi0:5 Na0:5
TiO3Bi0:5 K0:5 TiO3 ceramics modified with LiTaO3 was
reported by Do et al.118 Binary (1xÞBNTxBKT compo-
sitions within x ¼ 0 0.4 were strongly ferroelectric, how-
Temperature (oC)
ever, LT modification induced a ferroelectric-nonpolar phase

transition. The highest EFIS in BNTBKTLT ternary
system was observed at the triple point where ferroelectric
rhombohedral, tetragonal, and nonpolar pseudocubic phases
coexist. Giant strain was observed in Nb modified
Bi0:5 Na0:5 TiO3Bi0:5 K0:5 TiO3 ceramics.119 Nb doping
induced a phase transition to a pseudocubic phase with high
electrostriction coefficients. With 3 mol% Nb substitution, the
(Bi1/2Na1/2)TiO3 mol% (Bi1/2K1/2)TiO3
EFIS markedly enhanced up to Smax /Emax ¼ 641 pm/V. Lead-
Fig. 6. Phase diagram for the (Bi1=2 Na1=2 ÞTiO3(Bi1=2 K1=2 ÞTiO3 free Zr-modified Bi0:5 (Na0:78 K0:22 Þ0:5 TiO3 ceramics
solid solution.112 (BNKTZ-100x, with x ¼ 0 0.05) were synthesized by
Source: Reprinted with permission from IOP science. Hussain et al.120 by a conventional ceramic fabrication
1330002-6
process. The BNKTZ ceramics showed an enhanced unipolar Li et al. investigated a (13xÞBNT2xBKTxBT ternary
field-induced strain of 0.43%. A high dynamic piezoelectric system by keeping the BKT and BT ratio constant. They
coefficient (d33 ¼ Smax =Emax Þ ¼ 614 pm/V was obtained for concluded that the dielectric constant and d33 increases with
this composition, which is much higher than that of poly- increasing x, reaching a maximum value of 150 pC/N at
crystalline lead-free and hard Pb(Zr,Ti)O3 ceramics. x ¼ 0:035.125,126 Li et al. also prepared ð15xÞBNT
A new lead-free solid solution ð1 xÞBi0:5 (Na0:78 K0:22 Þ0:5 4xBKTxBT ceramic by conventional ceramic fabrication
TiO3x(Bi0:5 La0:5 ÞAlO3 (BNKTBLA) ceramics has been technique.127 The MPB of this system was demonstrated to
fabricated by conventional solid-state reaction method.121 be in the range of x ¼ 0:0240.030 between rhombohedral
The effect of (Bi0:5 La0:5 ÞAlO3 (BLA) content on the crys- and tetragonal phases. The highest d33 ¼ 149 pC/N at x ¼
talline structure, microstructure, ferroelectric properties, and 0:030 and planar electromechanical coupling factor kp ¼
electric field-induced strain was investigated. The ferro- 28:2% at x ¼ 0:028 were observed.127 The composition 0.90
electric order in the BNKT ceramics was significantly dis- (Bi0:5 Na0:5 ÞTiO30.05(Bi0:5 K0:5 ÞTiO30.05BaTiO3 (abbre-
rupted by the addition of BLA, resulting in a drastic viated as BNTBKTBT5) has been used as the driving
degradation in the remnant polarization, coercive field, and element in a cymbal actuator with titanium end caps with
negative strain. However, the degradation of the polarization performance comparable to those fabricated using hard PZT
values was accompanied by a significant enhancement in the ceramic.128 Further enhanced performance was found in Li-
strain behavior. In particular, a very large electric field- modified BTBNTBKT, exhibiting a d33 of 205 pC/N,
induced strain (S ¼ 0:40%) and a corresponding normalized with a depolarization temperature Td ¼ 210 C.35
strain (d33 ¼ 579 pm/V) was obtained for x ¼ 0:010. A new system of BNT-based multi-component lead-free
Bi0:5 (Na,K)0:5 TiO3BiGaO3 lead-free piezoelectric ce- piezoelectric ceramics, [Bi1z (Na1xyz Kx Liy Þ]0:5 Baz TiO3,
ramics with the composition ð1 x yÞBi0:5 Na0:5 TiO3 was studied.35 The ceramics demonstrate good piezoelectric
xBi0:5 K0:5 TiO3yBiGaO3 has been reported by Zhou et al.122 performances and strong ferroelectricity: d33 ¼ 205 pC/N,
The maximum d33 and the kp with values of 165 pC/N and kp ¼ 37:0%, Pr ¼ 38:5 C/cm2, Ec ¼ 28:0 kV/cm, and high
34.6%, respectively, were obtained in this work. depolarization temperature Td . The addition of Li signifi-
The ternary BTBNTBKT solid solution (phase dia- cantly improved the sintering performance and greatly
gram shown in Fig. 7) has also been widely investigated assisted the densification of BNT-based ceramics. Lin
owing to relatively high Tc and high piezoelectric properties. et al.129 performed further investigation on BNT system by
In comparison with BNTBT and BNTBKT, compositions substituting Na þ in BNT by K þ and Li þ . Thus obtained Bi
of the ternary system typically exhibit higher depolarization (Na,K,Li)TiO3 ceramics was a new group of BNT-based lead-
and/or Curie temperatures. BTBNTBKT presents a free system.129 The measurements of dielectric and piezo-
tetragonal (BKT and BT)rhombohedral (BNT) MPB while electric properties revealed that the ceramics with high
maintaining piezoelectric properties similar to its end mem- amount of K þ and low amount of Li þ provide relatively high
bers. Reported values of the piezoelectric coefficient (d33 Þ are piezoelectric coefficient d33 (up to 180 pC/N) and high planar
in the range 135191 pC/N.32,123 For compositions with a electromechanical coupling factor kp (up to 35.0%). Also,
more reasonable depolarization temperature (Td ¼ 197 C) a Lam et al. synthesized soft lead-free piezoelectric materials
maximum d33 of 135 pC/N was obtained.124 in the system BNKLT 13 composites.130 Zhang et al.131
studied the temperature-dependent electrical properties of
Bi0:5 Na0:5 TiO3BaTiO3Bi0:5 K0:5 TiO3 near the MPB.
Detailed analysis of the temperature dependence of polar-
izationelectric field (PE ) loops and bipolar/unipolar
strainelectric field (SE ) curves of this composition
revealed a ferroelectricantiferroelectric phase transition
around 100 C.
Recently, Trelcat et al.132 studied the xBi0:5 Na0:5 TiO3
yBaTiO3zBi0:5 K0:5 TiO3 piezoelectric ceramics. Detailed
structural measurements by X-ray diffraction with Rietveld
refinement allowed a more precise determination of the MPB
in this system. For ð1 xÞBNTxBT solid solution cera-
mics, the 0.94 BNT0.06 BT morphotropic composition
showed higher values with d33 ¼ 170 pC/N, kp ¼ 35:0 and
kt ¼ 53:0%. In the case of ð1 xÞBNTxBKT compo-
sitions, the d33 , kp and kt obtained were 137 pC/N, 39.0% and
Fig. 7. Ternary phase diagram for the BaTiO3(Bi1=2 Na1=2 Þ TiO3 54.0%, respectively for the 0.80 BNT0.20 BKT ceramic.
(Bi1=2 K1=2 ÞTiO3 solid solution.124 On the other hand, the ternary 0.865BNT 0.035BT
Source: Copyright 2005, The Japan Society of Applied Physics. 0.100BKT morphotropic composition shows high
1330002-7
Fig. 8. (Color online) The new MPB (in red lines) compared to
literature (in dotted black lines) as proposed by Trelcat et al.132
Source: Copyright 2012, reprinted with permission from Elsevier.
Fig. 9. Phase diagram for the KNN solid solution.138
Source: Copyright 2005, reproduced with permission from Elsevier.

piezoelectric constant and electromechanical coupling factors
(d33 ¼ 133 pC/N, kp ¼ 26:0% and kt ¼ 57:0%Þ. From these

summarized137,138 as displayed in Fig. 9. In contrast to
results, new morphotropic boundary limits on the ternary
the composition-dependent transition temperature of PZT,
diagram has been proposed (Fig. 8). Their results showed that
KNN exhibits composition-independent phase transition
the morphotropic area is larger than that proposed previously.
temperature between ferroelectric phases at 200 C and
Lead-free piezoelectric ceramics (Bi1=2 Na1=2 Þ1x
between ferroelectric and paraelectric phases at 400 C.
(Bi1=2 K1=2 Þx TiO30.03(Na0:5 K0:5 ÞNbO3 (x ¼ 0.100.40)
High Curie temperature, notable electromechanical
was studied by Yao et al.133 The materials near MPB show a
coupling factor, existence of MPB and environmentally
strong compositional dependence with the optimal properties
friendly constituents make KNN system advantageous for
of d33 167 pC/N, kp 35:5%, Pr 27:6 C/cm2 and Ec
various applications. A few drawbacks, however, still prevent
27:9 kV/cm. Very recently, Hao et al.134 reported on the lead-
wide scale industrial use. The material is difficult to sinter
free ternary ð1 yÞ[(1xÞ(Bi0:5 Na0:5 ÞTiO3x (Bi0:5 K0:5 Þ
using ordinary conditions and also the reactant powders
TiO3]y(K0:5 Na0:5 ÞNbO3 (BNTBKTKNN) system.
require special care.6 Volatility of the alkali species at high
KNN addition induced the MPB transition from (I) ferro-
temperatures37 and hygroscopic nature of the reactant
electric rhombohedral/tetragonal phase boundary to (II)
powders6 leads to nonstoichiometric, inhomogeneous com-
ferroelectric rhombohedral/relaxor pseudocubic phase
positions. All these problems require carefully controlled
boundary. A giant strain 0:46% was observed in a very
manufacturing conditions and low reaction temperatures. The
narrow region in the BNTBKTKNN system with
low sintering temperatures required to overcome the
x ¼ 0:20, y ¼ 0:01. Singh and Chatterjee135 studied the
instability of the KNN phase above 1140 C make it difficult
1 x y(Bi 0:5 Na 0:5 ÞTiO 3 x(Bi 0:5 K 0:5 TiO 3 Þy(Na 0:5 K 0:5 Þ
to obtain dense ceramics.139 Furthermore, KNN exhibits poor
NbO3 [BNTBKTKNN] ceramics series. Addition of
densification behavior under pressure-less sintering con-
KNN considerably lowered the depolarization temperature. A
ditions.139 The piezoelectric data for the air-fired samples are
large strain (strain of 0:80%) was observed for y ¼ 0:01;
in the range of d33 ¼ 8090 pC/N and density of the sample
x ¼ 0:20 series and strain of 0.50% was seen for y ¼ 0:04,
is around 4.25 g/cc.61 Various methods to overcome the
x ¼ 0:17 series.
drawbacks pertinent to KNN have been undertaken, e.g., both
Sodium potassium niobate — K0.5Na0.5NbO3 — (KNN): excess potassium and sodium oxide were introduced to
KNN is considered as one of the most promising candidates compensate the evaporation loss of the alkali ions.140 Also, in
for lead-free piezoelectric ceramics. It is a specific compo- some studies to avoid the oxygen vacancies, sintering under
sition (50/50) on a complete solid solution of antiferroelectric oxygen atmosphere was applied.141 Nevertheless, reasonable
NaNbO3 and ferroelectric KNbO3. This composition is close piezoelectric properties of KNN have been achieved by
to the MPB between two orthorhombic phases, resembling optimizing the conventional sintering process.139 A third way
the PZT system. High chemical inertness and compatibility to improve densification is by reducing the particle size of the
with human tissue allow for medical uses as well. Its high synthesized powders; however, since the conventional cer-
electromechanical coupling factor and low dielectric constant amic method does not achieve considerable reduction of
makes it interesting for ultrasonic applications.136 KNN has particlesize, the solgel,142,143 Pechini144 and hydrothermal
several thermally induced phase transitions and MPBs methods145147 have been used instead. Densification of
1330002-8
KNN ceramics is also improved by hot-pressing, with den- was attributed to the shift of orthorhombictetragonal phase
sities reaching 99% (of the theoretical density) and the transition ðTot Þ in the KNN phase diagram in the vicinity
resulting piezoelectric constant is about twice the value of of room temperature.167 Wang et al. achieved enhanced
conventionally sintered KNN.148150 Spark plasma sintering Tc ¼ 438 C and d33 ¼ 252 pC/N in the Ag-doped KNNLT
has also resulted in high-density KNN ceramics with ceramics prepared by normal sintering technique.168
enhanced piezoelectric coefficients (d33 ¼ 148 pC/N).151153 Recently, both \hard" and \soft" effects were observed due
Densification improvement via addition of sintering aids such to the CuO addition to the KNNLT system.169 It was ob-
as CuO, MnO2, K4CuNb8O23 (KCN), K5:4 CuTa10 O29 Bi2O3 served, that by increasing CuO content, d33 gradually
and CeO2 has been reported to greatly enhance the tem- decreases whereas Qm increases significantly. However, for
perature stability of the doped KNN ceramics and to improve CuO content lower than 1 mol%, both high Qm ( 323) and
its mechanical quality factor.154159 The incorporation of relatively high d33 (> 180 pC/N) were obtained. High-
such liquid phase sintering aids promotes densification with performance Nd-doped lead-free KNNLT piezoceramics
densities up to 97.5% theoretical. Liquid phase sintering were prepared by Bathelt et al.170 A large signal piezo-

results in reduced processing temperatures to as low as coefficient of d 33 ¼ 460 pm/V (E ¼ 2 kV/mm) was achieved
950 C, and yields d33 values of 180270 pC/N. Another for Nd content of 0.5 mol%. Lead-free piezoelectric ceramics
approach involved substitution of A- (Li þ , Ba 2þ , La 3þ , Bi 3þ , ( 1 xÞ( 0 . 9 8 K 0:5 N a 0:5 N b O 3 0 . 0 2 L i Ta O 3 Þx ( 0 . 9 6
etc.), and B- (Ti 4þ , Sb 5þ or Ta 5þ , etc.) sites in the ABO3 Bi0:5 Na0:5 TiO3 0.04BaTiO3 Þ [KNNLTBNTBT] were
structure of the KNN solid solution.160162 In spite of all prepared and studied by Yejing and Xiaowen.171 The addition
efforts, owing to the processing issues of KNN, it failed of BNTBT to KNNLT shifted the phase transition of Tc
to make an attractive contender for a PZT replacement. and Tot to lower temperatures, which contributed to the
However, the work by Saito et al.5 resurged much research on coexistence of orthorhombic and tetragonal phases at x ¼
this system. Since the publication of this paper, a great deal of 23 mol% and improved d33 ¼ 155 pC/N.
work on doping effects in KNN has been published. The
(K0.5Na0.5)NbO3LiSbO3 (KNNLS): The effect of LiSbO3
major contribution of this work was to show the modification
substitution on the KNN system was investigated by many
of the PPT, present in KNN by the addition of Li þ and Ta 5þ .
authors.172174 The addition of LiSbO3 to pure KNN results
Numerous compositionally engineered binary systems have
in shifting of the orthorhombic to tetragonal polymorphic
been explored to optimize the piezoelectric properties of
phase transition temperature down from 200 C to nearly
KNN materials. Nearly all of these approaches achieve
room temperature while increasing the room temperature d33
enhanced properties by shifting the Tot polymorphic phase
coefficient; reaching a maximum (d33 ¼ 250265 pC/N) at
transition temperature resulting in significant softening of the
approximately 5 mol% of LS content.172174 Zhang et al.174
piezoelectric properties (large d33 ); however this is achieved
studied the ð1 xÞKNNxLS composition, and showed that
at the cost of large temperature dependence of the piezo-
with x ¼ 0:052, considerable electromechanical coupling
electric response and poor stability of the poled domain state
factors of kp 27%, k33 62%, and k31 30%, and pie-
in most modified KNN compositions. Compositionally
zoelectric coefficients of d33 of 265 pC/N and d31 of
engineered KNN systems modified by LiTaO3 and LiSbO3
116 pC/N could be obtained. Similarly, Wu et al. showed
have been studied most intensively and are discussed in the
d33 ¼ 250265 pC/N at approximately 5 mol% of LiSbO3
following paragraphs.
content in KNN.173 The improvement in piezoelectric beha-
(K0.5Na0.5)NbO3LiTaO3(KNNLT): Solid solution of vior at room temperature was explained by a shift of the
KNN with tetragonal LiTaO3 exhibits a MPB between polymorphic phase transition from 200 C for the pure KNN
orthorhombic and tetragonal phases at 45 mol% of to approximately 35 C, thereby increasing the polarizability.
LiTaO3 accompanied with enhancement of piezoelectric Yang et al.172 reported that with increasing LS content, d33
properties (d33 coefficients have been reported in the range and kp values of the ceramics initially increased, however, for
200259 pC/N).10,163166 Hollenstein et al. reported quite higher LS concentration, the values began to decrease. In
high d33 300 pC/N and kt ¼ 52% for Li and Ta-substituted addition, dielectric study revealed that Tc is decreased and a
KNN ceramics, prepared using pressure-less sintering.6 A change from normal-ferroelectric to relaxor-type with
high d33 in the range 200259 pC/N was reported in the increasing LS content was observed. Recently, Palei et al.175
KNNLiTaO3 system.165 Additionally, Guo et al. observed reported on the properties of (1xÞ[K0:5 Na0:5 NbO3]x
an MPB between orthorhombic and tetragonal phases in [LiSbO3] system. They observed that the 0.95KNN0.05LS
ð1 xÞKNNxLT at x ¼ 5 to 6 mol% and achieved a d33 ceramics have better ferro- and piezoelectric properties
value of 200 pC/N and kp 36% in this MPB compo- with Pr ¼ 18:7 C/cm2, Ec ¼ 11:8 kV/cm, d33 ¼ 215 pC/N,
sition.10 Later, Saito and Takao reported their results on the kp ¼ 41:5%, and remnant strain ¼ 0:07%.
KNNLT system, exhibiting a d33 of 230 pC/N, kp 50:5% Effect of ions such as Ag þ , Nb 5þ , Ta 5þ , Bi 3þ , Cu 2þ ,
and a relative dielectric permittivity of 1256.166 The sig- Ca 2þ , etc. and combination of two or three ions in KNNLS
nificant enhancement in the piezoelectric properties of KNN ceramics have been investigated by many authors and
1330002-9
promising results were reported in Refs. 11 and 176187. substitutions of BiFeO3 and SrTiO3 in KNNLN ceramics
The effect of Ag þ content on the phase transition and elec- was studied.196 The 94.5(K0:5 Na0:5 ÞNbO34.5LiNbO3
trical properties of KNNLS ceramics were studied showing 0.5Sr TiO30.5BiFeO3 ceramics showed excellent piezo-
that for x ¼ 0:06, better piezoelectric and ferroelectric prop- electric properties of d15 ¼ 231 pC/N, d33 ¼ 155 pC/N, and
erties could be obtained: d33 ¼ 227 pC/N, kp ¼ 42.5% and d31 ¼ 70 pC/N.
Tc ¼ 368 C and Pr ¼ 21:9 C/cm2.188 The effects of ZnO,
KNNLTLS: In their work, Saito et al.5 reported that
CuO and MnO2 on the structure, dielectric and piezoelectric
with the addition of dopants such as lithium, tantalum, and
properties of KNNLS were investigated in Ref. 155. It was
antimony, high density samples of KNN can be achieved
reported that, for 1 mol% oxide dopants, KNNLS exhibits
with extremely high piezoelectric properties comparable to
\hard" piezoelectric properties: Qm value increased signifi-
typical actuator-grade PZT compounds. The optimization of
cantly with d33 93119 pC/N and Tc around 350 C.
this KNNLTLS system [(K0:44 Na0:52 Li0:04 Þ(Nb0:86 Ta0:10
Effects of sintering aid K4CuNb8O23 (KCN) on K0:5 Na0:5
NbO3LiSbO3 piezoceramics were studied by Liu et al.189 Sb0:04 ÞO3, the so-called LF4 composition] yielded a d33 of
KCN in addition to the KNNLS greatly improved the 300 pC/N. In the same work, the properties of the
Qm value. The ceramics with x ¼ 0:8 exhibited, Qm ¼ 192, LF4 composition were further enhanced by the reactive
d33 ¼ 135 pC/N, and kp ¼ 35:7%. The piezoelectric pro- template grain growth method, producing d33 values as high
perties of 1 mol% FeO-doped 0.95(K0:52 Na0:48 Þ NbO3 as 416 pC/N. The observed enhancement of the piezoelectric
0.05LiSbO3 ceramics were investigated, too.190 A high d33 coefficient was earlier attributed to an MBP between orthor-
value of 311 pC/N, with a relatively high kp of 42.0% was hombic and tetragonal phases. However, the authors them-
observed. selves and more recent studies indicated the temperature
dependence of the electromechanical properties near the

(K0.5Na0.5)NbO3LiNbO3 (KNNLN): The effect of Li room temperature and the existence of the orthorhombic
substitution in KNN compositions has been investigated tetragonal PPT near room temperature for both LF4 and
by several groups. Guo et al. first reported a large d33 of LF4T compositions.197 Later, Hagh et al.141 systematically
235 pC/N with a fairly high kp of 44% in ð1 xÞKNN studied the effect of varying processing parameters such as
xLiNbO3, x ¼ 0:06.11 Later, Du et al.191 optimized piezo- oxygen annealing and the purity of precursor materials. It was
electric, dielectric and ferroelectric properties for 0.94 shown that the samples prepared with high-purity raw ma-
(K0:5 Na0:5 ÞNbO30.06LiNbO3 ceramics with d33 ¼ 215 pC/ terials and sintered under oxygen flow exhibited much higher
N, kp ¼ 41:0%, kt ¼ 48:0%, Qm ¼ 80, Pr ¼ 20:0 C/cm2, relative permittivity as well as a high d33 of 350 pC/N.
Ec ¼ 13:4 kV/cm and Tc ¼ 450 C. In their report on Hagh et al. also studied the effect of the additive CuO in
KNNLN, Wang and Li192 reported highly enhanced pie- KNNLTLS composition,161 where an increase in grain
zoelectricity in bulk ceramics prepared by domain engineer- size and a change in growth behavior was observed. More-
ing. Aging and re-poling induced enhancement of over, the addition of CuO stabilized the orthorhombic phase
piezoelectricity was investigated and a high d33 of 324 pC/N through shifting the Tot to a higher temperature while
was obtained for the sample with x ¼ 0:080, after a second causing no change in Tc .
poling treatment following the first poling and room tem-
perature aging for two months. (K0.5Na0.5)NbO3(Bi0.5Na0.5)TiO3KNNBNT: Several
An addition of BNT to KNNLN ceramics shifted the different MPBs have been reported in the system of solid
polymorphic phase transition to below room temperature and solution of BNT with KNN. In the BNT-rich system an MPB
expanded its usable temperature range.193 (1xÞKNNxLN at 67 mol% KNN between a rhombohedral FE phase and a
nanoparticles with the mean particle size of about 2030 nm tetragonal AFE phase was reported.198 Addition of KNN
were prepared by solgel route using Nb2O5 as Nb made the material more antiferroelectric in its behavior,
source.194 Optimized parameters, such as d33 ¼ 170 pC/N however, it led to a much higher unipolar strain.198 On the
and kp ¼ 40:0% were achieved in the 0.90KNN0.10LN contrary, an MPB was reported at 23% BNT between fer-
system. An interesting study related to adding poly- roelectric orthorhombic and tetragonal phases in the KNN
vinylpyrrolidone (PVP) in the starting raw materials to be an rich system.199 A high d33 ¼ 195 pC/N and kp of 43% was
effective method for obtaining stoichiometric KNNLN was reported in the KNN rich system.
proposed by Tan et al.195 0.94KNN0.06LN ceramics were Solid solution of KNN with metal titanates, such as
prepared by solid-state reaction process modified by introdu- CaTiO3, BaTiO3, SrTiO3, etc., has also been explored by
cing PVP of different molecular weights ranging between 55 many groups and various studies have been reported on their
and 1300 K. Results revealed that the addition of PVP sup- electromechanical properties as a function of titanate end
pressed the loss of alkali ions and promoted the perovskite member content. Introducing metal titanates in KNN, aids in
phase formation. Ceramic samples obtained with PVP 55 K densification of the KNN samples via formation of a liquid
addition under normal air sintering exhibited an improved phase and results in large-grain microstructure.200204
d33 ¼ 140 pC/N and kp ¼ 35:0%. The effect of the Ahn et al. compared different sintering conditions for
1330002-10
0.95KNN0.05BT and found improved piezoelectric prop- constants for six langasite family crystals Ca3TaGa3Si2O14 ,
erties for this system.205 Guo et al. reported an MPB in this Sr3TaGa3Si2O14 , Ba3TaGa3Si2O14 , La3Ta0:5 Ga5:5 O14 ,
system at 6 mol% BT and another transition to a cubic La3Nb0:5 Ga5:5 O14 , La3Ga5SiO14 were reported by Dudka
phase at 20 mol% BT.206 KNNBT systems were also pre- using the density-functional perturbation theory.217 Among
pared with Li doping that yielded a piezoelectric constant all, LGS single crystals have been reported to exhibit high
> 200 pC/N at MPB compositions which were tetragonal- piezoelectric and electromechanical properties, with d11 values
rich.207 Modification of the KNN system by 1 wt.% CaTiO3 three times larger than quartz. Furthermore, nonoccurrence
significantly reduced the temperature dependence of the of phase transformation prior to its melting temperature
piezoelectric response in the range 50 C to 200 C, with (1470 C), makes it a promising candidate for high tem-
considerable piezoelectric properties (d33 ¼ 210 pC/N).208 perature sensing applications.218221 Dielectric, elastic and
However, with increasing CaTiO3 and BaTiO3 content, the piezoelectric parameters "ij , dij and sij of LGS single crystals
ferropara transition peak broadened with a diffuse phase have been measured by the resonance-antiresonance
transition from tetragonal to cubic phase, indicating a method.222 Coupling coefficients k12 , k26 and kt were deter-
change from a normal ferroelectric to a relaxor type. In mined as 11.8, 15.0, and 7.56%, respectively. Takeda et al.223
general, the addition of titanates, regardless of the A-site studied the effect of Al in LGS crystals (La3Ga5x Alx SiO14
elements, showed dramatic decrease in Tc and Tot transition (0 x 1)) and reported an increase of 1.3% in the piezo-
temperatures, with Tot showing no dependence on the A-site electric modulus jd11 j with the increasing Al content up to 1.0.
element.209 Chang et al.210 observed that adding Ca 2þ and Substitution of La by Pr (Pr3Ga5SiO14 Þ, Nd (Nd3Ga5
Sr 2þ to KNN promotes densification, decrease Tc , and SiO14 Þ improved the piezoelectric properties.224 Iwataki et al.
improve the electrical properties. There have been several clarified the reason behind improvement of the piezoelectric
reports on the incorporation of bismuth perovskites into solid properties with the increase in ionic radius of the rare-earth
solutions with KNN. The solid solution BiScO3KNN ions Pr, La and Nd.225 Further Araki et al.226 provided the
yielded d33 ¼ 253 pC/N and high Curie temperature origin of piezoelectricity for langasite A3Ga5SiO14 (A ¼ La
Tc ¼ 351 C.211 Bismuth ferrite solid solutions have also and Nd) by studying the crystal structure under high pressure.
been investigated in KNN ceramics.196 A complex KNN Recently, it has been reported that Ca3TaGa3Si2O14
solid solution with BiFeO3, SrTiO3 and lithium has been (CTGS) crystals with a fully ordered structure exhibit greatly
reported with d33 ¼ 155 pC/N and Tc ¼ 370 C.212 In ad- improved resistivity as well as thermal stability of dielectric
dition, number of reports exists on the effect of low amount of and electromechanical properties.227,228 Yu et al.229 studied
alkaline earth dopants, (0.5 at.%) Mg 2þ , Ca 2þ , Sr 2þ, and the Ca3TaGa3Si2O14 (CTGS) crystals, a promising material
Ba 2þ on KNN solid solution’s synthesis, sinterability, and for high temperature sensors. They obtained optimal values
functional response of corresponding ceramics.213215 of electromechanical coupling k26 (18.9%) and piezoelectric
coefficient d26 (11:5 pC/N).
Langasites: Crystals in the langasite family (general for-
mula A3BC3D2O14 ; A and B represent a decahedral and an BiAlO3 and their solid solutions: Recently, BiAlO3 (BA)
octahedral site coordinated by eight and six oxygen ions, has garnered much attention due to its excellent ferroelectric
respectively while both C and D represent tetrahedral sites properties. Theoretical calculations predicted a perovskite-
coordinated by four oxygen ions), generally, do not undergo like rhombohedral symmetry at room temperature for BA
phase transitions prior to their respective melting points with very large spontaneous polarization of about 76 C/cm2
(1300 C1500 C) making them ideally suited for high and a Curie temperature of about 800 K.230 Zylberberg et al.
temperature sensing applications. High temperature sensors synthesized BA and confirmed its ferroelectric nature and
require piezoelectric materials with a low temperature obtained a Tc > 520 C.231 However, its poor thermal stab-
dependence of dielectric, piezoelectric properties, and a high ility and the extreme conditions that are required for its
electrical resistivity, typically >1 10 6 cm. Piezoelectric synthesis hinders its practical applications in its pure form.
sensors commonly utilize quartz (SiO2 Þ and lithium niobate Therefore, attempts were made to stabilize BA either by using
(LiNbO3 Þ; however, the maximum operating temperature of high pressure techniques or solid-solutions with other stable
quartz-based devices is limited by crystal twinning around perovskite materials like BNT.
350 C, while the low resistivity of lithium niobate limits their Yu and Ye synthesized a (1xÞ(Bi0:5 Na0:5 ÞTiO3xBiAlO3
implementation to less than 600 C. Studies showed that (BNTBA) ceramic system and reported remarkable ferro-
langasite family compounds are characterized by an inter- electric and piezoelectric properties when compared to pure
esting combination of piezoelectric, luminescence, laser, and BNT ceramics.232 Watanabe et al. fabricated (Bi0:5 Na0:5 Þ
electromechanical characteristics. TiO3BiAlO3 ferroelectric ceramics and investigated their
The Ca3Ga2Ge4O14 compound, which served as a starting electrical properties.233 A high value of d33 ¼ 93 pC/N and
point for the family of langasite La3Ga5SiO14 (LaLGS), the electromechanical coupling factor, k33 ¼ 0:41 were

was synthesized at the Faculty of Physics, Moscow State obtained. Normalized strain d 33 ð¼ Smax =Emax Þ at 60 kV/cm
University.216 Elastic and electromechanical (piezoelectric) at the maximum field-induced strain was 122.2 pm/V.
1330002-11
ð1 xÞ(Bi0:5 Na0:5 ÞTiO3xBiAlO3 (BNTBA, 0 x environment, utilization of lead-free materials for piezo-
0.1) ceramics were also synthesized by Ullah et al.234 A electric energy harvesting is the most promising application.
rhombohedral to pseudocubic phase transition was observed In the following section, we briefly introduce this topic.
at x ¼ 0:075 and maximum values for the electric field-
induced strain (S ¼ 0:13%) and dynamic piezoelectric coef-

ficient (d 33 ¼ 163 pm/V) were obtained at this composition. 2.3. Piezoelectric energy harvesting
The effect of BA concentration on the dielectric and piezo- Energy harvesting is the process by which energy is derived
electric properties of lead-free (Bi0:5 Na0:5 Þ0:94 Ba0:06 TiO3
from external sources (e.g., solar power, thermal energy, wind
piezoelectric ceramics were also investigated.235 The com-
energy, mechanical vibrations, and kinetic energy), captured
position with x ¼ 0:020 showed maximum Pr ¼ 30 C/cm2,
and stored. Energy harvesting has been around for centuries
d33 ¼ 188 pC/N and kp ¼ 34:4%. Lead-free piezoelectric
in the form of windmills, watermills and passive solar power
ð1 xÞ(Bi0:5 (Na0:75 K0:25 Þ0:5 TiO3 ÞxBiAlO3(BNKT25BA,
systems. The objective of a power harvesting device is to
0 x 0:10) ceramics were synthesized and studied by
capture the untapped energy surrounding a system which is
Ullah et al.236 In particular, a large electric field-induced
normally lost, and convert it into usable energy for the
strain (S ¼ 0:29%) and a normalized strain (d 33 ¼ 484 pm/V)
electrical device. Recently, technologies such as biomecha-
were observed at x ¼ 0:025, near the tetragonalpseudocubic
nical, piezoelectric and pyroelectric energy harvesting are
phase boundary. Further, the effects of potassium concen-
attracting world interest. Vibration-based mechanical energy
tration (x) on the structure and electrical properties of the

is the most ubiquitous and accessible energy source in the
0.975[Bi0:5 (Na1x Kx Þ0:5 TiO3]0.025BiAlO3 piezoelectric
surroundings. For random vibrations with frequencies from
ceramics were also investigated.237 A large electric field
hundreds Hz to kHz, the available energy density is within

induced strain (S ¼ 0:33%) and a corresponding normalized
the range of a few hundred microwatt to milliwatts per cubic
strain (d 33 ¼ 533 pm/V) were obtained on the tetragonal side
centimeter.242244 Therefore, harvesting this type of energy
of the MPB composition (x ¼ 0:22).
Lead-free (1 x)Bi0:5 (Na0:78 K0:22 Þ0:5 TiO3x(Bi0:5 La0:5 Þ offers a great potential for remote/wireless sensing, charging
AlO3 (BNKTBLA) piezoelectric ceramics with x ranging batteries, and powering electronic devices.245250 Devices to
from 0 to 0.030 were synthesized and studied.238 A large harvest the vibration-based energy have been successfully
electric field-induced strain (S ¼ 0:40%) and a corresponding built on three different principles: piezoelectric transduction,
normalized strain (d 33
¼ 579 pm/V ) were observed under electrostatic and electromagnetic.251254 Williams and
70 kV/cm at a composition of x ¼ 0:010. Lee et al.239 Yates255 proposed a device, which generated electricity when
investigated the electrical properties and electric field- embedded in a vibrating environment. An electromagnetic
induced strain of Bi0:5 Na0:5 TiO3 (BNT) single particle-added transducer was chosen for their evaluation. For a typical
Bi0:5 (Na0:75 K0:25 Þ0:5 TiO3BiAlO3 (BNKTBA) ceramics. device they predicted a power generation of 1 W at an ex-
Strains of 0.27% and 0.29%, for 0.94BNKT0.06BA with citation frequency of 70 Hz, and 0.1 mW at 330 Hz (assuming
10% BNT and 0.93BNKT0.07BA with 20% BNT were a deflection of 50 m). Of the three modes of vibration har-
observed, respectively. vesting, the most promising technique is a mechanical energy
Effects of BA on the structure and electrical properties of harvesting e.g., by piezoelectric components where defor-
(Na0:5 Bi0:5 Þ0:94 Ba0:06 TiO3 (BNBT6) ceramics were investi- mations produced by different means is directly converted to
gated by Fu et al.240 The composition with x ¼ 0:0225 electrical charge via direct piezoelectric effect.249,251,256,257
showed a high Pr ¼ 42:5 C/cm2 with d33 ¼ 204 pC/N Subsequently the electrical energy can be regulated or stored
and kp ¼ 0:3292. Further, (Bi0:5 Na0:5 Þ0:94 Ba0:06 TiO3Bi0:5 for further use. Piezoelectric vibration harvesting is attractive
(Na0:82 K0:18 Þ0:5 TiO3BiAlO3 lead-free piezoelectric cer- mainly due to the simplicity of piezoelectric transduction and
amics were investigated by Fu et al.241 For composition with the relative ease of implementation of piezoelectric systems
x ¼ 0:030, a high d33 ¼ 217 pC/N, kp ¼ 0:308 and Pr ¼ into a wide variety of applications as compared to electro-
33:8 C/cm2 were obtained. static or electromagnetic methods.258,259 In addition to the
The above identified lead-free materials with significant advantage of being smaller and lighter, the piezoelectrics
recent advances, find a range of applications including have three times higher energy density as compared to their
transducer, actuator, bio-compatible microelectromechanical counterparts electrostatic and electromagnetic.249 Unlike
systems (MEMS), etc. Piezoelectric ceramics also hold great electrostatic transduction, which requires the application of
potential for efficient energy harvesting and undoubtedly, lead an initial voltage to produce usable energy, piezoelectric
free is a promising solution for a cleaner sustainable energy material inherently generates a direct voltage when strained.
source in future. Moreover, by virtue of the absence of lead, Additionally, where electromagnetic harvesting systems
these new lead-free materials signify a safer disposal of become increasingly difficult to fabricate at the micro-scale
electronic equipment. With the recent advances in MEMS and and electrostatic systems being generally restricted to the
NEMS technology; the rapidly growing demand for portable micro-scale, piezoelectric materials can easily be fabricated
electronics, wireless sensors and concern over cleaner as bulk materials at the macroscale or deposited as thin-films
1330002-12
at the micro-scale.260 Consequently, investigations on pie- and foldable power sources, ideal for applications like
zoelectric materials for scavenging energy from ambient vi- implantable biomedical sensors.276,277 It will be not out of
bration sources have recently witnessed a worldwide surge. place to mention that to generate high voltage and power a
Quoting Markys Cain, Knowledge Leader at NPL, UK: \The material with high (d g) product is considered most reliable.
energy harvesting market was worth $605 million in 2010 For application in energy harvesting devices, piezoelectric
but is predicted to reach $4.4 billion by the end of this ceramics should possess a high energy density i.e., the ma-
decade" — indicating a huge potential for piezoelectric terial should have a high transduction coefficient (d g). It has
energy harvesters.261 been reported that at low frequencies, far from the resonance,
The concept of utilizing piezoelectric materials for energy a piezoelectric behaves like a parallel plate capacitor and the
generation have been studied by many researchers over the electric energy per unit volume available under ac stress ex-
past few decades and have been developed widely for citation is given as249,278,279
different energy consumption and application areas. Hausler 2
1 F
and Stein262 investigated the ability to generate energy from U ¼ ðd gÞ ;
the expansion and contraction of the rib cage during breath- 2 A
ing of a dog. A prototype of the power harvesting system was where d is the piezoelectric strain constant and g is the piezo-
constructed using polyvinylidene fluoride (PVDF) film that electric voltage constant. Thus for a given material of fixed
was demonstrated to produce a peak voltage of 18 V (corre- area and thickness, a material with high (d gÞ product and
sponding to a power of about 17 W). Another investigation
high g constant will generate high voltage and power when

into the ability to use piezoelectric materials for power har- the piezoelectric ceramic is directly employed for energy
vesting from the motion of humans and animals was per- harvesting and sensing. Recently, the condition for obtaining
formed by Ramsey and Clark,263 who studied the ability to large magnitude of d g was derived to be as279,280
power a MEMS device. In another study, a piezoelectric
jdj ¼ " n ;
energy harvester based on impulse type excitations has been
developed for active RFID identification.264 Moreover, piezo- where " is permittivity of the material and n is a material
harvester with externally leveraged mechanism for force constant having lower limit of 0.5. It has been found that for
amplification was reported to be able to generate mean power all practical polycrystalline piezoelectric ceramic materials
of 0.4 mW from backpack movement.265 Sodano et al.266 the magnitude of n lies in the range of 1.11.30. For
formulated a model of a power harvesting system that con- example: quartz single crystal (d33 ¼ 2:3 pC/N, "33 ="0 ¼ 5,
sisted of a cantilever beam with piezoelectric patches g33 ¼ 51:9, n ¼ 1:124), PVDF piezoelectric polymer
attached. (d33 ¼ 33 pC/N, "33 ="0 ¼ 13, g33 ¼ 286:7, n ¼ 1:054)281
More recently, energy harvesting systems based on the and lead-based relaxor piezoelectric PZN7%PT single
transformation of vibrations into electrical energy are crystals (d33 ¼ 2500 pC/N, "33 ="0 ¼ 6; 700, g33 ¼ 42:1,
increasingly being used for niche applications due to the re- n ¼ 1:190).282
duction in power consumption of modern day electronic Owing to its very high electromechanical coupling ability,
systems-wireless sensing/data transmission. Typically these PZT has been the most commonly used piezoelectric ceramic.
applications involve extracting energy at remote or isolated However, since it is extremely brittle material there is
locations where local long term power is unavailable. The limitations to the strain that it can safely withstand without
advances in low power electronics, and wireless sensor net- being damaged.256,283 Alternatively, polyvinylidenefluoride
works (WSNs) in particular, have motivated numerous (PVDF), a common piezoelectric polymer, is more flexible
researches in the field of energy harvesting in the last and can be employed in energy harvesting applications.283
decade.245,248,267 Thousands of spatially distributed wireless The pioneering work by Zhong L. Wang and his Nano
sensors can be developed which can be embedded virtually Research Group at the Georgia Institute of Technology, USA,
anywhere in civil structures, bridges, or in the human body. has greatly influenced the current research efforts in the
WSN technology has gained increasing importance in conversion of nanoscale mechanical energy into usable
industrial automation,268,269 structural health monitoring,270 electrical energy using nanogenerators. They introduced
healthcare,271 agriculture,272 and civil and military appli- piezoelectric nanogeneration (converting nanoscale mechan-
cations.273275 Further energy harvesting is the most cost- ical energy into electrical energy) by means of piezoelectric
effective and environment friendlier way of overcoming the zinc oxide nanowire (NW) arrays.284 In their work, the
challenges currently presented by finite life power sources aligned NWs were deflected with a conductive atomic force
(like batteries) commonly used in WSNs. Piezoelectric microscope tip in contact mode.284 Since then, piezoelectric
energy harvesting devices in the form of MEMS generators semiconductor materials such as ZnO,285287 indium nitride
or nanogenerators are a novel technology and therefore are (InN),288,289 gallium nitride (GaN),290,291 zinc sulphide
a reliable alternative energy source for powering wireless (ZnS),292 cadmium sulphide293 and piezoelectric insulator
sensor devices. Unlike conventional MEMS generators, materials, such as PVDF,294 BaTiO 2953 and PZT,
296
have been
nanogenerators have an added advantage of being flexible studied for potential electrical power generation. Chen
1330002-13
3
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4
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Homma, T. Nagaya and M. Nakamura, Lead-free piezoceramics,
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7
generators on plastic substrates that generated an output vol- Y. Saito and H. Takao, High performance lead-free piezoelectric
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and a power density of 7 mW/cm3. This subject will assume 8
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9
3. Conclusion R. Wang, R. J. Xie, K. Hanada, K. Matsusaki, H. Bando, T.
Sekiya and M. Itoh, Phase diagram of the (Na0:5 K0:5 )NbO3

The properties of various lead-free piezoelectric materials ATiO3 solid solution, Ferroelectrics 336, 39 (2006).
10
belonging to the bismuth layer-structured (BLSF) and per- Y. Guo, K. Kakimoto and H. Ohsato, (Na0:5 K0:5 )NbO3LiTaO3
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11
the presently available nonlead piezoceramics can compete Y. Guo, K. Kakimoto and H. Ohsato, Phase transitional behavior
with PZT, they can be considered as alternatives to PZT for and piezoelectric properties of (Na0:5 K0:5 )NbO3LiNbO3 cer-
special applications. The families of potassium sodium nio- amics, Appl. Phys. Lett. 85, 4121 (2004).
12
G. Z. Zang, J. F. Wang, H. C. Chen, W. B. Su, C. M. Wang, P. Qi,
bate, bismuth sodium titanate have the advantages of low
B. Q. Ming, J. Du, L. M. Zheng, S. J. Zhang and T. R. Shrout,
dielectric constants, high coupling coefficient and higher
Perovskite (Na0:5 K0:5 Þ1x (LiSb)x Nb1x O3 lead-free piezo-
mechanical strength in general than lead containing ceramics ceramics, Appl. Phys. Lett. 88, 212908 (2006).
that make them suitable for high frequency transducers. Apart 13
S. B. Lang, W. Zhu and L. E. Cross, Piezoelectric and pyro-
from being nontoxic, their lower acoustical impedance makes electric properties of (K0:5 Na0:5 Þ1x (Nb1y Tay )O3 ceramics,
them suitable for medical imaging. While, BLSF ceramics Ferroelectrics 336, 15 (2006).
14
seem to be suitable candidates as piezoelectric sensors for H. Takao, Y. Saito, Y. Aoki and K. Horibuchi, Microstructural
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and doping schemes will have to be explored for identifying ceramics with a sintering Aid of CuO, J. Am. Ceram. Soc. 89,
extraordinary properties for device fabrication. As the pro- 1951 (2006).
15
gress in the development of the power harvesting continues it S. Tashiro and K. Ishii, Grain size and piezoelectric properties of
(Ba, K, Na)NbO3 lead-free ceramics, J. Ceram. Soc. Jpn. Int. Ed.
will be important to standardize the characterization methods
114, 386 (2006).
so that a prominent lead-free system could be realized. 16
M. Matsubara, K. Kikuta and S. Hirano, Piezoelectric properties
of (K0:5 Na0:5 )(Nb1x Tax )O3 K5:4 CuTa10 O29 ceramics, J. Appl.
Phys. 97, 114105 (2005).
17
M. Matsubara, T. Yamaguchi, W. Sakamoto, K. Kikuta, T. Yogo and
Acknowledgments
S. Hirano, Processing and piezoelectric properties of lead-free
The authors I. C. and N. P. would like to thank the Portuguese (K,Na) (Nb,Ta) O3 ceramics, J. Am. Ceram. Soc. 88, 1190 (2005).
18
foundation FCT through their grants SFRH/BPD/81032/2011 J. Yoo, J. Hong, H. Lee, Y. Jeong, B. Lee, H. Song and J. Kwon,
and SFRH/BPD/71289/2010, respectively. Financial support Piezoelectric and dielectric properties of La2O3 added Bi(Na, K)
from FCT through the projects PTDC/FIS/108025/2008 and TiO3SrTiO3 ceramics for pressure sensor application, Sens.
PTDC/CTM-CER/115085/2009 is also acknowledged. Actuat. A Phys. 126, 41 (2006).
19
S. H. Choy, X. X. Wang, H. L. W. Chan and C. L. Choy, Study of
compressive type accelerometer based on lead-free BNKBT
piezoceramics, Appl. Phys. A 82, 715 (2006).
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Lead-Free Piezoelectrics Current Status and Perspe

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Review

JOURNAL OF ADVANCED DIELECTRICS

Lead-free piezoelectrics: Current status and perspectives

recent developments in the area of piezoelectric energy harvesting is also encompassed.

1. Introduction remain in the range 0.11 kHz.1 Therefore, much of

2. Lead-Free Piezoelectric Materials

sensors, filters and ceramic resonators with large figures of

temperature coefficient of resonance frequency). Moreover,

still low. Structural engineering approaches by several groups

an exceptional change. Xiao et al. were able to increase the

electricity is expected in the BNT-based solid solutions with a

character over a relatively wide temperature range. Zhou

at the MPB were investigated. Dense BNTBZT ceramics

BNTBZT binary system, a high piezoelectric constant,

Table 2. Piezoelectric properties of BKTBT10, 20 and 30 prepared by ordinary

BKTBT10 BKTBT20 BKTBT30

OF RTGG OF RTGG OF RTGG

k33 0.35 0.37 0.36 0.33 0.38 0.38

properties (d33 in the range 140192 pC/N) of the MPB

ever, LT modification induced a ferroelectric-nonpolar phase

Source: Copyright 2005, reproduced with permission from Elsevier.

(d33 ¼ 133 pC/N, kp ¼ 26:0% and kt ¼ 57:0%Þ. From these

dependence of the electromechanical properties near the

tration (x) on the structure and electrical properties of the

hundreds Hz to kHz, the available energy density is within

high g constant will generate high voltage and power when

Sekiya and M. Itoh, Phase diagram of the (Na0:5 K0:5 )NbO3

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