ARTICLE IN PRESS

Journal of Physics and Chemistry of Solids 69 (2008) 1996–2003

www.elsevier.com/locate/jpcs

Effect of bismuth deficiency on structure and electrical properties

of (Na0.5Bi0.5)0.93Ba0.07TiO3 ceramics
Qing Xua,, Yu-Heng Huanga, Min Chena,b, Wen Chena, Bok-Hee Kimb, Byung-Kuk Ahnb
a
School of Materials Science and Engineering, Wuhan University of Technology, Wuhan 430070, People’s Republic of China
b
Faculty of Advanced Materials Engineering, Chonbuk National University, Chonju 561756, Republic of Korea
Received 1 August 2007; received in revised form 13 January 2008; accepted 15 February 2008

Abstract

(Na0.5Bix)0.93Ba0.07TiO3 (x ¼ 0.500–0.492) ceramics were prepared by a citrate method, and the structure and electrical properties of
the ceramics were investigated with respect to the amount of Bi deficiency. It was detected that the Bi deficiency had a considerable
impact on the crystal structure and microstructure. The inspection of both the temperature dependence of the dielectric properties (free
permittivity eT33/e0 and dielectric loss tan d) and the evolution of the polarization–electrical field (P–E) hysteresis loops with measuring
temperature suggests that the Bi deficiency served to increase the depolarization temperature (Td). The Bi deficiency led to an increase in
the coercive field (Ec) and mechanical quality factor (Qm) together with a decrease in the remanent polarization (Pr) and piezoelectric
constants (d33). The variation of the structure and electrical properties with Bi deficiency amount was qualitatively interpreted in terms of
the formation of Bi and oxygen vacancies in the Bi-deficient specimens. This research indicates the importance of adequately controlling
Bi stoichiometry of (Na0.5Bi0.5)0.93Ba0.07TiO3 ceramics in obtaining the desired ferroelectric and piezoelectric properties.
r 2008 Elsevier Ltd. All rights reserved.

Keywords: A. Ceramics; B. Chemical synthesis; D. Electrical properties; D. Ferroelectricity; D. Piezoelectricity

1. Introduction considerable attention on account of the existence of a

In the past decades, there has been a continuous research
effort towards lead-free piezoelectric materials as potential
alternatives to the widely used lead zirconate titanate
(PZT)-based piezoelectric ceramics. Sodium bismuth tita-
nate, (Na0.5Bi0.5)TiO3 (NBT), is a perovskite-type (ABO3)
ferroelectric with a relatively large remanent polarization
(Pr ¼ 38 mC/cm2) at room temperature and a relatively
high Curie temperature (Tc ¼ 320 1C) [1]. Due to its strong
ferroelectricity at room temperature, NBT has been
considered to be a promising candidate material for lead-
free piezoelectric ceramics. However, pure NBT suffers
from its high coercive field (Ec ¼ 73 kV/cm), making it
difficult in obtaining the desired piezoelectric properties.
To solve this problem, varieties of NBT-based solid
solutions have been developed [2–7]. Among them,
(Na0.5Bi0.5)1xBaxTiO3 (NBT–BT) system has attracted
Corresponding author. Tel.: +86 27 87863277; fax: +86 27 87864580.
E-mail address: xuqing@whut.edu.cn (Q. Xu).
rhombohedral–tetragonal morphotropic phase boundary
(MPB) near x=0.06. Compared with pure NBT, the
NBT–BT compositions near the MPB offer obviously
reduced coercive fields and appreciably improved piezo-
electric properties [2,8].
Among the constituents of PZT-based ceramics, Pb2+
plays an exceptionally important role on the ferroelectric
and piezoelectric properties, related to the onset of
hybridization between Pb-6p and O-2p orbitals and large
displacement of Pb2+ in response to strain [9]. Bi3+ has an
identical valence shell electron configuration (6s26p0) to
that of Pb2+. It has been considered that the ferroelec-
tricity of NBT system materials is attributable to
(Na0.5Bi0.5)2+ complex ions, especially Bi3+ ions, at the
A site of the perovskite structure [10,11]. Research results
on NBT crystals revealed that the volatilization of Bi
during crystal growth caused a deviation in chemical
stoichiometry, which consequently affected the structure
and physical properties of the crystals [12,13]. Considering
the volatility of Bi at high temperatures, it is of great

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doi:10.1016/j.jpcs.2008.02.009
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Q. Xu et al. / Journal of Physics and Chemistry of Solids 69 (2008) 1996–2003
importance to examine the influence of Bi deficiency on the
structure and electrical properties of NBT system ceramics.
There have been several previous researches concerning
nonstoichiometry issue of NBT system ceramics, involving
the role of (Na0.5Bi0.5)2+ nonstoichiometry, Bi3+ excess
and Ti4+ nonstoichiometry on the electrical properties,
respectively [8,14,15]. However, the effect of Bi deficiency
on the structure and electrical properties of NBT–BT
ceramics with compositions near the MPB has not been
given sufficient consideration. This thus warrants further
research on the topic from the viewpoint of providing a
guideline to adequately controlling the composition and
preparation process of the ceramics.
In this work, (Na0.5Bi0.5)0.93Ba0.07TiO3 was selected as a
representative of MPB compositions in the NBT–BT
system. In continuation of our earlier research regarding
the syntheses of the NBT–BT system by a citrate method
[16], (Na0.5Bix)0.93Ba0.07TiO3 (x ¼ 0.500–0.492) ceramics
were prepared by the method. Moreover, the structure and
electrical properties of the ceramics were investigated with
regard to the amount of Bi deficiency.
2. Experimental
The powders with the nominal composition of
(Na0.5Bix)0.93Ba0.07TiO3 (x ¼ 0.500–0.492) were synthe-
sized by a citrate method. Reagent-grade NaNO3,
Bi(NO3)3  5H2O, Ba(NO3)2, tetrabutyl titanate and citric
acid were used as starting materials. Tetrabutyl titanate
was first dissolved into a citric acid solution and various
nitrates were then added, followed by stirring to yield a
transparent aqueous solution. The mole ratio of citric acid
to the total metal cation content was 1.25. The precursor
solution was heated to form a sol and subsequently a gel.
The resulting gel was pulverized and calcined at 600 1C for
1 h in air. The details of the synthesis process have been
described elsewhere [16]. The calcined powders were
uniaxially pressed under a pressure of 300 MPa into discs
of 19 mm diameter and 1 mm thickness. The discs were
embedded into pre-prepared powder with similar composi-
tion in a sealed crucible and sintered at 1150 1C for 2 h
in air.
The phase purity of calcined powders and crystal
structure of ceramic specimens were examined by a Philips
X’pert PBO X-ray diffractometer using Cu Ka radiation.
The morphology of calcined powders was observed at a
Hitachi S-4700 field emission scanning electron microscope
(FESEM). The microstructure of ceramic specimens was
investigated by a Jeol JSM-5610LV scanning electron
microscope (SEM) using polished and thermally etched
surfaces. The ceramic specimens were polished to ensure
surface flatness and painted with silver paste on both
surfaces as electrodes for measuring electrical properties.
The specimens were poled in a silicon oil bath at 60 1C
under 3.0 kV/mm for 15 min. The temperature dependence
of dielectric properties (free permittivity eT33/e0 and
dielectric loss tan d) was measured using the poled speci-
1997
mens by a TH2818 automatic component analyzer
(0.02–300 kHz) with a programmable furnace at 10 kHz
upon heating with a heating rate of 1 1C/min. The
piezoelectric constant (d33) was measured using a quasi-
static d33 meter based on the Berlincourt method at 110 Hz.
The electromechanical coupling factor (kp) and mechanical
quality factor (Qm) were measured by the resonance–anti-
resonance method using a HP4294 impedance analyzer.
The polarization–electrical field (P–E) hysteresis loop was
measured at varied temperatures by a radiant precision
workstation based on a standard Sawyer–Tower circuit at
50 Hz.
3. Results and discussion
Fig. 1 shows the X-ray diffraction (XRD) patterns of the
calcined powders. A perovskite phase was certified for
the powders and no secondary phase can be found within
the sensitivity of XRD. Fig. 2 shows typical morphology
of the calcined powders. One can observe fine and uniform
particles around 100 nm.
XRD analysis identified a pure perovskite structure for
the ceramic specimens. Fig. 3 shows the XRD patterns of
the ceramic specimens in the 2y ranges of 38–421 and
45–481, respectively. A rhombohedral (0 0 3)/(0 2 1) peak
splitting and a tetragonal (0 0 2)/(2 0 0) peak splitting were
detected for the specimen with x ¼ 0.500. It characterizes a
coexistence of rhombohedral and tetragonal phases, which
is consistent with the nature of the specimen with a MPB
composition [2,8]. In the 2y range of 38–421 (Fig. 3a), the
rhombohedral splitting keeps evident until x ¼ 0.496 and
then the two peaks tend to combine into a single peak with
further increasing the Bi deficiency amount. A basically
symmetrical single peak appears at x ¼ 0.492, assignable to
tetragonal (1 1 1) peak. In the 2y range of 45–481 (Fig. 3b),
one can see a distinct tetragonal (0 0 2)/(2 0 0) peak splitting
when xX0.496 and an obscure tetragonal (0 0 2)/(2 0 0)
splitting is still distinguishable at higher Bi deficiency
Fig. 1. XRD patterns of calcined powders.
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1998 Q. Xu et al. / Journal of Physics and Chemistry of Solids 69 (2008) 1996–2003

Fig. 2. FESEM micrographs of the calcined powders with (a) x ¼ 0.500 and (b) x ¼ 0.495.

Fig. 3. XRD patterns of ceramic specimens in the 2y ranges of (a) 38–421 and (b) 45–481.
 ARTICLE IN PRESS
Q. Xu et al. / Journal of Physics and Chemistry of Solids 69 (2008) 1996–2003
Fig. 4. SEM micrographs of the ceramic specimens with (a) x ¼ 0.500, (b) x ¼ 0.496, (c) x ¼ 0.495 and (d) x ¼ 0.492.
amounts. Additionally, it can be noticed that the XRD
peaks progressively shift to higher diffraction angle
directions with increasing Bi deficiency amount. These
changes indicate an influence of the Bi deficiency on the
crystal structure, which can be tentatively explained with
respect to the defects in the specimens. It is plausible that
the Bi deficiency design in the present work caused Bi
vacancies at the A site of the perovskite structure. For
charge compensation purposes, oxygen vacancies were
created to maintain an overall electrical neutrality. The
presence of these vacancies resulted in a lattice distortion
and unit cell shrinkage. It is rational to deduce that the
lattice distortion and unit cell shrinkage would become
pronounced with increasing Bi deficiency amount. The
XRD peak shift to higher diffraction angle directions
agrees well with a decrease in the dimension of the
unit cells. From the viewpoint of crystal chemistry, the
increase in the magnitude of the lattice distortion allowed
a change in the symmetry of the unit cells. This is
presumably responsible for the variation tendency in the
crystal structure from a rhombohedral–tetragonal phase
coexistence to a tetragonal symmetry with increasing Bi
deficiency amount.
1999
Fig. 4 shows SEM micrographs of the ceramic specimens
with various amounts of Bi deficiency. There is a change in
the grain size and shape with Bi deficiency amount.
Compared with the specimen with x ¼ 0.500, the Bi-
deficient specimens have relatively larger gains. It can be
attributed to the formation of oxygen vacancies in these
specimens. It is commonly recognized that oxygen vacan-
cies are beneficial to the mass transport of oxide systems at
high temperatures and thus promote grain growth during
sintering. Moreover, the specimens with relatively low Bi
deficiency amounts presented pebble-like grains (Fig. 4a
and b), while the grain shape turned to be more rectangular
with higher Bi deficiency amounts, which is especially
evident when x ¼ 0.492 (Fig. 4d). The evolution in the
grain shape with Bi deficiency amount corresponds well
with that in the symmetry of the crystal structure.
Fig. 5 shows the temperature dependence of the di-
electric properties of the ceramic specimens with various
amounts of Bi deficiency. For the specimen with x ¼ 0.500
(Fig. 5a), one can observe an obvious dispersion of the free
permittivity (eT33/e0) with increasing measuring temperature.
There are two permittivity anomalies within the measuring
temperature range, a weak hump and a broad permittivity
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2000 Q. Xu et al. / Journal of Physics and Chemistry of Solids 69 (2008) 1996–2003
Fig. 5. Temperature dependence of the free permittivity (eT33/e0) and dielectric loss (tan d) of ceramic specimens with various amounts of Bi deficiency.
peak. Moreover, one can find a dielectric loss (tan d) peak,
corresponding to the weak hump of the permittivity. This
behavior is rather analogous to those previously observed
in NBT–BT ceramics with MPB compositions, with the
two permittivity anomalies being referable to a ferroelec-
tric–antiferroelectric transition and a subsequent transition
to paraelectric state, respectively [2,17]. The dashed lines in
Fig. 5a indicate two characteristic temperatures. The
temperature corresponding to the ferroelectric–antiferro-
electric transition is termed as depolarization temperature
(Td), as the specimen is basically depolarized and loses
piezoelectric activity over the temperature [18]. The value
of the depolarization temperature can be determined
according to the dielectric loss peak [19]. The specimen
shows a depolarization temperature around 85 1C, which is
relatively lower compared with that of (Na0.5Bi0.5)0.94
Ba0.06TiO3 (100 1C) determined by a thermally stimulated
depolarization current measurement [8]. The temperature
where the peak value of the permittivity occurs is named as
maximum temperature (Tmax). The diffuse phase transition
behavior of the specimen is in agreement with the nature of
the NBT–BT system as a relaxor ferroelectric. The
mechanism of diffuse phase transition in complex per-
ovskite-type relaxor ferroelectrics has been elucidated from
different viewpoints [20,21]. In the present work, it is
considered that this behavior should be closely related to
the coexistence of complex ions (Na+, Bi3+ and Ba2+),
which possess similar radii but different charges and
electron configurations, at an equivalent crystallographic
site.
The Bi-deficient specimens showed a rather similar
variation of the dielectric properties with measuring
temperature (Fig. 5b–d). Compared with the specimen
with x ¼ 0.500, the Bi-deficient specimens offered obscurer
low-temperature permittivity humps coupled with more
dispersive permittivity peaks. This is ascribable to the
formation of Bi and oxygen vacancies in the Bi-deficient
specimens, increasing local compositional inhomogeneity
and therefore leading to a more diffusive dielectric
response. In addition, one can find that the Bi deficiency
resulted in an increase in the depolarization temperature
and maximum temperature relative to those of the speci-
men with x ¼ 0.500. The increase of the depolarization
temperature in the Bi-deficient specimens was further
confirmed by the inspection of the P–E hysteresis loops
of the specimens at varied temperatures, which will be
provided in the following part.
At room temperature, saturated P–E hysteresis loops
were observed over the entire investigated composition
range. The values of the remanent polarization (Pr) and
coercive field (Ec) were determined from measured loops,
as shown in Fig. 6. The coercive field displayed an
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Q. Xu et al. / Journal of Physics and Chemistry of Solids 69 (2008) 1996–2003
enhancement with increasing Bi deficiency amount, while
the remanent polarization, generally, presented an inverse
trend. This occurrence can be qualitatively interpreted with
regard to the formation of Bi and oxygen vacancies in the
Bi-deficient specimens. As well known, oxygen vacancies in
perovskite-type ferroelectrics have a clamping effect on the
motion of domain walls [22]. The clamping effect restrains
the reversal of the spontaneous polarization of ferroelectric
domains under applied electrical field, resulting in an
Fig. 6. Remanent polarization Pr and coercive field Ec at room
temperature for ceramic specimens as a function of Bi content.
Fig. 7. P–E hysteresis loops at varied temperatures for ceramic specimens with various amounts of Bi deficiency.
2001
increase of the coercive field. On the other hand, as well
established, the spontaneous polarization in a perovskite-
type ferroelectric mainly originates from the displacement
of the B site cations within the [BO6] octahedra [8,10]. For
the Bi-deficient specimens, the decrease of the unit cell
dimensions caused by the generation of Bi and oxygen
vacancies is unfavorable to such displacement and thus
acted as a detrimental factor to the spontaneous polariza-
tion. This is assumed to be the cause for the reduction of
the remanent polarization with increasing Bi deficiency
amount.
The P–E hysteresis loops of the specimens were also
examined at elevated temperatures. Fig. 7 shows the P–E
hysteresis loops at varied temperatures for the ceramic
specimens with various amounts of Bi deficiency. The P–E
hysteresis loops of the specimens displayed a similar
evolution, becoming narrower with elevating measuring
temperature. For the specimen with x ¼ 0.500, the loop
measured at 80 1C kept a typical ferroelectric feature and
further elevating the temperature to 120 1C yielded a
double-like loop, reflecting the appearance of an antiferro-
electric state. The result is generally in accordance with the
depolarization temperature of the specimen around 85 1C,
as indicated by the dashed line in Fig. 5a. It was noticed
that the double-like hysteresis loop still reserved a small
degree of remanent polarization. This can be ascribed to a
coexistence of ferroelectric and antiferroelectric states in
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2002 Q. Xu et al. / Journal of Physics and Chemistry of Solids 69 (2008) 1996–2003

the specimen at the temperature [23]. For the Bi-deficient

specimens, no double-like hysteresis loop occurred over the
whole measuring temperature range except a very slight
deformation of the loop measured at 120 1C when
x ¼ 0.498. Then, it can be suggested that the Bi deficiency
served to increase the depolarization temperature of
(Na0.5Bi0.5)0.93Ba0.07TiO3. This result roughly coincides
with that obtained from the investigation of the tempera-
ture dependence of the dielectric properties in Fig. 5.
The depolarization temperature can be visualized as an
indication of the temperature stability of ferroelectric
domains [8]. For piezoelectric ceramics, the depolarization
temperature is an important parameter in view of practical
applications, which basically determines the applicable
temperature range [7,24]. The increase of the depolariza-
tion temperature in the Bi-deficient specimens can find an
explanation in terms of the presence of oxygen vacancies in
these specimens. Successive ferroelectric–antiferroelectric–
paraelectric transitions with temperature have been pre-
viously observed in varieties of lead-based complex
perovskite-type compounds and NBT-based compositions
[23,25]. The intermediate antiferroelectric state has been
defined as an incommensurate structure, which may not be
strictly classified as a normal antiferroelectric state and can
be explained in light of a subtle modulation of spontaneous
polarization [23,26,27]. The weak permittivity humps and
the loss peaks in Fig. 5 can be viewed as a dielectric
response to such incommensurate modulation. Based upon
transmission electron microscopy observation, it has been
revealed that there is a direct interaction between ferro-
electric domains and the incommensurate modulation, with Fig. 8. Piezoelectric properties of ceramic specimens as a function of Bi
ferroelectric domain walls playing a role as barriers [26]. content.
For the Bi-deficient specimens, the clamping effect of
oxygen vacancies on the motion of ferroelectric domain increasing Bi deficiency amount. Comparatively, the
walls can dynamically suppress the degree of the sponta- electromechanical coupling factor (kp) appears to be
neous polarization modulation. Thus, compared with the somewhat insensitive to the Bi efficiency, with the
specimen with x ¼ 0.500, these specimens necessitate parameter fluctuating within 21.2–25.6%. The variation
higher temperatures to overcome the clamping effect and of the piezoelectric constant and mechanical quality factor
thermally drive the ferroelectric–antiferroelectric transi- with Bi deficiency amount can be understood in relation to
tion. This is considered to be the reason for the increase of the clamping effect of oxygen vacancies on ferroelectric
the depolarization temperature with introducing of Bi domains. The clamping effect hindered sufficient reorienta-
deficiency. tion of ferroelectric domains during electrical poling, which
Fig. 8 shows the piezoelectric properties of the ceramic is greatly detrimental to the piezoelectric constant [29].
specimens as a function of Bi content. The specimen with Correspondingly, the internal attrition resulting from the
x ¼ 0.500 gives a relatively large piezoelectric constant motion of ferroelectric domains was also reduced, leading
(d33) of 176 pC/N, which is rather similar to our previous to an increase in the mechanical quality factor.
result of 180 pC/N achieved from (Na0.5Bi0.5)0.94Ba0.06TiO3 With respect to the data of the present work, it is
ceramics prepared by the citrate method [16]. These values noteworthy that even a slight Bi deficiency can cause a
are much larger than those obtained from the NBT–BT remarkable deterioration of the ferroelectric and piezo-
ceramics with MPB compositions, which were prepared by electric properties, including an increase of the coercive
the conventional solid-state method [2,8,28]. It demon- field, a decline of the remanent polarization and a
strates the advantage of the citrate method in producing reduction of the piezoelectric constant. It suggests a
the NBT–BT ceramics, attributable to the fine and uniform necessity of carefully controlling Bi stoichiometry of
morphology together with high chemical homogeneity of (Na0.5Bi0.5)0.93Ba0.07TiO3 ceramics during the preparation
the powders derived from the citrate method [16]. One can process in order to achieve the desired electrical properties.
find a monotonic decrease of the piezoelectric constant and This may be given as a clue to further research on the
a steady increase of the mechanical quality factor (Qm) with ceramics.
 ARTICLE IN PRESS
Q. Xu et al. / Journal of Physics and Chemistry of Solids 69 (2008) 1996–2003
4. Conclusions
Fine and uniform (Na0.5Bix)0.93Ba0.07TiO3 (x ¼ 0.500–
0.492) powders have been produced by a citrate method.
The structure and electrical properties of the resulting
ceramic specimens have been examined with respect to the
amount of Bi deficiency. A significant influence of the Bi
deficiency on the crystal structure and microstructure has
been detected. The inspection of both the temperature
dependence of the dielectric properties and the evolution of
the P–E hysteresis loops with measuring temperature
suggests that the Bi deficiency served to increase the
depolarization temperature (Td). At room temperature, the
Bi deficiency brought about an increase in the coercive filed
(Ec) and mechanical quality factor (Qm) along with a
decline in the remanent polarization (Pr) and piezoelectric
constants (d33). The effect of the Bi deficiency on the
structure and electrical properties has been qualitatively
explained in terms of the formation of Bi and oxygen
vacancies in the Bi-deficient specimens. This research
demonstrates the necessity of adequately controlling Bi
stoichiometry of (Na0.5Bi0.5)0.93Ba0.07TiO3 ceramics in
obtaining the desired ferroelectric and piezoelectric
properties.
Acknowledgments
This work was financially supported by the Program for
New Century Excellent Talents in University (Grant no.
NCET-04–0724). It is grateful to the Natural Science
Foundation of China (Grant nos. 50272044 and 50410529)
and Korea Science and Engineering Foundation (Grant
no. F01-2004–000–10084–0) for jointly supporting the
research. The Program for the Training of Graduates in
Regional Innovation conducted by the Ministry of
Commerce, Industry and Energy of the Korean Govern-
ment also supported the research.
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