Acta Materialia 52 (2004) 5177–5183

www.actamat-journals.com

Diffuse phase transition and dielectric tunability of Ba(ZryTi1
y)O3

relaxor ferroelectric ceramics
X.G. Tang *, K.-H. Chew, H.L.W. Chan
Department of Applied Physics and Materials Research Centre, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, PR China

Received 11 May 2004; received in revised form 15 July 2004; accepted 18 July 2004
Available online 24 August 2004

Abstract

Barium zirconate titanate Ba(ZryTi1
y)O3 (BZT, y = 0.2, 0.25, 0.30, 0.35) ceramics have been prepared by a sol–gel process. The
temperature dependence of dielectric permittivity of the ceramics has been investigated. The results show that the phase transition
temperature TC (or Tm) is suppressed with increasing Zr content. The degree of diffuseness of the phase transition is more pro-
nounced for higher Zr content, implying the existence of a composition-induced diffuse phase transition of the ceramics with
0.20 6 y 6 0.35. For BZT ceramics with y > 0.25, a relaxor ferroelectric characteristic is observed. High tunability and figure of
merit are obtained in BZT compositions investigated, which imply that these ceramics are promising materials for tunable capacitor
applications.

2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: BZT ceramic; Diffuse phase transition; Relaxor behavior; Electric field; Tunability

1. Introduction ture (Tm) of BZT bulk ceramics is known to change

strongly with Zr content. For Zr contents y > 0.08, the
Barium strontium titanate (Ba,Sr)TiO3(BST) is a Ba(ZryTi1
y)O3 bulk ceramics show a broad dielectric
high-K (dielectric constant) material commonly used constant-temperature (e  T) curve near Tm, which is
to replace silicon dioxide (SiO2) as the dielectric in ad- caused by the inhomogeneous distribution of Zr ions
vanced memory devices. The high dielectric constant on Ti sites and mechanical stress in the grain [6]. As
combined with a low dissipation factor makes BST the Zr content increases, the phase transition tempera-
one of the promising candidates for dynamic random tures approach each other, until, at a Zr content of
access memory (DRAM) applications [1]. Recently, y  0.20, only one phase transition exists [11]. Despite
Ba(ZryTi1
y)O3(BZT) has been chosen as an alternative the high e values of Ba(ZryTi1
y)O3 bulk ceramics, a de-
to BST in the fabrication of ceramic capacitors because tailed description on sol–gel fabrication and dielectric
Zr4+ is chemically more stable than Ti4+ [2–9]. The solid properties of Ba(ZryTi1
y)O3 ceramics under dc electric
solution of barium titanate BaTiO3 and barium zirco- field found is still scarcely in the literatures.
nate BaZrO3, i.e., Ba(ZryTi1
y)O3, shows great similar- In perovskites, the relaxor behavior mainly occurs in
ity to the BST solid solution [10,11]. The nature of the lead-based compositions (PMN, PSN, PLZT, etc.) with
ferroelectric phase transition at the transition tempera- more than one type of ions occupying the equivalent six-
coordinated crystallographic sites [12]. Lead-free com-
*
Corresponding author. Tel.: +86 852 276 64616; fax: +86 852 233
positions could be of great interest for environmentally
37629. friendly applications (such as dielectrics for capacitors,
E-mail address: [email protected] (X.G. Tang). actuators, etc.). In this work, lead-free Ba(ZryTi1
y)O3

1359-6454/$30.00
2004 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.actamat.2004.07.028
5178 X.G. Tang et al. / Acta Materialia 52 (2004) 5177–5183

(y = 0.20, 0.25, 0.30, 0.35) ceramics were prepared by a 12,480 at 100 Hz for the BZT25 sample). The results
sol–gel method. The influence of Zr content on the die- also show that the temperature Tm corresponding to
lectric properties of the Ba(ZryTi1
y)O3 ceramics with the maximum value of the dielectric permittivity em is
0.20 6 y 6 0.35 were examined and discussed. The elec- decreased with increasing Zr content, implying the Zr
tric field-dependence of permittivity of the ceramics was substitution in BaTiO3 influence the transition tempera-
explored for possible application as tunable capacitors. ture Tm. An interesting feature can be found from
Fig. 1(a) is that the transition temperature Tm of the
BZT20 sample is located at the vicinity of room temper-
2. Experimental ature Tm  297 K. At temperature near to the transition
temperature, the permittivity become very high and the
Ba(ZryTi1
y)O3 (with compositions y = 0.20, 0.25, polarization that can be induced by even a small field
0.30, 0.35; abbreviated as BZT20, BZT25, BZT30 and can be quite large [1,15,16]. This indicates that the die-
BZT35, respectively), powders and ceramics were pre- lectric non-linearity for the BZT20 ceramics at room
pared by a sol–gel process [13,14]. The chemical method temperature is expected to be very strong.
has the advantage that it is relatively simple, with easy The dielectric loss of the samples is decreased with
stoichiometric composition control and low cost. increasing temperature, as shown in Fig. 1. In particular,
Weighted amounts of the appropriate proportions of the loss tangent values were suppressed significantly
high purity barium acetate, zirconium-n-propoxide and at temperatures above Tm. The loss tan d above Tm is
titanium n-butoxide were used as precursors. Acetic acid smaller for samples with a high Zr content such as
and 2-methoxyethanol were selected as solvents. Barium BZT30 and BZT35. For example, the loss tan d for the
acetate was dissolved in acetic acid, and the two alk- BZT35 sample measured at f = 100 Hz is 0.0014 at
oxides were dissolved in 2-methoxyethanol, respectively. 300 K, which is lower than that of the BZT25 sample
By controlling the hydrolysis condition of the complex (tan d = 0.0035).
solution, a BZT gel was formed. The dry gel was then Fig. 1(c) and (d) show that the dielectric response of
annealed at 1100 C for 5 h in atmosphere. After grind- BZT30 and BZT35 ceramics at various frequencies,
ing, BZT powders were obtained. The annealed powders which shows a diffuse phase transition around the tran-
were pressed into disks. The pellets were sintered at sition temperature Tm. The diffuse transition behavior is
1400 C for 5 h and cooled in a furnace. Silver paste enhanced with increasing Zr content, indicating a com-
was coated to form electrodes on both sides of the sin- position-induced diffuse transition. The Tm is moved to-
tered ceramic specimens for dielectric measurements. ward higher temperatures with increasing frequency. In
The bulk densities of the sintered samples were meas- BZT20 and BZT25 samples, however, there are almost
ured by the Archimedes method using distilled water as no shifts in Tm. The full-width of half-maximum
medium. The measurement on the bulk densities of the (FWHW) of BZT20 is 48 K (from 283 to 331 K)
BZT specimens (sintered at 1400 C) shows that the den- and is 60 K (from 235 to 295 K) for BZT25, respec-
sity of the ceramics are as high as 95–96% of the theo- tively. The BZT20 and BZT25 ceramics can be easily
retical density. The capacitance and loss tan d of the distinguished from the high Zr content samples by look-
samples were measured using an HP4194A impedance ing at their dielectric behavior e(T) at T 6 Tm. The
analyzer in the frequency range of 100 Hz to 1000 low-temperature (temperatures below Tm) frequency
kHz. The capacitance was also measured under various dispersion of the dielectric maximum em(T) clearly dem-
dc biases by using a blocking circuit, a multi-frequency onstrates a relaxation nature, namely, a relaxor-type dif-
LCR meter (Model SR720 of Stanford Research Sys- fused permittivity, for BZT30 (Fig. 2(c)) and BZT35
tem), and a dc power source (Keithley 6517A). (Fig. 2(d)) ceramics, respectively. The Tm of BZT35
sample increases from 153 K at 100 Hz to 174 K at
100 kHz, with the FWHM about 164 K (for 100 Hz,
3. Results and discussion from 90 to 254 K), which is 22 K wider than that of
BZT30 (the FWHM is 142 K) ceramics.
3.1. Temperature dependence of dielectric constant and
loss 3.1.1. Diffuse phase transition behaviors
Let us first discuss the diffuse transition behavior of
Fig. 1 shows the dielectric constant dependence of the BZT ceramics. A diffuse phase transition is generally
temperature for the BZT samples at 100 Hz, 1 k, 10 k, characterized by: (a) broadening in the dielectric con-
and 100 kHz. The dielectric constant of the BZT20 stant (e) versus temperature (T) curve; (b) a relatively
and BZT25 samples are generally higher than those large separation (in temperature) between the maximum
ceramics with higher Zr content such as BZT30 and of the real (dielectric constant) and imaginary (dielectric
BZT35. For the BZT20 and BZT25 ceramics, the dielec- loss) parts of the dielectric spectrum; (c) a deviation
tric constant can be as high as 8000 and 12,500 (e.g., from Curie–Weiss law in the vicinity of Tm; (d)
 X.G. Tang et al. / Acta Materialia 52 (2004) 5177–5183 5179

(a) 0.20 (b) 15000 0.20

100 Hz 100 Hz
8000
1 kHz 1 kHz
0.16 12000 0.16
10 kHz 10 kHz

Dielectric constant
Dielectric constant

100 kHz 100 kHz

6000
0.12 9000 0.12

Loss tanδ
Loss tanδ
4000 0.08 0.08
6000

2000 0.04 0.04

3000

0.00 0.00
0 0
100 150 200 250 300 350 400 450 500 50 100 150 200 250 300 350 400 450 500
Temperature (K) Temperature (K)

(c) 6000 0.4 (d) 5000 0.4

100 Hz 100 Hz
5000 1 kHz
4000 1 kHz
10 kHz 0.3 10 kHz 0.3
Dielectric constant

Dielectric constant
4000 100 kHz 100 kHz
3000
Loss tanδ

Loss tanδ
3000 0.2 0.2
2000
2000
0.1 0.1
1000 1000

0 0.0 0 0.0
50 100 150 200 250 300 350 400 450 50 100 150 200 250 300 350 400 450
Temperature (K) Temperature (K)
Fig. 1. Temperature (T) dependence of dielectric constant e and loss tan d of: (a) BZT20; (b) BZT25; (c) BZT30; (d) BZT35 ceramics.

frequency dispersion of both e and tan d (dielectric loss) It is known that the dielectric permittivity of a normal
in the transition region thereby implying a frequency ferroelectric above the Curie temperature follows the
dependence of Tm [12,17–19]. Curie–Weiss law described by
1=1=e ¼ ðT
T 0 Þ; ðT > T C Þ; ð1Þ
0.005 where T0 is the Curie–Weiss temperature and C is the
BZT20 Curie–Weiss constant. A T0 of 383 K and C of
BZT25 1.56 · 105 K have been obtained for a pure BaTiO3 crys-
0.004
BZT30 tal [20]. For the BZT ceramics, the dielectric constant (e)
BZT35 was fitted to the Curie–Weiss law. The parameters ob-
0.003 tained from the fittings are listed in Table 1. Fig. 2 shows
the plots of inverse dielectric constant (at 10 kHz) versus
1/ε

0.002 temperature. The solid lines are plotted for the four
samples using the parameters obtained from the fittings
(Table 1) and Eq. (1). A deviation from the Curie–Weiss
0.001
law can be seen, being more evident for samples with
high Zr content, i.e., BZT30 and BZT35.
0.000 The parameter DTm, which describes the degree of the
100 200 300 400 500
deviation from the Curie–Weiss law, is defined as
Temperature (K)
DT m ¼ T cw
T m ; ð2Þ
Fig. 2. The inverse dielectric constant (1/e) as a function of temper-
ature at 10 kHz for the four samples. (The symbols: experimental data; where Tcw denotes the temperature from which the per-
the solid line: fitting to the Curie–Weiss law.) mittivity starts to deviate from the Curie–Weiss law and
5180 X.G. Tang et al. / Acta Materialia 52 (2004) 5177–5183

Table 1 Table 2
The Curie–Weiss temperature (T0), the Curie–Weiss constant (C), and The temperature of dielectric constant maximum (Tm), dielectric
the temperature above which the dielectric constant follows the Curie– constant maximum (em), and diffuseness constant (c) for the four
Weiss law (Tcw) for the four samples at 10 kHz samples at 10 kHz
Samples BZT20 BZT25 BZT30 BZT35 Samples BZT20 BZT25 BZT30 BZT35
T0 (K) 322 290 255 221 Tm (K) 297 257 198 166
C (·105 K) 0.945 1.28 1.10 1.17 em (K) 7620 12250 5376 4343
Tcw (K) 354 349 344 336 c 1.62 1.81 1.93 2.01
DTm = Tcw
Tm (K) 57 92 146 170

100 kHz, clearly implying the BZT ceramics exhibit a

strong diffuse phase transition for higher Zr content.
Tm represents the temperature of dielectric maximum.
For BZT20, BZT25, BZT30 and BZT35, the values of 3.1.2. Vogel–Fulcher relationship
DTm are 57, 92, 146 and 170 K, respectively, as shown The plot of ln (m) vs Tm is shown in Fig. 5 for BZT30
in Table 1. The values of DTm increases with increasing and BZT35 samples with frequency dispersion. The non-
Zr concentration, which further provides the evidence of linear ln (m) vs Tm curve indicates that the data cannot
a compostion-induced diffuse phase transition behavior be fitted with a simple Debye equation. In order to ana-
in the BZT ceramics with 0.20 6 y 6 0.35. lyze the relaxation features of the BZT30 and BZT35
A modified Curie–Weiss law [21–23] has been pro- ceramics, the experimental curves (Fig. 4) were fitted
posed to describe the diffuseness of a phase transition using the Vogel–Fulcher formula [21,22]
c
1=e
1=em ¼ ðT
T m Þ =C 0 ; ð3Þ m ¼ m0 exp½Ea =k B ðT
T VF Þ; ð4Þ
where c and C 0 are assumed to be constant. The param- where m0 is the attempt frequency, Ea is a measure of
eter c gives information on the character of the phase average activation energy, and kB is the BoltzmannÕs
transition: for c = 1, a normal Curie–Weiss law is ob- constant, and TVF is the freezing temperature. The fit-
tained, c = 2 describes a complete diffuse phase transi- ting curves are shown in Fig. 4 (solid lines). For
tion [19,22]. BZT30, the fitting parameters are Ea = 0.0156 eV,
The plots of ln (1/e
1/em) as a function of ln (T
Tm) TVF = 181 K, and m0 = 3.82 · 108 Hz. For BZT35, the
for the four samples are shown in Fig. 3. A linear rela- fitting parameters are Ea = 0.110 eV, TVF = 103 K, and
tionship is observed for the four samples. The slope of m0 = 4.51 · 1012 Hz. The empirical relaxation strength
the fitting curves (using Eq. (3)) is used to determine describing the frequency dispersion of Tm, which is de-
the c value. The determine value of c are listed in Table 2. fined as
The c = 1.62, 1.81, 1.93 and 2.01, respectively, for
DT res ¼ T mð1 MHzÞ
T mð100 HzÞ ; ð5Þ
BZT20, BZT25, BZT30 and BZT35 ceramics. For the
BZT35 sample, the fitted values of c decreases from where DTres was derived from the dielectric measure-
2.06 to 1.94 when frequency increases from 100 Hz to ments of the BZT solid solutions. The values of DTres

-6 15
γ=1.62 BZT30
γ=1.81 BZT35
-8
γ=1.93 12
γ=2.01
-10
ln(1/ε-1/εm)

10 kHz
ln(ν) (Hz)

-12
BZT20
BZT25 6
-14 BZT30
BZT35

-16 3
0 1 2 3 4 5 6 150 160 170 180 190 200 210
ln(T-Tm) (K) Tm (K)

Fig. 3. Plot of ln (1/e
1/em) as a function of ln (T
Tm) for the four Fig. 4. Plot of ln (m) as a function of Tm for the BZT30 and BZT35
samples. (The symbols: experimental data; the solid line: fitting to the ceramic. (The symbols: experimental data; the solid curve: fitting to the
Eq. (3).) Vogel–Fulcher relation.)
 X.G. Tang et al. / Acta Materialia 52 (2004) 5177–5183 5181

for BZT20, BZT25, BZT30 and BZT35 samples are 2, 3, (a) 7500
17 and 32 K, respectively, indicating a transformation BZT20
from a normal ferroelectric to a relaxor-like ferroelectric BZT25
6000 BZT30
for higher Zr content.
BZT35

Dielectric constant
The relaxor behavior as observed in these BZT
ceramics can be induced by many reasons such as a 4500
microscopic composition fluctuation, the merging of
micropolar regions into macropolar regions, or a cou- 3000
pling of order parameter and local disorder mode
through the local strain [12,18,19]. Vugmeister and
1500
Glinichuk reported that the randomly distributed elec-
trical field/or strain field in a mixed oxide system was
the main reason leading to the relaxor behavior [24]. 0
-20 -10 0 10 20
In the solid solution of BaZryTi1
yO3 Ba ions occupy
the A sites of the ABO3 perovskite structure. Zr and Electric field (kV/cm)
Ti ions occupy the B sites, and the ionic radius of Zr4+
(0.98 Å) is larger than that of Ti4+ (0.72 Å), therefore, (b) 0.012
at higher Zr contents, the BaZryTi1
yO3 bulk ceramics BZT20
BZT25
show a broad dielectric constant-temperature (e  T)
0.009 BZT30
curve at the vicinity of the transition temperature Tm, BZT35
which is caused by an inhomogeneous distribution of
Zr ions in the Ti sites and mechanical stress in the grain.
Loss tan
0.006
Stress was introduced into the lattice during cooling
after the sintering process, which is due to the transition
from a cubic to rohombohehedral phase below the Curie
0.003
temperature [11]. On the other hand, it is known that the
BaZrO3 show non-ferroelectic (cubic paraelectric phase)
behavior at room temperature because, the Zr ion lo- 0.000
cates at the central equilibrium position of BaZrO3 lat- -20 -10 0 10 20
tice. In this case, the macrodomains in BaTiO3 could Electric field (kV/cm)
be divided into the microdomains with increasing Zr
ions doping, which result in the appearance of the relax- Fig. 5. (a) e and (b) tan d as a function of electric field at room
temperature for the four samples at 10 kHz and 20 kV/cm.
or behavior.

3.2. Electric field-dependence of dielectric constant

(room temperature T = 300 K) is near to the transition
With a detailed understanding of the dielectric prop- temperature Tm of the two samples with a lower Zr con-
erties of the BZT ceramics, we are now exploring the tent (i.e., BZT20 and BZT25). Thus, the dielectric non-
possible applications of these materials in tunable capac- linearity of the two ceramics particularly BZT20 is very
itor applications. In particular, the ability to adjust the strong [7,16]. This is in accordance with the strong field-
dielectric constant via a dc electric field with emphasis dependence of permittivity as observed for BZT20 sam-
at room temperature is studied and discussed in this sec- ples with Tm  297 K.
tion. The dielectric behaviors were measured under a dc In the BZT20 and BZT25 ceramics, the presence of a
field of 20 kV/cm and at a frequency of 10 kHz in the weak hysteresis behavior in the dc field-dependence of e
temperature range from 253 to 373 K. The dc field- (Fig. 5(a)) clearly suggests the presence of ferroelectric-
dependence of e and tan d for the four samples at room ity over the investigated temperature although the mate-
temperature (300 K) are shown in Figs. 5(a) and (b), rial should be in the paraelectric phase at temperatures
respectively. In general, the tunability and dielectric loss as it is higher than the Tm of the two ceramics (see
are suppresed with increasing Zr content. Both the Table 2). One of the reasons might be due to the local-
BZT20 and BZT25 samples show higher tunablities than ized charges at the grain boundaries or defects are
that of the BZT30 and BZT35 ceramics. On the other moved and trapped in a new location under the effect
hand, the values of the loss tangent for the relaxor-type of the dc biasing field which causes the hysteretic char-
ceramics BZT30 and BZT35 are about 0.0020  0.0025, acteristics [25,26]. The BZT30 and BZT35 have a ‘‘slim’’
which is smaller than the ceramics with a lower Zr con- hysteresis behavior, which is the typical behavior of a re-
tent such as BZT20 and BZT25. One of the reasons for a laxor ferroelectric owing to the existence of micropolar
higher tunability is that the investigated temperature regions [12,19].
5182 X.G. Tang et al. / Acta Materialia 52 (2004) 5177–5183

The tunability (k) can be calculated by using the at room temperature can be found at y = 0.25. These
expression as following FOM values of the BZT ceramics at 0.20 6 y 6 0.35
k ¼ ½eð0Þ
eðEÞ=eð0Þ; ð6Þ are comparable to all the currently studied tunable
materials, such as (Ba,Sr)TiO3 and (Sr,Pb)TiO3, etc.,
where e(0) and e(E) represent the dielectric constant at [1,15]. In addition, the high e value permits more room
zero and a non-zero E field, respectively. The tunability for further decreasing the loss tan d. It is expected that
as a function of temperature measured at E = 20 kV/cm the properties, in particular the dielectric loss can be fur-
for the four samples is depicted in Fig. 6. ther improved by adding additives to this solid solution
At room temperature, the tunability of the ceramics is and the dielectric constant can be tailored to the suitable
decreased with increasing Zr content. For example, the values for tunable capacitor applications.
tunabilities measured at 300 K under the biasing field
of E = 20 kV/cm for the BZT20, BZT25, BZT30 and
BZT35 are 86%, 58%, 26% and 19%, respectively. It is 4. Conclusions
noted that the tunability of the BZT20 ceramics is more
than 80% at room temperature and the optimum value We have prepared the Ba(ZryTi1
y)O3 ceramics using
of the tunability is located at the transition temperature the sol gel method. The effect of the Zr content on the
Tm (with k  87% at Tm  296 K). The high tunability dielectric behaviors of the Ba(ZryTi1
y)O3 ceramics with
of the BZT20 ceramics near the transition temperature 0.20 6 y 6 0.35 were studied in detail for possible appli-
is expected for the obvious reason as discussed earlier cations in tunable capacitor applications. The Zr substi-
[1,15,16]. tution in BaTiO3 affects the transition temperature Tm
The figure of merit (FOM) is calculated based on the by shifting the Tm to a lower temperature region with
expression below [1] increasing Zr content. A normal ferroelectric with a
FOM ¼ k= tan d: ð7Þ weak diffuse transition behaviors is observed for the
Ba(ZryTi1
y)O3 ceramics at y = 0.20 and 0.25, in accord-
The value of the figure of merit is listed in Table 3 meas- ance with the results reported by Hennings and co-
ured at room temperature, under a bias field of 20 kV/ workers [11]. The diffuse phase transition behaviors of
cm. The values of the figure of merit versus composition the ceramics become pronounced at a high Zr content,
with a maximum value of FOM = 135 is found at implying a composition-induced diffuse transition. The
y = 0.25. The result also implies that the optimum con- ferroelectric behaviors of the ceramics, however, become
ditions of the ceramics for possible tuning applications a relaxor-like behavior at a high Zr content (as found in
BZT30 and BZT35) with a strong frequency dispersion
of the em(T) at T 6 Tm. The high Zr content ceramics
100 BZT20 obey the empirical Vogel–Fulcher relation, which con-
10 kHz,20 kV/cm
BZT25 firms the relaxor behavior of the BZT30 and BZT35
BZT30 ceramics.
80 BZT35
The tunability and dielectric loss measured at room
Tunability (%)

temperature decrease with increasing Zr content. At

60 room temperature, the BZT20 ceramic exhibits a strong
dielectric non-linearity with the tunability of 86%. The
40 high tunability of the BZT20 is attributed to the strong
field-dependence of permittivity with a transition tem-
20 perature Tm near to the investigated temperature. In
the present study, the optimum value of the figure of
0 merit is expected to locate around Zr = 0.25. The high
240 260 280 300 320 340 360 380 tunability and figure of merit of the BZT ceramics at
Temperature (K) 0.20 6 y 6 0.35, indicate that this ceramics is a pro-
Fig. 6. Temperature dependence of tunability (k) for the four samples
mising material for tunable capacitor applications.
at E = 20 kV/cm and 10 kHz.

Acknowledgements
Table 3
Tunabilities (k) and figures of merit (FOMs) for the four samples at
This work is supported by Centre for Smart Materi-
room temperature (300 K), E = 20 kV/cm and 10 kHz
als of the Hong Kong Polytechnic University. The
Samples BZT20 BZT25 BZT30 BZT35
authors (X.G.T. and K.H.C.) gratefully acknowledge
k (%) 86 58 26 19 the Postdoctoral Fellowship Scheme of the Hong Kong
FOM 80 135 104 76
Polytechnic University for the support of this work.
 X.G. Tang et al. / Acta Materialia 52 (2004) 5177–5183 5183

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