Dielectric behavior of single

crystals
Cite as: Journal of Applied Physics 88, 410 (2000); https://doi.org/10.1063/1.373674
Submitted: 20 December 1999 . Accepted: 22 March 2000 . Published Online: 19 June 2000

Zhi Yu, Ruyan Guo, and A. S. Bhalla

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© 2000 American Institute of Physics.

JOURNAL OF APPLIED PHYSICS VOLUME 88, NUMBER 1 1 JULY 2000

Dielectric behavior of Ba„Ti1À x Zrx …O3 single crystals

Zhi Yu,a) Ruyan Guo, and A. S. Bhalla
Materials Research Laboratory, The Pennsylvania State University, University Park, Pennsylvania 16802
共Received 20 December 1999; accepted for publication 22 March 2000兲
In this article, we report the successful growth of Ba共Ti1⫺x Zrx 兲O3 (x⫽0.05– 0.2) single-crystal
fibers by the laser-heated pedestal growth technique. A single-phase perovskite structure of the
materials has been identified by the x-ray diffraction technique. The phase diagram for
Ba共Ti1⫺x Zrx 兲O3 single crystals is established for x⭐0.2. Dielectric properties as function of
temperature and frequency and room-temperature hysteresis loops are measured. The remnant
polarization ( P r ) and coercive fields (E c ) are obtained and compared for both single crystals and
ceramics. The small dielectric relaxation has been observed for the lower-temperature phase
transition 共around 40 °C at 1 kHz兲 of the sample with x⫽0.08. The relaxation times follow the
Arrhenius law with ␶ 0 ⫽0.4⫻10⫺13 s and E relax⫽0.53 eV. A common feature of the
low-temperature relaxation mode in the sample is also observed, which follows the Arrhenius law
with the ␶ 0 ⫽0.8⫻10⫺10 s and E relax⫽0.46 eV. © 2000 American Institute of Physics.
关S0021-8979共00兲00313-3兴

I. INTRODUCTION diameter single crystals. The crystal can be grown from ce-
ramics, and thus the composition of the solid solution can be
It has recently been demonstrated that single crystals of easily adjusted. In this work, we use the LHPG technique to
relaxor ferroelectrics, like Pb(Zn1/3Nb2/3兲O3 – PbTiO3 solid grow several selected compositions of Ba共Ti1⫺x Zrx 兲O3 (x
solutions, exhibit enhanced piezoelectric performance com- ⫽0.05– 0.2) single crystals, and study the phase structure,
pared to alternative polycrystalline forms.1,2 It is also shown crystal quality, and the primary dielectric properties; the re-
that the piezoelectricity and strain can be enhanced in single sults are compared with those for Ba共Ti1⫺x Zrx 兲O3
crystals poled along certain suitable directions.1–4 It is, there- ceramics.11–14
fore, desirable to examine if some known piezoelectric ma-
terials in the single-crystal form may give enhanced piezo-
electric performance. Recent interest in single-crystal
II. EXPERIMENTAL PROCEDURE
piezoelectrics is increasing and many single crystals have
been grown to search for the high level of piezoelectric ac- Ba共Ti1⫺x Zrx 兲O3 共x⫽0.05, 0.08, 0.15, and 0.2兲 ceramics
tivity. were prepared by solid-state reaction. The starting materials
Barium titanate (BaTiO3) is one of the most studied (BaCO3, TiO2, and ZrO2 with high purity兲 were weighed
ferroelectric materials.5 Single crystals of BaTiO3 were and wet mixed in alcohol. After drying, the powders were
grown by various methods.6,7 Recently, the influence of crys- calcined at 1200 °C. The calcined powders were mixed
tallographic characteristics on the piezoelectric behavior of again, dried, and pressed into disks 35 mm in diameter and
BaTiO3 single crystals has been investigated as function of ⬃1.2 mm thick. The pellets were sintered at 1335–1580 °C
temperature and dc bias.8 Both the orthohombic and rhom- for 2–8 h. The ceramic pellet was polished and cut into
bohedral crystals exhibited enhanced piezoelectric perfor- square rods as feeds with dimension of about 1⫻1
mance by poling along the pseudocubic 具001典 direction. A ⫻25 mm3. The LHPG equipment used in this work consists
stable domain configuration was obtained at ⫺100 °C in the of a tunable gas CO2 laser source, an optical layout, and a
rhombohedral phase.8 It is expected that the enhanced piezo- growth chamber. The circular laser radiation of the TEM00
electric performance can be also achievable at around room mode was chosen and transformed into an annulus by a
temperature by shifting the phase transitions of BaTiO3 reflaxicon.10 The annulus was directed onto a parabolic mir-
through forming solid solution with suitable end members. ror that focused the radiation back to its focal point, forming
By using the templated grain growth 共TGG兲 method, some the hot zone. The molten zone temperature was monitored
Ba共Ti1⫺x Zrx 兲O3 共x⫽0.045 and 0.085兲 crystals of millimeter during growth by using an optical pyrometer with a linear
size were grown.9 Promising dielectric and piezoelectric dimension resolution of 0.1 mm. Details can be found in Ref.
properties were reported on the TGG samples at room tem- 10.
perature. To date, however, bulk single crystals with various The phase and crystallographic structure of both the ce-
Zr concentration are not available. ramics and the crushed single crystals was examined by
The laser-heated pedestal growth 共LHPG兲 technique10 is x-ray diffraction analysis 共XRD兲. The crystal quality was
a rapid growth 共generally, ⭓10 mm/h兲 method for small- examined and the crystal orientation was identified by the
Laue back-reflection technique 共Northstar real-time orienta-
a兲
Electronic mail: [email protected] tion system兲.

0021-8979/2000/88(1)/410/6/$17.00 410 © 2000 American Institute of Physics

J. Appl. Phys., Vol. 88, No. 1, 1 July 2000 Yu, Guo, and Bhalla 411

TABLE I. Growth conditions for Ba共Ti1⫺x Zrx 兲O3 crystals (x⫽0.05– 0.2).

x⫽0.05 x⫽0.08 x⫽0.15 x⫽0.2

Molten zone
temperature 共°C兲 1780⫾30 1810⫾30 1840⫾30 1870⫾30

Molten zone shape Concave

Pulling/feeding rates 11–25 mm/h

Gold electrodes were sputtered on the crystal specimens

for dielectric measurements. The complex-dielectric constant
of the samples was measured using an HP4284 LCR meter
from 100 Hz to 1 MHz in the temperature range ⫺100 to
⫹175 °C with the cooling/heating rate of 1 °C/min. The hys-
teresis loops were measured by a modified Sawyer–Tower
circuit.

III. RESULTS
A. Growth and structure of Ba„Ti1À x Zrx …O3 single-
crystal fibers FIG. 1. Real-time Laue back-reflection pattern of the Ba共Ti1⫺x Zrx 兲O3 (x
1. Growth of single-crystal fibers of Ba „ Ti 1À x Zr x … O 3 ⫽0.05) as-grown fiber for the 关 001兴 SrTiO3 seeded growth, where the x-ray
(x Ä0.05 and 0.08) by the LHPG technique beam was perpendicular to the growth direction, hitting on the facet 共110
face兲 on the side of the as-grown crystal.
The ceramic rods used in this work were all single phase
as examined by XRD analysis. In general, ceramic rods were
used as feeding rods and either 具001典 or 具110典 oriented ⫽0.15 and 0.2, as seeded by either the 具110典 or 具001典 ori-
SrTiO3 single-crystal rods were used as seed crystals. ented SrTiO3 single crystals. The as-grown fibers were uni-
It is known that BaTiO3 – BaZrO3 is a fully solid solution form in diameter, but with small facets on the side. Laue
system,15 with the end members melting temperatures of back-reflection patterns for the grown fibers indicated the
1625 and 2620 °C, respectively.5,16 The melting temperatures single-crystal quality of the material. Taking x⫽0.05 as an
are determined by Zr content in the solid solutions. example for the 关001兴 SrTiO3 seeded growth, the Laue back-
By proper selection of the TEM00 mode and alignment reflection photograph is shown in Fig. 1, where the x-ray
of the optical beam path, the hot zone was defined. After the beam was perpendicular to the growth direction, hitting on
alignment of the feed rod and the seed, the assembly can be the facet 共110 face兲 on the side of the as-grown crystal. The
introduced into the hot zone. A suitable laser power level growth direction was identified by the Laue patterns to be the
was selected to form a stable molten zone for selected same as that of the seed crystal. For the 具110典 seeded case,
growth parameters, as determined by the Zr content of the the growth was more stable and fewer cracks were observed
materials. It is found that stable growth is easier to initiate than for the 具001典 SrTiO3 seeded growth.
when the zone exhibits a concave shape. The normal pulling/
feeding rates used were between 11 and 25 mm/h. The tem- B. Dielectric properties of Ba„Ti1À x Zrx …O3 „x Ä0.05,
perature distribution was uniform, as examined by tempera- 0.08, 0.15, and 0.2…
ture measurements at different locations of the zone within 1. Temperature dependence of the dielectric constant
the resolution of the pyrometer. The shape of the molten The temperature dependence of the dielectric constant
zone was also uniform, as observed from the front and back 共⑀兲 for the single-crystal samples as a function of composi-
view. During the growing period, the shape and the tempera- tion at 1 kHz is shown in Fig. 2. Compared with the three
ture of the molten zone were reasonably stable. Continuous phase transitions5 in pure BT at T c ⫽120 °C, T 2 ⫽0 °C, and
growth could be realized and 20-mm-long, ⬃1-mm-diam T 3 ⫽⫺90 °C, the paraelectric to ferroelectric phase transi-
crystals were obtained, with the length restricted by the di- tion T c for Ba共Ti1⫺x Zrx 兲O3 crystals is shifted to lower tem-
mension of the feed ceramic rods. peratures with increasing Zr concentration. For x⫽0.05, the
The recent growth conditions for Ba共Ti1⫺x Zrx 兲O3 for x other two low-temperature transitions are present and obvi-
⫽0.05 and 0.08, together with data for the previous growth ously shifted to higher temperatures. This is the well-known
for x⫽0.15 and 0.2,17 are listed in Table I. pinching effect in these compositions. With further increase
in Zr content, the temperatures of the two lower-temperature
2. Phase structure and crystal quality phase transitions increase while the T c decreases. For x
XRD analysis of the crushed crystal powder shows that ⫽0.08, two peaks at T c and T 2 in the dielectric constant plot
the grown crystals of the solid solution of Ba共Ti1⫺x Zrx 兲O3 are clear but the third transition is not obvious. For x
are of single phase with a perovskite structure. The fibers ⭓0.15, the three phase transitions merge together in one
were translucent for x⫽0.05 and 0.08, and opaque for x broad peak. The phase transition temperatures are summa-
412 J. Appl. Phys., Vol. 88, No. 1, 1 July 2000 Yu, Guo, and Bhalla

FIG. 3. Phase diagram for the Ba共Ti1⫺x Zrx 兲O3 (x⭐0.2) based on the mea-
sured parameters in single crystals.

FIG. 2. Temperature dependence of the dielectric constant 共⑀兲 at 1 kHz for

the Ba共Ti1⫺x Zrx 兲O3 crystals with x⫽0.05, 0.08, 0.15, and 0.2.
2. Fit to the Curie – Weiss law
The temperature dependence of the inverse dielectric
constant 共1/⑀兲 is shown in Fig. 4. By fitting the experimental
rized in Table II. The data collected on current ceramic data to the Curie–Weiss law,
samples and those gathered from the literature are also listed
for comparison. It can be seen that the data are in good ⑀ ⫽C/ 共 T⫺⌰ 兲 , 共1兲
agreement with each other, indicating the compositions of
the grown fibers retained the starting stoichiometry of the
the fit parameters of Curie constant C and Curie temperature
ceramics. This also indicates that a near-congruent melting
⌰ are obtained, as listed in Table III. The fit parameters
growth condition was met, which allowed the successful
show that the C and ⌰ are almost the same for x⫽0.05 and
single-crystal growth by LHPG. It is noticed that the orien- 0.08. With further increasing x, ⌰ decreases.
tation of the crystal cuts has less influence on the phase tran-
sition temperatures, however, the magnitude of the dielectric
constant may vary.
The phase transition temperatures 共T c , T 2 , and T 3 兲 as a 3. Hysteresis loops
function of x for the single crystals are shown in Fig. 3. It is Hysteresis loops were measured for the single-crystal
seen that T c is decreased and T 2 and T 3 are increased with x samples with applied ac fields up to ⬃25 kV cm⫺1 at 1 Hz at
for x⬍0.15. For x⬎0.15, the three phase transitions merge room temperature, as shown in Fig. 5. Remnant polarization
together and the phase transition temperature decreases with ( P r ) and coercive fields (E c ) are 17.1 ␮C/cm2 and 2.2
further increase in Zr content. This diagram is reasonably in kV/cm for x⫽0.05; 18.3 ␮C/cm2 and 1.2 kV/cm for x
accordance with that obtained from the ceramics,11–13 with ⫽0.08, 7.5 ␮C/cm2 and 2.5 kV/cm for x⫽0.15, and 4.0
minor differences as the phase transition temperatures could ␮C/cm2 and 6.5 kV/cm for x⫽0.2. The P r values of the
be influenced by different sintering conditions.14 At room single crystals are much higher than those of the ceramic
temperature, the sample with x⫽0.05 is orthorhombic, and samples 共P r ⫽12.0, 10.8, 3.0, and 2.0 ␮C/cm2 for ceramic
the samples with x⫽0.08 and x⫽0.15 are rhombohedral. samples with x⫽0.05, 0.08, 0.15, and 0.2, respectively兲.

TABLE II. Phase transition temperatures 共T c , T 2 , T 3 , or T m 兲 at 1 kHz for both Ba共Ti1⫺x Zrx 兲O3 crystals and
ceramics.

x⫽0.05 x⫽0.08 x⫽0.15 x⫽0.2

T c , T 2 , T 3 , or T m
共°C兲 共1 kHz兲 Tc T2 T3 Tc T2 T3 Tm Tm

Fibers
共cooling兲 110 51 0 102 71 30a 65 32
共heating兲 111 55 ¯ 102 74 ¯ ¯ ¯

Ceramics 共this
work, cooling兲 110 51 0 99 71 33a 67 32
b
Ceramics 109 54 2 100 68 25 65 37
a
Data from loss peak at 1 kHz.
b
References 5 and 13.
J. Appl. Phys., Vol. 88, No. 1, 1 July 2000 Yu, Guo, and Bhalla 413

FIG. 4. Temperature dependence of the inverse dielectric constant 共1/⑀兲 for

the Ba共Ti1⫺x Zrx 兲O3 crystals with x⫽0.05, 0.08, 0.15, and 0.2. Solid lines
are fittings to the Curie–Weiss law.

4. Dielectric relaxation behavior in the sample with FIG. 5. Hysteresis loops of the Ba共Ti1⫺x Zrx 兲O3 crystals with x⫽0.05, 0.08,
x Ä0.08 0.15, and 0.2.

It is well known that impurity-doped BaTiO3 共Refs. 18–

23兲 shows a transition from a traditional ferroelectric to a
‘‘relaxor-like ferroelectric’’ 24 with increasing concentration the dielectric loss is more sensitive to a small distortion or
of the impurity. One of the characteristics of the ‘‘relaxor appearance of polar microregions in the samples; similar
ferroelectric’’ is the frequency dispersion, i.e., the tempera- phenomena were also observed in Bi-doped SrTiO3. 25,26
ture (T m ) of the dielectric constant maximum increases with In order to characterize these dielectric modes, Cole–
increasing frequency. The first example for the ‘‘ferroelectric Cole plots for these two dielectric relaxation modes are
relaxor’’ is found in Sn-doped BaTiO3 solid solutions.18 One drawn in Fig. 7. The data points for both peaks fit into two
of the authors has also observed the obvious transition from semicircular arcs with the centers lying underneath the ab-
typical traditional ferroelectric to a ‘‘relaxor ferroelectric’’ in scissa, deviated from the ideal Debye model to some extent.
Ce- or Y-doped BaTiO3. 19,20 The ‘‘relaxor’’ behavior in Zr- Hence, the modified Debye equation is adopted to evaluate
doped BaTiO3 ceramics was reported earlier by Hennings the dielectric relaxation. The complex permittivity can em-
and Schnell,13 and recently by Ravez and Simon.21–23 Ravez pirically be described by the equation27
and Simon reported that Ba共Ti1⫺x Zrx 兲O3 ceramics show tra-
ditional ferroelectric behavior for 0⭐x⬍0.1 and a typical ⑀ * ⫽ ⑀ ⬁ ⫹ 共 ⑀ 0 ⫺ ⑀ ⬁ 兲 / 关 1⫹ 共 i ␻ ␶ 兲 ␤ 兴 , 共2兲
‘‘relaxor ferroelectric’’ behavior for 0.26⬍x⭐0.4. In the re-
gion of 0.1⭐x⭐0.26, the transition at T m is only rounded
共i.e., diffuse兲 without any frequency dispersion.21–23
In the present work, indeed, we have not observed any
frequency dispersion for the x⫽0.05 single crystal. For the
samples with higher Zr concentration 共x⫽0.15 and 0.2兲, only
one dielectric peak is observed, which is rounded with the
T m being independent of frequency. However, the tempera-
ture dependence of the dielectric constant 共⑀兲 and loss (tan ␦)
for the sample with x⫽0.08 at different frequencies shows
that there is no frequency dispersion at the first peak T c or
second peak T 2 , but the two dielectric relaxation processes
are observed at the third phase transition T 3 共denoted as the
T 3 mode, shown by dash curves兲 and at lower temperatures
共denoted as the LT mode, shown by solid curves兲, as shown
in Fig. 6. It should be pointed out that this behavior can be
seen clearly in the dielectric loss curves. This indicates that

TABLE III. Fit parameters of the Curie–Weiss law for the Ba共Ti1⫺x Zrx 兲O3
single crystals at 10 kHz.

Composition x⫽0.05 x⫽0.08 x⫽0.15 x⫽0.2

Curie– ⌰ 373 K 373 K 338 K 293 K FIG. 6. Temperature dependence of the dielectric constant 共⑀兲 and loss
Weiss law C 1.7⫻105 K 1.8⫻105 K 1.6⫻105 K 2.1⫻105 K (tan ␦) at different frequencies for the Ba共Ti1⫺x Zrx 兲O3 single crystal with
x⫽0.08 along the 具110典 direction.
414 J. Appl. Phys., Vol. 88, No. 1, 1 July 2000 Yu, Guo, and Bhalla

For the middle doping concentration x⫽0.08, the T m of the

first and second peaks are independent of frequency, which
could be due to the higher phase transition temperatures;
however, for the third phase transition at relatively lower
temperatures, its long-range ordering is easier to disturb by
the doping impurity, and frequency dispersion occurs. In ad-
FIG. 7. Cole–Cole plot 共⑀ ⬙ vs ⑀ ⬘ 兲 for the T 3 mode and the LT mode in the
Ba共Ti1⫺x Zrx 兲O3 single crystal with x⫽0.08 共open circles: experimental dition, this mode might couple with the dielectric relaxation
data; circular arcs: fitting curves兲. process—the LT mode. The clear understanding needs fur-
ther investigation.
In the earlier literature, a dielectric relaxation mode was
where ⑀ 0 is the static permittivity, ⑀ ⬁ is the permittivity at
reported at the low-temperature side of a ferroelectric 共or
high frequency, ␻ is the angular frequency, ␶ is the mean
relaxor ferroelectric兲 peak,19,28 similar to the LT mode ob-
relaxation time, and ␤ ⫽1⫺ ␣ , where ␣ is the angle of the
served in the present work. In the Ba共Ti1⫺x Cex O3) ceramics
semicircular arc.
The real and imaginary parts of the permittivity can be with x⫽0.1, below the ferroelectric–paraelectric phase tran-
rewritten from Eq. 共2兲 in the following way: sition, an extra dielectric relaxation mode occurs.19 The co-
existence of the LT mode and a ferroelectric–paraelectric
⑀ ⬘ ⫽ ⑀ ⬁ ⫹ 共 ⌬ ⑀ ⬘ /2兲 兵 1⫺sinh共 ␤ z 兲 / 关 cosh共 ␤ z 兲 phase transition in the tungsten bronze ferroelectric relaxor
⫹cos共 ␤ ␲ /2兲兴 其 , 共3兲 PbNb2O6 – BaNb2O6 system has been also reported, and ex-
plained by a polarization fluctuation mechanism.28 It seems
⑀ ⬙ ⫽ 共 ⌬ ⑀ ⬘ /2兲 sin共 ␤ ␲ /2兲 / 关 cosh共 ␤ z 兲 ⫹cos共 ␤ ␲ /2兲兴 , 共4兲 this type of relaxation behavior is the common feature of the
where z⫽ln(␻␶) and ⌬ ⑀ ⬘ ⫽ ⑀ 0 ⫺ ⑀ ⬁ . solid solution regardless of the sample being a single-crystal
By fitting the experimental data to Eqs. 共2兲–共4兲, we can or polycrystalline ceramic; this also indicates that the relax-
obtain the parameters, ⑀ 0 , ⑀ ⬁ , ␤, and ␶ as a function of ation behavior is not associated with the grain-boundary phe-
temperature. The obtained relaxation times for the T 3 mode nomenon.
and for the LT mode are plotted as a function of inverse
temperature in Fig. 8. It is found that the relaxation time
follows the Arrhenius law
␶ ⫽ ␶ 0 exp关 E relax / 共 k B T 兲兴 , 共5兲
IV. CONCLUSIONS
where ␶ 0 is the relaxation time at infinite temperature, E relax
共1兲 Single crystals for Ba共Ti1⫺x Zrx 兲O3 with x⫽0.05, 0.08,
the activation energy for relaxation, k B the Boltzmann’s con-
0.15, and 0.2 have been successfully grown by the
stant, and T the temperature. The parameters, ␶ 0 ⫽0.4
LHPG technique, and the compositions of the grown
⫻10⫺13 s 共i.e., f 0 ⫽4⫻1012 Hz兲, E relax⫽0.53 eV for the T 3
mode, and ␶ 0 ⫽0.8⫻10⫺10 s 共i.e., f 0 ⫽2⫻109 Hz兲, E relax crystals are found to retain the starting compositions.
⫽0.46 eV for the LT mode, are obtained. 共2兲 The dielectric properties of the single crystals have been
‘‘Why does the dielectric relaxation behavior 共T 3 mode兲 measured. The results are overall in agreement with
occur only for the third phase transition in the sample with those obtained from the corresponding ceramics.
x⫽0.08?’’ A tentative explanation could be as follows. For 共3兲 The phase diagram has been established for the single
x⫽0.05, the doping concentration is small and the three crystals for x⭐0.2.
sharp phase transition peaks are clearly observed without fre- 共4兲 The P r values obtained from single crystals are higher
quency dispersion. For x⫽0.15 and 0.2, the three phase tran- than those of the corresponding ceramics, as expected.
sitions are pinched into a rounded peak without frequency 共5兲 The small dielectric relaxation mode has been observed
dispersion; for the pinched peak it is probable that the Zr for the third phase transition of the sample with x
concentration is not high enough to show a relaxor behavior. ⫽0.08. The relaxation times follow the Arrhenius law
with ␶ 0 ⫽0.4⫻10⫺13 s (4⫻1012 Hz) and E relax
⫽0.53 eV.
共6兲 A common feature—the low-temperature relaxation
mode in the solid solution—is also observed, which fol-
lows the Arrehenius law with typical ␶ 0 ⫽0.8⫻10⫺10 s
(2⫻109 Hz), E relax⫽0.46 eV.

In order to study the high electric-field dependence of

the strain behavior and potential induced phase transitions, it
is necessary to grow and study single crystals of various
orientations. The authors are currently carrying on additional
growth efforts and characterization on the strain, electric
FIG. 8. Relaxation times ␶ vs 1/T for the T 3 mode and the LT mode in the
Ba共Ti1⫺x Zrx 兲O3 single crystal with x⫽0.08 共open circles: experimental field, and orientation dependence, which would be the sub-
data; solid lines: fitting to the Arrhenius law兲. ject of future publications.
J. Appl. Phys., Vol. 88, No. 1, 1 July 2000 Yu, Guo, and Bhalla 415

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