Enhanced piezoelectricity of barium titanate

single crystals with engineered domain

configuration
S. Wada and T. Tsurumi

Engineered domain configurations with diVerent domain

sizes were induced in [111] oriented tetragonal barium
c
titanate BaT iO single crystals, and their piezoelectric
3
properties investigated as a function of domain size.
Prior to this study, the dependence of domain configuration on temperature and electric field E was investigated using polarised light microscopy to establish the
optimum conditions for domain size control. As a result,
above the Curie temperature T of 132.2C, when E
c
greater than 6 kV cm1 was applied along the [111]
c
direction, an engineered domain configuration with fine
domain structure appeared. Moreover, it was also found
that this fine domain structure was still stable at room
temperature in the absence of electric field. Finally, the
piezoelectric properties were measured using 31
resonators with three domain sizes, and it was found
that piezoelectric properties such as d and k
31
31
increased significantly with decreasing domain size.
BCT /707

using [111] oriented tetragonal BaTiO crystals.7,8 The

c
3
d of [111] poled tetragonal BaTiO crystals with engine33
c
3
ered domain configuration was #203 pC N1, over twice
as large as the value for [001] poled BaTiO single domain
c
3
crystals (90 pC N1). What is more, d for a [001] poled
33
c
rhombohedral PZNPT crystal with engineered domain
configuration was almost 30 times larger than for a [111]
c
poled PZNPT single domain crystal (83 pC N1).3 To
explain this huge difference, attention in the present study
was focused on the domain size in the engineered domain
configuration. This is because the domain structure of the
[001] poled PZNPT crystal was composed of fine fibrec
like domains with a width of #1 mm,9,10 while that of
[111] poled BaTiO crystals was made up of very coarse
c
3
domains (300400 mm width7). Thus it is proposed that
when a fine domain structure is induced in [111] poled
c

Keywords: Barium titanate, Domain engineering,

Domain size, Piezoelectricity, Single crystals.
T he authors are in the Department of Metallurgy and
Ceramic Science, Graduate School of Science and
Engineering, T okyo Institute of T echnology, 2-12-1
Ookayama, Meguro-ku, T okyo 1528552, Japan
(swada@ceram.titech.ac.jp). Paper presented at the
symposium 55 years of ferroelectrics held in L eeds,
UK on 2123 September 2003. Manuscript accepted
without revision 24 February 2004.
2004 IoM Communications L td. Published by Maney for
the Institute of Materials, Minerals and Mining.

INTRODUCTION
Domain engineering is a very important technique for
obtaining enhanced piezoelectric and ferroelectric properties in ferroelectric single crystals. In [001] oriented
c
rhombohedral PZNPT single crystals, ultrahigh piezoelectric activity was found by Park et al.13 and Kuwata
et al.,4,5 with strain >17%, piezoelectric constant d
33
>2500 pC N1, electromechanical coupling factor k
33
>93% and hysteresis free strain v. electric field behaviour.
These ultrahigh piezoelectric properties resulted from the
use of a domain engineering technique. This technique
utilises the anisotropy of ferroelectric single crystals, however crystal structure is also very important.6
Single crystals of BaTiO have tetragonal P4mm phase
3
at room temperature. To induce an engineered domain
configuration into tetragonal crystals, E field should be
applied along the [111] direction as shown in Fig. 1. In
c
this manner, piezoelectric properties have been investigated
DOI 10.1179/096797804225012747
bct0000707 12-03-04 17:48:28 Rev 14.05
The Charlesworth Group, Huddersfield 01484 517077

1 Schematic diagram of engineered domain configuration

in tetragonal crystal
British Ceramic Transactions 2004 Vol. 103 No. 2

Wada and T surumi Enhanced piezoelectricity of barium titanate single crystals

2 Dependence of domain size on E field and temperature

for [111] oriented BaTiO single crystal with engineered
c
3
domain configuration
tetragonal BaTiO crystals with engineered domain con3
figuration, it may be possible to obtain much enhanced
piezoelectricity.
In the present study, the piezoelectric properties of
BaTiO single crystals were investigated as a function of
3
domain size. To this end, domain size was investigated in
[111] oriented tetragonal BaTiO crystals with engineered
c
3
domain configuration as a function of field strength and
temperature.

EXPERIMENTAL PROCEDURES
BaTiO single crystals were grown by a top seeded solution
3
growth (TSSG) method at Fujikura Ltd. In TSSG grown
BaTiO single crystals, the concentration of most impurities
3
(Cr, Mn, Fe, Co, Ni, Cu) is below 23 ppm. The details of
preparation of BaTiO single crystals and their characteris3
ation are described elsewhere.1113 These crystals were
oriented along the [111] direction using a back reflection
c
Laue method.
For in situ domain observation at various E fields and
temperatures, crystals were prepared by cutting and
polishing to an optimum size of 020520 mm
(02 mm//[1-10] , 05 mm//[111] , 2 mm//[11-2] ). Top
c
c
c
and bottom surfaces (0520 mm) were mirror polished
to give a thickness between top and bottom of #200 mm
along an incident direction of light. Gold electrodes
were sputtered on both sides (0220 mm) parallel to the
light. Domain configuration was always observed under
crossed nicols using a polarising microscope (Nikon,
Labophoto2-POL). A unipolar E field exposure was carried
out along the [111] direction, normal to incident polarised
c
light, using a Kepco BOP-1000M high voltage dc amplifier.
The crystal was placed in a cryostat with an optical isotropic
glass window (Linkam, LK-600PM) in dry air. Temperature
just below the bottom of the crystal was measured, and
then changed from 0 to 200C at a rate of 041 K min1.
The temperature in the cryostat was measured to an
accuracy of 01C and controlled to within 0.1C.
For piezoelectric measurement using 31 resonators,
BaTiO single crystals were sized to 4.01.20.4 mm
3
(40 mm//[1-10] , 12 mm//[11-2] , 04 mm//[111] ) by
c
c
c
cutting and polishing using fine Al O powders. Gold
2 3
electrodes were sputtered on both sides (4012 mm).
Poling treatment for the preparation of BaTiO crystals
3
with different domain sizes was performed on the basis of
the observed dependence of domain size on E field and
temperature. After poling, domain configuration was
investigated using polarised light microscopy. Finally,
piezoelectric properties were measured using an impedance
analyser (Agilent, HP-4294A) by a conventional resonance
antiresonance method.14
British Ceramic Transactions 2004 Vol. 103 No. 2
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The Charlesworth Group, Huddersfield 01484 517077

3 Domain configurations in seven regions (AG) of [111]

c
oriented BaTiO single crystal with engineered domain
3
configuration

RESULTS AND DISCUSSION

Dependence of domain size on E field and temperature
To understand the dependence of domain size on E field
and temperature for [111] oriented BaTiO crystals,
c
3
domain structures were observed at various temperatures
from 0 to 200C and various E fields from 0 to 20 kV cm1.
Before domain observation, BaTiO crystals were heated
3
up to 140C, and then cooled down to the observation
temperature at a cooling rate of 04 K min1 without E
field. At constant temperature, E field was applied very
slowly along the [111] direction.
c
Figure 2 shows the variation of domain size with E field
and temperature for [111] oriented BaTiO crystals with
c
3
engineered domain configuration. In addition, Fig. 3 shows
typical domain structures observed in various regions in
Fig. 2. In Fig. 2, the A and B regions were assigned to
orthorhombic mm2 phase. At 25C, E field exposure
along the [111] direction for tetragonal BaTiO crystals
c
3
resulted in E field induced phase transition from 4mm to
mm2, consistent with previous reports.68,15 Figures 3a
and b demonstrate that these domain structures were composed of fine domains, but when E field was removed,
domain structure easily returned to the normal tetragonal
domain configuration as shown in Fig. 3c. Thus the
fine domain structure in the A and B regions cannot exist

Wada and T surumi Enhanced piezoelectricity of barium titanate single crystals

5 Schematic diagram of engineered domain configurations

induced by poling treatment: a >40 mm domain size,
b 133 mm, 65 mm
gence is unknown. In the F region, coexistence of the bright
state without domain walls and a fine domain state was
observed. In the G region, only fine domain structure was
clearly observed, and all domain walls were assigned to
{110} planes. In the A, B, C and D regions, symmetries
c
were assigned on the basis of previous reports.68,15
However, there is no published information about the E,
F and G regions. Thus these symmetries were measured
in situ with additional use of polarised light microscopy.

Domain size dependence of piezoelectricity

On the basis of the results of domain size dependence on
E field and temperature, three kinds of domain size were
induced in BaTiO single crystals with engineered domain
3
configuration. The engineered domain BaTiO crystal with
3
large domain size was poled at just below T , while the
c
crystal with finer domain size was poled at just above T .
c
Figure 4 shows BaTiO single crystals with three domain
3
sizes, >40 mm (Fig. 4a), 133 mm (Fig. 4b) and 65 mm
(Fig. 4c). All domain walls observed in Fig. 4 were assigned
to the 90 type on (011) . Under crossed nicols, Fig. 4a was
c
monochrome, suggesting that these domain walls were
continuous from top to bottom as shown in Fig. 5a. On
the other hand, in Fig. 4b and c, a distribution of various
colours (birefringence) was clearly observed, suggesting that
along [111] direction, there were laminated fine domain
c
structures as shown in Fig. 5b and c. At present, it is
considered that the above poling treatment induced the
schematic engineered domain configurations shown in
Fig. 5 in the [111] poled BaTiO single crystals.
c
3
Using the 31 resonators with three domain sizes, piezoelectric properties were measured by a conventional resonanceantiresonance method. Figures 6 and 7 show the
frequency dependence of impedance and phase for the 31
resonators with domain sizes of >40 and 65 mm respectively. If the poling treatment is completely successful, the

4 Variation of domain configuration with domain size:

a >40 mm domain size, b 133 mm, c 65 mm
stably at room temperature without E field. The C region
was assigned to tetragonal 4mm symmetry. By poling treatment in this region, domain structure was modified, but all
observed domain walls were completely assigned to the 90
type along {110} planes, as shown in Fig. 3c. The D region
c
was assigned to the optical isotropic state with cubic m3m
symmetry, as shown in Fig. 3d. On the other hand, the E
region was very unclear. The brightness in the E region
suggested that this domain state was not optically isotropic,
but an anisotropic state. When E field is applied along the
[111] direction for cubic m3m symmetry, the cubic m3m
c
symmetry can be slightly distorted to rhombohedral or
monoclinic symmetry. At present, the origin of this birefrin-

6 Frequency dependence of impedance and phase for [111]

c
poled BaTiO crystals with domain size >40 mm
3
British Ceramic Transactions 2004 Vol. 103 No. 2

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The Charlesworth Group, Huddersfield 01484 517077

Wada and T surumi Enhanced piezoelectricity of barium titanate single crystals

CONCLUSIONS

7 Frequency dependence of impedance and phase for [111]

c
poled BaTiO crystals with 65 mm domain size
3
phase between resonance and antiresonance frequencies
should be close to +90. In Figs. 6 and 7, the maximum
phase angles were +50 and +15 respectively. These low
phase angles suggest an inadequate poling treatment.
Using these resonance and antiresonance frequencies,
piezoelectric constants were estimated and are summarised
in Table 1. Measurements by Zgonik et al.16 for [001]
c
oriented BaTiO single domain crystals and calculated d
3
31
values for [111] oriented BaTiO single domain crystals
c
3
are included in Table 1. An engineered domain BaTiO
3
crystal with domain size >40 mm possessed much higher
piezoelectricity than [001] and [111] oriented BaTiO
c
c
3
single domain crystals. The most surprising result, however,
is that piezoelectric properties depend clearly on domain
width. Piezoelectric properties such as d and k increased
31
31
significantly with decreasing domain size. Moreover, Table 1
gives the high piezoelectric properties of soft PZT ceramics
reported by Jaffe et al.17 For a BaTiO crystal with a
3
domain size of 65 mm, d of 1801 pC N1 and k of
31
31
414% were close to the d of 1710 pC N1 and k of
31
31
344% of these soft PZT ceramics. It was therefore concluded that the engineered domain configurations with fine
domain sizes were very important in inducing enhanced
piezoelectric properties in lead free piezoelectric materials.
Furthermore, these results suggested that 90 domain walls
can contribute significantly to piezoelectricity for an engineered domain configuration. Thus the role of 90 domain
walls on piezoelectric properties must be considered. Liu
et al. reported a model for the role of non-180 domain
walls in engineered domain configurations,18 and it is
believed this will be useful in explaining the enhanced
piezoelectric properties observed in this study.
Table 1 Piezoelectric properties of BaTiO single crystals
3
poled along [001] and [111] directions
c
c
BaTiO single crystal
3

eT
33

sE ,
11
pm2 N1

d ,
31
pC N1

k ,
31
%

[001] (single domain)*

c
[111] (single domain)
c
[111] (>40 mm domain size)
c
[111] (133 mm domain size)
c
[111] (65 mm domain size)
c
Soft PZT ceramic

129

2185
2087
2441
1700

74

737
768
880
164

33.4
620
978
1347
1801
1710

259
357
414
344

* Measured by Zgonik et al.16

Calculated using values measured by Zgonik et al.16
Measured by Jaffe et al.17
British Ceramic Transactions 2004 Vol. 103 No. 2
bct0000707 12-03-04 17:48:28 Rev 14.05
The Charlesworth Group, Huddersfield 01484 517077

In the present study, engineered domain configurations

with different domain sizes were induced in tetragonal
BaTiO single crystals, and their piezoelectric properties
3
investigated as a function of domain size. Prior to this
study, the dependence of domain configuration on temperature and E field was investigated using a polarised light
microscope to establish the optimum conditions for fine
and coarse domain structures. As a result, at 1330C, when
an E field of >6 kV cm1 was applied along the [111]
c
direction, an engineered domain configuration with a fine
domain size of 65 mm appeared. Moreover, it was found
that this fine domain structure was still stable at room
temperature without E field. On the other hand, coarse
domain structure was obtained by poling at 128.0C.
Finally, piezoelectric properties were measured using 31
resonators with different domain sizes. As a result, BaTiO
3
single crystals with engineered domain configurations
exhibited much enhanced piezoelectric properties. It was
also found that piezoelectric properties such as d and k
31
31
increased significantly with decreasing domain size. These
results show that non-180 domain walls can contribute
significantly to piezoelectric properties in engineered
domain configurations.

ACKNOWLEDGEMENTS
The authors would like to thank Mr O. Nakao of Fujikura
Ltd for preparing TSSG grown BaTiO single crystals with
3
excellent chemical quality, Dr J. Erhart of ICPR of the
Technical University of Liberec for helpful discussions on
the analysis of domain configuration, and especially Dr
L. E. Cross, Dr T. R. Shrout and Dr S.-E. Eagle Park for
the opportunity to study engineered domain configurations.
This study was partially supported by the Japan Securities
Scholarship Foundation.

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