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Journal of the European Ceramic Society 34 (2014) 1445–1448

Short Communication

Grain size effect on piezoelectric and ferroelectric properties

of BaTiO3 ceramics
Yu Huan, Xiaohui Wang ∗ , Jian Fang, Longtu Li
State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering, Tsinghua University, Beijing 100084, China
Received 26 September 2013; received in revised form 19 November 2013; accepted 21 November 2013
Available online 19 December 2013

Abstract
A series of dense barium titanate (BaTiO3 , BTO) ceramics with different grain sizes (GS) were prepared by two-step sintering method. The effect
of GS on piezoelectric coefficient (d33 ) and planar electromechanical coupling factor (kp ) displayed a trend similar to that on relative permittivity
(ε ). The values of d33 , kp , and ε increased significantly with decreasing GS, reaching maximum values (ε = 6079, d33 = 519 pC/N and kp = 39.5%)
at approximately 1 ␮m, and then decreased rapidly with further decreasing GS. The results revealed that high-performance BTO ceramics could
be effectively prepared by controlling GS. Polarization–electric field hysteresis loops and temperature dependence of ε were also investigated.
© 2013 Elsevier Ltd. All rights reserved.

Keywords: Barium titanate; Grain size; Piezoelectric and ferroelectric properties

1. Introduction In this study, a series of dense BTO ceramics with different

Barium titanate (BTO) ceramics are historically the first poly-
crystalline piezoelectric materials and extensively applied for
piezoelectric actuators, sensors, and transducers. For several
decades, BTO-based ceramics have been believed to exhibit
modest piezoelectric activity, with piezoelectric coefficient (d33 )
of approximately 191 pC/N, incomparable to certain commer-
cial lead zirconate titanate ceramics,1 posing potential hazard to
the environment. Moreover, recent studies revealed that values
of piezoelectric properties namely, d33 , planar electromechani-
cal coupling factor (kp ), and relative permittivity (ε ) increased
by controlling grain size (GS),2,3 thus; significantly revitalizing
the BTO-based lead-free piezoceramics, in consideration of the
miniaturization and integration of microelectronics industry.4,5
However, dependence of polarization–electric field hysteresis
(P–E) loops on GS, and ε dependence on temperature for the fine
ceramics having GS below 500 nm have rarely been investigated.
Therefore, the development of the next generation lead-free
piezoelectric devices is indispensable to understand the effect
of GS on the piezoelectric properties of BTO ceramics.
∗ Corresponding author. Tel.: +86 010 62792689; fax: +86 010 62771160.
E-mail address: wxh@mail.tsinghua.edu.cn (X. Wang).
GS in the range from 0.29 ␮m to 8.61 ␮m are successfully syn-
thesized by two-step sintering method,6,7 and the effect of GS on
piezoelectric, ferroelectric properties and phase structures were
systematically investigated. Thus kp , d33 and ε exhibited the
similar dependence on GS. Furthermore, a possible mechanism
leading to the aforementioned novel phenomenon was explained
from the aspects of domain structure and grain boundary.
2. Experimental procedure
Hydrothermal synthesized BTO powder with an average par-
ticle size of 100 nm (BT-01, Sakai Chemical, Osaka, Japan) is
used as the raw powder. BTO ceramics with several GS were
prepared by two-step sintering method following the exper-
imental procedures reported in literature.8 ε was measured
at room temperature and 1 kHz using a capacitance meter
(HP4278A, Hewlett-Packard, Palo Alto, CA). A quasistatic
d33 meter (ZJ-3A, Institute of Acoustics, Chinese Academy of
Sciences, Beijing, China) was used to measure d33 . kp is deter-
mined by an impedance analyzer (HP4194A, Hewlett-Packard,
Palo Alto, CA) using the resonance–anti-resonance method.
P–E hysteresis loops were measured at room temperature by a
ferroelectric tester (RT6000HVA, Radiant Technologies, North-
ford, Connecticut). Temperature dependence of ε is measured

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1446 Y. Huan et al. / Journal of the European Ceramic Society 34 (2014) 1445–1448

Fig. 2. (a) XRD patterns of the BTO ceramics with different GS and (b) the
corresponding expanded XRD patterns in the 2θ from 44◦ to 46◦ .

samples exhibited high density and uniform grain size distribu-

tion, suggesting that two-step sintering method is an effective
approach to prepare dense and fine-grained BTO ceramics. Fur-
thermore, fine grain and homogenous microstructure led to high
mechanical strength and enhanced piezoelectric properties.
Fig. 2 shows that all the BTO ceramics are in the tetragonal
phase (JCPDS-ICDD file no. 05-0626) owning to the appar-
ent splitting of the (0 0 2) and (2 0 0) peaks. Moreover, Bragg
Fig. 1. SEM images of the BTO ceramics with average GS of (a) 0.29 ␮m, (b) angle of (0 0 2) peak decreased and (2 0 0) peak shifted to higher
0.36 ␮m, (c) 0.56 ␮m, (d) 0.62 ␮m, (e) 0.99 ␮m, (f) 1.97 ␮m, (g) 3.64 ␮m and angle. Thus, lattice parameter a decreases, c increases; hence, the
(h) 8.61 ␮m. tetragonal distortion (c/a) increases continuously with increas-
ing GS (Table 1), which are in agreement with the previously
by multi-frequency inductance capacitance resistance analyzer reported results.9
(Agilent E4980A, Santa Clara, CA) with an automated tem- ε , d33 , and kp dependence on GS of BTO ceramics is shown in
perature controller with heating rate of 2 ◦ C/min. Crystalline Fig. 3. Remarkably, d33 and kp exhibited a trend similar to ε : The
structure of the ceramics was determined by X-ray diffraction values of d33 , kp , and ε increased significantly with decreasing
(XRD; Rigaku 2500, Rigaku, Tokyo, Japan) using a monochro- GS, reaching maximum values (ε = 6079, d33 = 519 pC/N and
mator for Cu K␣ radiation. The GS were measured by scanning kp = 39.5%) at approximately 1 ␮m, and then decreased rapidly
electron microscope (SEM, Leo-1530, Oberkochen, Germany). with further decreasing GS. The coarse-grained BTO ceramic
with GS of 8.61 ␮m exhibited d33 value of 160 pC/N, which
3. Results and discussion is in agreement with the reported value of 191 pC/N.1 In con-
stant, the fine-grained samples with GS of approximately 1 ␮m
The density of the specimens was measured by the showed a very high d33 value of 519 pC/N, proclaiming that the
Archimedes method using distilled water. Relative density (RD) synthesized BTO ceramics were of good quality and the obtained
was calculated using the theoretical density of 6.02 g/cm3 for the experimental results were significant and reliable, which indi-
pure BTO ceramics as shown in Fig. 3. The RD was more than cated that the high-performance BTO piezoceramics could be
95% for all the samples. The GS of the BTO ceramics were
measured by SEM micrographs after being polished and etched Table 1
thermally under 1000 ◦ C for 1 h as shown in Fig. 1. The GS Lattice parameters and tetragonal distortion of the BTO ceramics with different
was measured as follows. First, four straight lines connecting GS.
two diagonal lines; and two straight lines across midpoint were GS (␮m) ´
a = b (Å) ´
c (Å) c/a
drawn in the micrograph. Second, the total length of the four
0.29 3.9992 4.0296 1.0076
straight lines was measured using the scale and the total grain 0.5 3.9982 4.0302 1.0080
number was calculated. Finally, the total length was divided by 0.59 3.9982 4.0334 1.0088
the total grain number to obtain the average GS. Several graphs 1.19 3.9968 4.0348 1.0095
were plotted to improve the accuracy. However, the error range 1.28 3.9955 4.0350 1.0099
of the non-uniform GS was approximately ± 30%. A series of 2.21 3.9948 4.0352 1.0101
4.32 3.9938 4.0353 1.0104
BTO ceramics with the GS in the range of 0.29–8.61 ␮m were 8.61 3.9926 4.0358 1.0108
successfully synthesized by two-step sintering method. All the
 Y. Huan et al. / Journal of the European Ceramic Society 34 (2014) 1445–1448
Fig. 3. ε , d33 , kp , and relative density dependence on GS of the BTO ceramics.
effectively prepared by controlling GS. Moreover, the significant
similarity between the dependence of d33 and ε on GS indicated
that both of them possibly had the same physical origin.
The piezoelectric properties of the piezoceramics could be
strongly attributed to intrinsic and extrinsic contribution.10
Though there was a little difference of the XRD profiles among
the BTO ceramics, the slight variation of the phase structure
apparently did not account for the strong GS dependence of
piezoelectric properties because they were directly connected to
spontaneous polarization from the viewpoint of intrinsic contri-
bution. Subsequently, extrinsic factors, in particular, the domain
structure are considered likely to make a substantial contribu-
tion. The relationship between domain structure and GS has
been reported in our previous research.8 For GS > 1 ␮m, the
90◦ domain width decreased with decreasing GS. Smaller the
domain width indicated the smaller the areas of domain walls
and the piezoelectric properties were influenced by the move-
ment of 90◦ domain walls.11 The domain walls with small areas
rotate easily and response more actively to the external elec-
tric or stress signal, contributing to the excellent piezoelectric
properties.12 For GS < 1 ␮m, the domain width decreased with
decreasing GS, leading to an increase in the volume proportion
of the domain walls. Moreover, the volume ratio of the grain
boundary increased significantly, resulting in a “dilution” effect
in domain density, similar to the “brick-wall” model,13 leading
Fig. 4. (a) ε versus temperature curves of the BTO ceramics with different GS and (b) evolutions of TO–T and TT–C as functions of GS.
1447
to a decrease in ε . Consequently, the increase in domain and
grain boundary led to a decrease in domain density resulting in
the degradation of piezoelectric properties.
Temperature dependence of ε for the BTO ceramics with
characteristics GS values measured during the heating process
at a rate of 2 ◦ C/min and 1 kHz is shown in Fig. 4(a). The two
peaks in either curve correspond to the orthorhombic–tetragonal
phase transition (TO–T ) and tetragonal–cubic ferroelectric phase
transition (TT–C ), respectively. The peak corresponding to TO–T
is quite broad, the one corresponding to TT–C is relatively
sharp. In this study, the peak value of ε first increased, and
then decreased with increasing GS and the trend is consistent
with the previous reports about GS dependence of ε for BTO
ceramics.11 The depression of the fine-ceramics ε is explained
by a “brick-wall” model of the ceramics corresponding to a
diphasic system consisting of ferroelectric grain cores and the
lower ε grain boundary region.13 The evolutions of TO–T and
TT–C as a function of GS are shown in Fig. 4(b) indicating that
TT–C decreased but TO–T increased with decreasing GS. The
variation trend is in accordance with our previous result, calcu-
lated by Landau–Ginzburg–Devonshire theory14 : with reducing
GS, TO–T becomes higher and TT–C becomes lower due to the
effect of internal stress.
P–E hysteresis loops for the BTO ceramics with charac-
teristics GS values are shown in Fig. 5(a). Although the P–E
hysteresis loops of the BTO ceramics are well saturated, their
remnant polarization (Pr ) and coercive field (Ec ) are distinct.
The evolutions of Pr and Ec as functions of GS are illustrated
in Fig. 5(b). Pr enhances rapidly with the increase of GS for
GS < 1 ␮m and the increasing tendency slows down with a fur-
ther increase in GS. For the fine-grained ceramics, the increase
in grain boundary and internal stress reduce the orientation of
polarization along electric field, and strongly influence ferro-
electric properties.15 For the significantly larger values of GS,
the grain boundary has a “dilution” effect resulting in a weak
influence on the ferroelectric properties. The variation trend
of Ec is contrary to that of Pr as shown in Fig. 5(b). As is
well known, Ec is a variable accounting for the ferroelectric
domain inverses. With a decrease in the GS, the grain boundary
and defects had the pinning effects on the domain, inducing an
increase in Ec .
1448 Y. Huan et al. / Journal of the European Ceramic Society 34 (2014) 1445–1448
Fig. 5. (a) P–E hysteresis loops of the BTO ceramics with different GS and (b) evolutions of Pr and Ec as functions of GS.
4. Conclusions
A series of dense BTO ceramics with different GS are suc-
cessfully prepared by two-step sintering method, and effects of
GS on piezoelectric, ferroelectric properties and phase struc-
tures are systematically explored in this study. The values of
d33 , kp , and ε increased significantly with decreasing GS, reach-
ing maximum values (ε = 6079, d33 = 519 pC/N and kp = 39.5%)
at approximately 1 ␮m, and then decreased rapidly with further
decreasing GS. For GS > 1 ␮m, the 90◦ domain width diminishes
with decreasing GS, inducing higher activity of the 90◦ domain
walls and enhanced piezoelectric properties. For GS < 1 ␮m,
the domain density dropped because of the increased volume
proportion of domain wall and grain boundary, resulting in the
degraded piezoelectric properties. The results revealed that high-
performance BTO ceramics could be effectively prepared by
controlling GS; thus, revitalizing the BTO-based ceramics as a
significant lead-free piezoelectric material.
Acknowledgements
The work was supported by Ministry of Sciences and Tech-
nology of China through National Basic Research Program of
China (973 Program 2009CB623301), National Natural Science
Foundation of China for Creative Research Groups (grant no.
51221291), National Natural Science Foundation of China for
distinguished young scholars (grant no. 50625204), National
Natural Science Foundation of China (grant no. 51272123), and
CBMI Construction Co., Ltd.
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