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Ceramics International 41 (2015) 24972501

www.elsevier.com/locate/ceramint

Enhanced temperature stability in Tb-doped (Ba0.99Ca0.01)(Ti0.98Zr0.02)O3

lead free ceramics
Jinghan Gaoa, Qiang Lia,n, Hairui Liua, Jaeshik Shima, Qingfeng Yana,
Yiling Zhangb, Xiangcheng Chub
b

a
Department of Chemistry, Tsinghua University, Beijing 100084, China
State Key Laboratory of New Ceramics and Fine Processing, Tsinghua University, Beijing 100084, China

Received 28 September 2014; received in revised form 12 October 2014; accepted 12 October 2014
Available online 27 October 2014

Abstract
Lead-free (Ba0.99Ca0.01)(Ti0.98Zr0.02)O3 (BCZT) x mol% Tb (x 00.6) ceramics were prepared using a solid-state reaction technique. Phase
structure, dielectric constant, ferroelectricity and temperature-dependent piezoelectric coefcient were explored. With an increasing Tb content,
the orthorhombictetragonal phase transition temperature (TOT) shifted to lower temperature while its Curie temperature (Tc) remained at 130 1C.
The temperature stability of piezoelectric coefcient (d33) could be enhanced from 30 to 120 1C in Tb-doped BCZT ceramics. A piezoelectric
coefcient of d33 542 pm/V was obtained at x 0.2 with low temperature-dependent degradation from 30 to 120 1C. The results indicated that
Tb-doped BCZT ceramics could be a promising candidate for commercial purposes.
& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: C. Electrical properties; BCZT; Piezoelectric ceramics; Tb-doped; Temperature stability

1. Introduction
Lead-based piezoelectric ceramics, such as PZT etc. with highperformances are widely used in sensors, actuators and medical
ultrasonic transducers owing to their excellent electrical properties
and ability to be operated over a wide temperature range [13].
Nevertheless, there are nearly more than 50 wt% lead in it, which
would cause serious environmental issues either in its synthesis or
waste treatment processes [4,5]. Therefore, lead-free piezoceramics are urgently needed to replace lead-based piezoceramics as a
result of growing environmental concerns.
Recently, Ba(Zr0.2Ti0.8)O3(Ba0.7Ca0.3)TiO3 (BZT50BCT), a
fresh lead-free system with high piezoelectric performance, has
already become the research hotspot since reported by Ren et al.,
making it one of the most promising candidates for lead-free
piezoelectric materials [69]. However, its optimal composition
n

Corresponding author. Tel.: 86 10 62797871; fax: 86 10 62771149.

E-mail addresses: gjinghan@163.com (J. Gao),
qiangli@mail.tsinghua.edu.cn (Q. Li).
http://dx.doi.org/10.1016/j.ceramint.2014.10.071
0272-8842/& 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

with high d33 value exhibits low Tc and heavily temperaturedependent degradation in the common usage temperature [10,11].
The Curie temperature is only 90 1C, which would restrict its
operating temperature range [7,12]. Taken this matter into account,
a composition (Ba0.99Ca0.01)(Ti0.98Zr0.02)O3 (BCZT) with relatively
lower Ca2 and Zr2 contents is chosen to improve its Curie
temperature for application consideration [13,14]. Meanwhile, the
coexistence of orthorhombic and tetragonal phases slightly above
room temperature, which is considered to be accompanied with the
enhanced piezoelectric property, leads to heightened temperature
dependence in the piezoelectric response, making the composition
unsuitable for a variety of applications [11,13]. This phase
transition limits their implementation greatly because of the
property variation and domain instability between the two ferroelectric phases [15]. To enhance its temperature stability, a lower
orthorhombictetragonal phase transition temperature (TOT) is
needed. However, this always comes at an expense of decrement
in the piezoelectric response [16]. Therefore, a balance should be
considered between piezoelectric performance and temperature
stability. Recently, Ho, Er and Dy-doped BCZT were reported to

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J. Gao et al. / Ceramics International 41 (2015) 24972501

move this phase transition (TOT) to lower temperature [1719]. As

a rare earth element, Tb together with Dy, Ho and Er, has the [Xe]electron conguration for their electrons in the closed shells [20].
Therefore, Tb is believed to have a similar effect on TOT which
would help to improve the stability of temperature-dependent
piezoelectricity. In this paper, we report on the above mentioned
issues in Tb-doped BCZT ceramics.
2. Material and methods
The (Ba0.99Ca0.01)(Ti0.98Zr0.02)O3 x mol% Tb (x 0, 0.2,
0.4, 0.6) ceramics (T0, T2, T4 and T6) were prepared by the
conventional solid-state reaction technique. Raw materials of
BaCO3 (99.9%), CaO (99.99%), ZrO2 (99.99%), TiO2 (99.99%)
and Tb4O7 (99.99%) were mixed with the addition of alcohol
according to the stoichiometric ratio. Then the mixed powders
were calcined at 1300 1C after being ball-milled for 4 h.
Thereafter, calcined powders were remixed and pressed into
disks of 10 mm in diameter and 1.5 mm in thickness under
7 MPa with 5 wt% polyvinyl alcohol (PVA) as the binder. Then
as-pressed pellets were sintered at 1400 1C for 4 h. After that,
both the circular surfaces of ceramics were polished and coated
with silver as electrodes.
XRD patterns of as-prepared ceramics at room temperature
were recorded by a diffractometer (D8 ADVANCE; Bruker Inc.,
Karlsruhe, Germany) using CuK ( 1.5406 ) radiation. The
dielectric properties of silver-coated specimens were measured
as a function of temperature by an impedence precision analyzer
(HP4192A; Agilent Inc., Bayan, Malaysia) in the temperature
range from  20 1C to 145 1C. The ceramics were poled under
5 kV/mm DC elds at room temperatures. The temperature
dependence of d33, electric-eld-induced polarization (PE) and
strain (SE) measurements were carried out using an analyzer
(TF 2000; aix ACCT Co., Aachen, Germany).

Fig. 1. X-ray diffraction patterns between the 2 range of 15701 (a) and 44
461 (b) for the Tb-doped BCZT ceramics (T0, T2, T4 and T6).

Fig. 2. Temperature dependence of dielectric constant for the Tb-doped BCZT

ceramics (T0, T2, T4 and T6) measured at 1 kHz as a function of temperature
from 20 1C to 145 1C.

3. Results and discussion

Fig. 1(a) shows the X-ray diffraction patterns of as-sintered
ceramics (T0, T2, T4 and T6). As can be seen, all as-sintered
ceramics are of pure perovskite phase without any trace of
impurity, suggesting that Tb has diffused into BCZT lattice to
form a solid solution. The enlarged angles ranging from 441 to
461 are shown in Fig. 1(b) to detect difference among these
samples. It can be seen that peak intensity in the right side
becomes stronger with increasing Tb content, which conrms that
a composition-dependent phase evolution from orthorhombic to
tetragonal phase has happened [21,22]. In addition, it is known
that for stable trivalent ions, small ion (ro0.87 ) would occupy
B-site, large ion would occupy A-site (r40.94 ), and intermediate ion could occupy both A-site and B-site [23,24].
However, Tb is a special case with mixed 3 and 4 valances.
According to a previous research, Tb3 could substitute at both
A-site and B-site whereas Tb4 would substitute at the B site
[25]. As Tb3 is acknowledged to show typical emission bands
in the range of 450650 nm, emission spectra are detected at
room temperature with a uorescence spectrophotometer (HITACHI F-7000) in order to further conrm the position and valence

of Tb ions [26,27]. And the valence of Tb ions was proved to be

4 as the uorescence spectrum did not show the emission
bands of Tb3 . Therefore, Tb ions are conrmed to occupy the
B-site of BCZT with the valence of 4 to form a solid solution.
Fig. 2(a) shows the temperature dependence of dielectric
constant (r) for the Tb-doped BCZT ceramics (T0, T2, T4 and
T6) with different Tb content measured at 1 kHz as a function
of temperature from  20 1C to 145 1C. Two obvious phase
transitions above  20 1C corresponding to the orthorhombic
tetragonal (TOT) and tetragonalcubic (Tc) phase transitions,
respectively, are observed for all the samples. It is noted that Tc
(130 1C) is not strongly affected, while the broad TOT shifts to
lower temperature with increasing Tb content. Therefore, Tb
doping in (Ba0.99Ca0.01)(Ti0.98Zr0.02)O3 ceramics pushes the
TOT to low temperature without reduction of Tc and weakens
the phase transition which is coincident with the XRD results.
Fig. 3 shows ferroelectric hysteresis loops and bipolar electriceld-induced strain of as-prepared Tb-doped BCZT ceramics (T0,
T2, T4 and T6) measured at room temperature and 1 Hz. Under
an electric eld of 2 kV/mm, all samples possess typical ferroelectric polarization hysteresis loops. As can be seen in Table 1,

J. Gao et al. / Ceramics International 41 (2015) 24972501

2499

Fig. 3. Ferroelectric hysteresis loops and electric- eld-induced strain of Tb-doped BCZT ceramics: (a) T0, (b) T2, (c) T4, (d) T6 measured at 1 Hz and room
temperature.
Table 1
The Curie temperature (Tc), the orthorhombictetragonal phase transition
temperature (TOT), saturation polarization (Ps), coercive eld (Ec), the bipolar
electric-eld-induced strain and d33 decreased ratio from 30 1C to 120 1C for
T0, T2, T4 and T6 ceramics.
Composition Tc
(oC)

TOT
(oC)

Ps (C/
cm2)

Ec (kV/
mm)

Strain
(%)

d33/d33
d33
(pm/V) (%)

T0
T2
T4
T6

30
26
22
19

15.33
17.69
17.34
16.79

0.21
0.28
0.30
0.29

0.077
0.110
0.103
0.097

566
542
410
355

130
130
130
130

68
23
23
16

saturation polarization (Ps) rst increases to 17.69 C/cm2 for T2,

and then degrades with increasing Tb content. It could be seen
that coercive eld (Ec) of Tb-doped BCZT increased compared to
pure BCZT ceramics (T0). Higher c/a ratio in T phase brings
about larger local internal stresses caused by structural distortion,
hence hindering domain switching and increasing Ec [21,28].
Typical buttery shape is observed for all samples. And under
an applied eld of 2 kV/mm, T2 also exhibits the highest strain.
Fig. 4(a) shows the piezoelectric coefcients (d33) as a function
of the temperature for Tb-doped BCZT ceramics (T0, T2, T4 and
T6) from 30 1C to 150 1C. These results are calculated according

Fig. 4. (a) Temperature dependence of piezoelectric coefcient for Tb-doped

BCZT ceramics (T0, T2, T4 and T6). The inset (b) shows the decreased
percentage of d33 with temperature range from 30 1C to 120 1C. (c) unipolar
eld induced strain (SE) curves for illustrating the calculation of d33.

to the converse piezoelectric effect as is shown in Fig. 4(c) [29].

Therefore, d33 is calculated by exploring the temperaturedependent unipolar electric-eld-induced strain (SE) curves at

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J. Gao et al. / Ceramics International 41 (2015) 24972501

the frequency of 0.5 Hz, the slope of which is the piezoelectric

coefcient. The decrements of piezoelectric coefcient (d33/d33)
from 30 1C to 120 1C are shown in Fig. 4(b). It is well known
that room-temperature coexistence of orthorhombic and tetragonal phases results in the dramatical increment of roomtemperature d33 while it also dictates instability in the electrical
properties with temperature [30]. Improved temperature stability
is achieved by doping of Tb which weakens the phase transition.
It can be seen from the inset of Fig. 4 that d33 of pure BCZT (T0)
decreased 68% from 30 1C to 120 1C while the decrement of T6
is only 16%. Room temperature d33 should also be listed in
Table 1. The highest room temperature d33 of T0 should be
related to the phase coexistence occurring at 30 1C, which allows
optimum domain reorientation and enhances the piezoelectric
performance. The reduced piezoelectric properties of T2, T4 and
T6 should be due to the polymorphic orthorhombic-tetragonal
phase transition being shifted to lower temperatures [16]. In this
way a balance should be made to obtain high temperature
stability and piezoelectricity. Values of the Curie temperature
(Tc), the orthorhombictetragonal phase transition temperature
(TOT), saturation polarization (Ps), coercive eld (Ec), the
electric-eld-induced strain and d33 decreased ratio from 30 1C
to 120 1C for T0, T2, T4 and T6 ceramics are summarized in
Table 1. It could be demonstrated that the piezoelectricity,
ferroelectricity and temperature stability of T2 is relatively better
compared to other compositions, Therefore, T2 is a balanced
choice which has a potential application considering both
relatively higher d33 (542 pm/V) and better temperature stability
(d33/d33 23%).

4. Conclusion
Tb-doped BCZT lead-free ceramics were prepared using the
solid-state reaction technique. The effect of Tb on phase
structures, dielectric constants and temperature-dependent d33 of
BCZT ceramics were investigated. With increasing Tb content, Tc
still remains at 130 1C while TOT turns to lower temperature. An
enhanced temperature stability of piezoelectric property is
obtained by doping Tb in BCZT ceramics. T2 ceramics are
believed to have potential piezoelectric application with relatively
high Tc (1301C) and enhanced temperature stability of d33. This
work may also provide a way to design piezoelectric material for
practical applications.

Acknowledgments
This work was supported by the National Basic Research
Program of China (Grant no. 2013CB632900), the National
Natural Science Foundation of China (Nos. 50972071 and
51172118) and the funds of State Key Laboratory of New
Ceramics and Fine Processing, Tsinghua University, Beijing
100084, China. The authors also thank Prof. Jingfeng Li and
Mr. Fangzhou Yao for their help on the measurement of
temperature-dependent piezoelectric coefcients.

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