Journal of Crystal Growth 343 (2012) 17–20

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Journal of Crystal Growth

journal homepage: www.elsevier.com/locate/jcrysgro

Growth and characterization of lead-free Ba(1  x)CaxTi(1  y)ZryO3 single crystal

Yiming Zeng, Yanqing Zheng n, Xiaoniu Tu, Zhiping Lu, Erwei Shi
Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 201800, People’s Republic of China

a r t i c l e i n f o abstract

Article history: A lead-free Ba(1  x)CaxTi(1  y)ZryO3 (BCZT) single crystal (x ¼ 0.08, y ¼ 0.26) was grown by the Czochralski
Received 24 March 2011 (CZ) method in a mixed flux of TiO2 and ZrO2. The composition of as-grown BCZT was analyzed by
Received in revised form electron probe micro-analysis. The structure, dielectric properties and phase transition were investi-
5 January 2012
gated at different temperatures. The X-ray diffraction results confirmed that the structure of the
Accepted 8 January 2012
as-grown BCZT crystal was cubic both at 25 1C and 500 1C. The temperature dependence of the
Communicated by V. Fratello
Available online 20 January 2012 dielectric constant and Raman spectra characterization revealed that there was a phase transition from
cubic to tetragonal, which happened between 200 K and 250 K. With increasing frequency, the Curie
Keywords: temperature shifted towards high temperature.
A1. Dielectric properties
& 2012 Elsevier B.V. All rights reserved.
A1. Raman spectrum
A2. Single crystal growth
B2. BCZT

1. Introduction
PbZrxTi(1 x)O3 (PZT)-based ferroelectrics, as the most employed
piezoelectric materials, are widely used in actuators, sensors and
transducers due to their outstanding piezoelectric properties. How-
ever, the high toxicity of lead oxide and its volatilization during
processing has caused extreme concern, which greatly motivates the
need for substitutes. In recent years, researchers have devoted
considerable efforts to developing alternative lead-free materials,
such as (K0.5Na0.5)NbO3 (KNN) [1,2], (Na0.5Bi0.5)TiO3 (NBT),
(Na0.5Bi0.5)TiO3–BaTiO3(NBBT) [3–5], BaZrxTi(1 x)O3 (BZT), and
Ba(1 x)CaxTiO3 (BCT) [6,7] and so on. In spite of that, lead-free
substitutes generally have inferior piezoelectricity compared with
PZT. Among all lead-free materials, the BZT system is the one closest
to the PZT system in structure, composition and adjustability. Thus,
BZT-based substitutes are regarded as promising candidates.
Although single substitution on the A-site or B-site in the ABO3
structure of BZT has been widely studied, there are few reports
on co-substitutions both on the A-, and B-sites [8,9]. Recently,
Liu et al. reported a large piezoelectric effect (d33 ¼560–620 pC/N)
in the pseudobinary ferroelectric system (1 x)Ba(Zr0.2Ti0.8)O3 
x(Ba0.7Ca0.3)TiO3, especially for x¼0.5, which is located near the
morphotropic phase boundary (MPB) in the phase diagram [10].
Subsequently, Li et al. observed a high piezoelectric d33 coefficient in
Ba(1 x)CaxTi0.98Zr0.02O3 ceramics, and the d33 was up to 375 pC/N
when x¼0.01 [11]. Additionally, Xue et al. discussed the piezoelectric
properties of 50% Ba(Zr0.2Ti0.8)O3–50%(Ba0.7Ca0.3) TiO3 ceramic at the
morphotropic phase boundary [12]. It should be noted that all the
above works have focused on the same BZT-based system, Ba(1 x)-
CaxTi(1 y)ZryO3 (BCZT), which suggests that binary, ternary or even
more complex co-substitutions in BZT could obtain high piezoelec-
tricity. Therefore, BCZT may open a new route of ferroelectric
research on lead-free materials with high piezoelectricity.
The piezoelectric properties of a single crystal are much better
than those of its ceramic counterpart. Now that the BCZT ceramics
have achieved high piezoelectricity, it is intriguing to grow BCZT
single crystals. However, it is difficult to grow large scale single
crystals with the perovskite structure directly from the melt [13],
particularly for solid solution crystals. So far, several methods
have been used to grow perovskite structure crystals, such as the
laser-heated pedestal technique, Bridgman method and flux
method [14–17]. Many of the available single crystals were grown
by the flux method. In order to lower the growth temperature
effectively and avoid introducing impurities, oxide precursors
that contain the same elements as the crystal are usually chosen
as the flux, for example, Na2O for NBBT, and PbO for Pb((Mg1/3
Nb2/3)(1  x)Tix)O3 (PMNT) [5,18]. To our knowledge, no BCZT single
crystal has been reported to date. In this work, we focused on
exploring the growth of BCZT single crystals with high piezo-
electricity near the MPB using TiO2 and ZrO2 as flux by the CZ
method, and then characterizations such as phase, composition,
dielectric properties and phase transition were performed.
2. Experiment

n
Corresponding author. Tel.: þ86 21 69987762; fax: þ 86 21 59927184. The starting materials were prepared from mixed powders of
E-mail address: zyq@mail.sic.ac.cn (Y. Zheng). BaCO3, CaCO3, TiO2 and ZrO2 with 4 N purity at the stoichiometric

0022-0248/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.jcrysgro.2012.01.009
18 Y. Zeng et al. / Journal of Crystal Growth 343 (2012) 17–20

ratio of 0.5Ba(Zr0.2Ti0.8)O3–0.5(Ba0.7Ca0.3)TiO3 (Ba0.85Ca0.15Zr0.1-

Ti0.9O3), which had the highest d33 according to Ref. [10]. Mean-
while, TiO2 and ZrO2 were chosen as flux at a ratio of 9:1 with a
25 wt% excess of above raw materials in order to lower the
growth temperature and to maintain the composition ratio. The
starting materials and the flux were ground together, mixed
uniformly and pressed into blocks which were sintered at
1250 1C for 20 h in air atmosphere to react completely and to
synthesize polycrystalline materials. Then the polycrystalline
materials were charged into a Pt crucible for crystal growth. The
single crystal BCZT was grown in a conventional CZ furnace
without an after heater in air atmosphere. Before growth, the
melt had been maintained about 50–80 1C above the melting
point for several hours to homogenize the melt. The pulling and
rotation rates were optimized after a few rounds and finally a
single crystal was obtained. After growth, the temperature was
cooled down to 800 1C at a rate of 50 1C/h and then cooled down
to room temperature at a rate of 100 1C/h.
The phase and structure of the as-grown BCZT crystal was
examined by X-ray diffraction (XRD) using a Rigaku D/max
2550 V diffractometer with Cu Ka radiation (l ¼1.5406 Å) at
25 1C and 500 1C. An Electron Probe Micro-Analyzer (EPMA, JXA-
8100) was used to characterize the elemental composition.
Several c-cut samples were processed from the as-grown single
crystal and coated with silver electrodes for dielectric measure-
ment. The dielectric permittivity (e) versus temperature (T) curves
were measured with a modified HP4194A impedance analyzer in
the temperature range 120–490 1C. Raman spectra were
recorded in the temperature range 11.6–297 K with intervals of
50 K using a Renishaw invia Raman Microscope equipped with a
liquid-nitrogen-cooled charge-coupled device (CCD). The
514.5 nm line of an Ar þ laser was used for excitation.

3. Crystal growth and characterization

3.1. Crystal growth and elemental analysis

The BCZT crystal was grown along the /001S direction using a
BaTiO3 seed. The pulling and rotation rates were optimized to be Fig. 1. (a) The as-grown BCZT crystal pulled along /001S and (b) a piece of the
1 mm/day and 3–5 rpm, respectively, in order to obtain high quality crystal that fell off from the boule along cracks and a c-cut plate.

crystals. Finally, a BCZT single crystal with a size of f25  5 mm was

grown by the CZ method in a TiO2 and ZrO2 mixed flux, which was a
25 wt% excess of BCZT raw materials. Fig. 1a shows the as-grown
crystal, which has some micro-cracks due to the fast cooling below
800 1C. Fig. 1b shows a piece of the crystal that fell off the boule
along cracks and a c-cut plate. From Fig. 1, it can be seen that even
though the whole crystal is brown, the crystal has high optical
quality and no inclusions (Fig. 1b). However, it is hard to increase
the thickness of the crystal, even when prolonging the growth time
and lowering the temperature as well.
EPMA is a well-established method for microanalysis of major
and minor elements with a typical accuracy of 1% [19]. A c-cut
plate (4  3.8  0.58 mm) of the BCZT crystal was polished and
used for electron probe microanalysis. The microanalysis was
performed in three different areas and Table 1 shows the atomic
percentage of initial melt and analysis results. Considering impu-
rities, oxygen vacancies and the accuracy, the atomic percentage
of oxygen is not listed. As can be seen from the table, the
compositions differ from each other in different areas. The
average values are 19.84%, 1.74%, 19.56% and 7.04% for Ba, Ca,
Ti and Zr, respectively in crystal. The site specific effective
segregation coefficients keff of Ba and Zr are larger than 1, while
those of Ca and Ti are less than 1. Thus, the Ba2 þ take more
A-sites than Ca2 þ , similarly the Zr4 þ take more B-sites than Ti4 þ .
According to the EPMA results, the average chemical formula of
the as-grown BCZT crystal is Ba0.92Ca0.08Zr0.26Ti0.74O3, which
deviates from the expectation. There may be two reasons for this
result: first, it is hard or unstable for Ca2 þ to occupy an A-site
compared with Ba2 þ ; secondly, the concentration of Zr2 þ may be
too high in the melt, from TiO2 volatilization during growth. So
the composition of starting materials and mixed flux should be
adjusted in future work.
3.2. X-ray diffraction analysis
Fig. 2 shows the XRD patterns of the BCZT crystal at 25 1C and
500 1C. It can be seen that the crystal shows a pure perovskite
structure, suggesting that Ca2 þ and Zr2 þ form a solid solution in
the BaTiO3 lattice. Moreover, the features of all diffraction peaks
are identical at 25 1C and 500 1C, indicating that the crystal
structure of the as-grown BCZT crystal is the cubic phase rather
than the tetragonal or rhombohedral phase at room temperature.
Obviously, the deviation of chemical composition is the main
reason for the phase shift. As can be seen from the phase diagram
of this pseudobinary ferroelectric system [10], the crystal struc-
ture tends to form the cubic phase with increasing Zr2 þ . From the
above analysis, the symmetry of the BCZT crystal can be identified
as Pm 3̄ m. In addition, the lattice parameters and theoretical
density can be calculated from the XRD data by the Jade
 Y. Zeng et al. / Journal of Crystal Growth 343 (2012) 17–20 19

Table 1
Compositions of flux grown BCZT single crystal analyzed by EPMA methods.

Element Atomic% Measured atomic% keff Formula

Melt I II III Average Error EPMA Expected

Ba 11.23 19.39 19.62 20.52 19.84 7 0.5 1.08 0.92 0.85

Ca 1.98 1.6 1.86 1.76 1.74 7 0.2 0.53 0.08 0.15
Ti 22.08 18.07 19.58 21.04 19.56 7 0.5 0.82 0.74 0.9
Zr 2.45 7.17 7.02 6.94 7.04 7 0.2 2.60 0.26 0.1

Fig. 2. XRD pattern of as-grown BCZT crystal at 25 1C and 500 1C.

5.0 program. They are a ¼b¼c¼ 4.047 Å, V¼ 66.28 Å3, and the
density is 5.89 g/cm3 at 25 1C.

3.3. Dielectric properties

Fig. 3 shows the temperature dependence of the dielectric

constant and dielectric loss with applied frequencies of 1 kHz,
10 kHz, 100 kHz and 1000 kHz. It can be seen that the dielectric
constant decreases with increasing frequency. This can be
explained from the relaxation polarization mechanism that the
dielectric constant will decrease when the resonance frequency of
the electric charge carriers in the crystal cannot follow the
alternation of the applied electric fields beyond a certain critical
frequency [20]. Corresponding to the phase transition from
paraelectric to ferroelectric state in BCZT crystal, there is only
one peak for each frequency in the temperature range of Fig. 3. Temperature dependence of the (a) dielectric constant and (b) loss (tan d)
120–490 1C, indicating that the Curie temperature (Tc) shifts at various frequencies for BCZT crystal.

to higher temperature with increasing frequency, which is a

typical characteristic for perovskite solid solutions [21–24]. The
Tc are  65 1C,  59 1C, 52 1C and 43 1C for different frequen-
cies. The dielectric loss is about 0.12–0.22 for the four frequencies
near Tc due to the phase transition and then decreases up to room
temperature, while the dielectric loss rises sharply above 400 1C,
as shown in Fig. 3b inset, possibly due to the motion of defects.
3.4. Raman spectrum and phase transition
Zr-related feature [25] appears below 200 K and is strengthened
with the decrease in temperature. These changes indicate that the
BCZT crystal undergoes a phase transition from cubic to tetra-
gonal between 200 K and 250 K. This is consistent with the
dielectric data shown in Fig. 3. However, it is hard to distinguish
any other phase transition from the present Raman spectra. It
should be noted that the tendency and some features of the
Raman spectra are similar to previous results [25,26].

Fig. 4 shows the Raman spectra of the BCZT crystal as a

function of temperature. All the Raman spectra contain three
clear modes: a broad A (LO) mode at 720–780 cm  1, an A (TO)
mode at  526 cm  1 and an E (TO) mode at  300 cm  1. The
mode at  172 cm  1 disappears below 200 K and gradually
evolves into a shoulder around 200 cm  1. Moreover, careful
investigation of the region around 120 cm  1 reveals that a weak
4. Conclusion
A lead-free Ba(1 x)CaxTi(1 y)ZryO3 single crystal has been grown
by the CZ method in a mixed flux of TiO2 and ZrO2 when trying to
grow high piezoelectricity Ba0.85Ca0.15Zr0.1Ti0.9O3. The EPMA results
shows a composition of x¼0.08 and y¼0.26 for the BCZT crystal.
20 Y. Zeng et al. / Journal of Crystal Growth 343 (2012) 17–20
Fig. 4. Raman spectra of BCZT crystal at different temperatures.
The XRD characterization indicates a cubic structure both at 25 1C
and 500 1C. The temperature dependence of the dielectric constant
and Raman spectra analysis reveal that the phase transition from
cubic to tetragonal occurs between 200 K ( 73.15 1C) and 250 K
( 23.15 1C). The Tc shifts towards higher temperature with increas-
ing frequency. It is well known that the phase and Tc of the
perovskite structure are very sensitive to the chemical composition.
So, even though there is no piezoelectricity observed at room
temperature for the BCZT crystal of this composition, and it is
difficult to obtain BCZT single crystals due to the volatilization,
segregation and polycrystals during growth, we believe that BCZT
single crystals with high Tc and piezoelectricity will be grown by
tuning the chemical composition and improving the growth tech-
nique in the future. This work provides meaningful reference for
exploring high piezoelectricity crystals from the BCZT system.
Acknowledgments
Financial support from the National Nature Science Founda-
tion of China (Grant nos. 50772121, 50802104, 51002167) and
the Knowledge Innovation Program of Chinese Academy of
Sciences (Grant nos. KGCX-2-YW-206 and YYYJ-1117-2) are
gratefully acknowledged.
References
[1] Y. Kizaki, Y. Noguchi, M. Miyayama, Applied Physics Letters 89 (2006) 142910.
[2] H. Ursic, A. Bencan, M. Skarabot, M. Godec, M. Kosec, Journal of Applied
Physics 107 (2010) 033705.
[3] G.S. Xu, Z.Q. Duan, X.F. Wang, D.F. Yang, Journal Crystal Growth 275 (2005) 113.
[4] X.Y. Zhou, H.S. Gu, Y. Wang, W. Li, T.S. Zhou, Materials Letters 59 (2005) 1649.
[5] Q.H. Zhang, Y.Y. Zhang, F.F. Wang, Y.J. Wang, D. Lin, X.Y. Zhao, H.S. Luo,
W.W. Ge, D. Viehland, Applied Physics Letters 95 (2009) 102904.
[6] Z. Yu, R.Y. Guo, A.S. Bhalla, Journal of Applied Physics 88 (2000) 410.
[7] L.B. Barbosa, D.R. Ardila, J.P. Andreeta, Journal of Crystal Growth 231 (2001)
488.
[8] P.K. Panda, Journal of Materials Science 44 (2009) 5049.
[9] J. Ravez, C. Broustera, A. Simon, Journal of Materials Chemistry 9 (1999) 1609.
[10] W.F. Liu, X.B. Ren, Physical Review Letters 103 (2009) 257602.
[11] W. Li, Z.J. Xu, R.Q. Chu, P. Fu, G.Z. Zang, Materials Letters 64 (2010) 2325.
[12] D.Z. Xue, Y.M. Zhou, H.X. Bao, C. Zhou, J.H. Gao, X.B. Ren, Journal of Applied
Physics 109 (2011) 054110.
[13] D. Fu, M. Itoh, S.Y. Koshihara, Applied Physics Letters 93 (2008) 012904.
[14] Z. Yu, R.Y. Guo, A.S. Bhalla, Journal of Applied Physics 88 (2000) 410.
[15] H.S. Luo, G.S. Xu, H.Q. Xu, P.C. Wang, Z.W. Yin, Japanese Journal of Applied
Physics 39 (2000) 5581.
[16] Y. Hosono, K. Harada, Y. Yamashita, Japanese Journal of Applied Physics 40
(2001) 5722.
[17] S.J. Zhang, L. Lebrun, S. Rhee, R.E. Eitel, C.A. Randall, T.R. Shrout, Journal of
Crystal Growth 236 (2002) 210.
[18] M. Dong, Z.G. Ye, Journal of Crystal Growth 209 (2002) 81.
[19] Z.N. Dai, C.G. Ren, J.J. Zhang, G.Z. Ma, F.J. Yang, Nuclear Instruments and
Methods B 104 (1995) 489.
[20] H.L. Du, X. Yao, Materials Science and Engineering B 99 (2003) 437.
[21] A. Ochi, T. Mori, M. Furuya, Applications of ferroelectrics, Proceedings of 8th
IEEE International Symposium, 1992, p. 66.
[22] I. Ki Vin, K. JaiHyun, C. Woong Kil, Applications of ferroelectrics, Proceedings
of 11th IEEE International Symposium, 1998, p. 467.
[23] L. Xifa, Y. ZuoGuang, Applications of ferroelectrics, Proceedings of 16th IEEE
International Symposium, 2007, p. 493.
[24] X. Long, Z.G. Ye, Applied Physics Letters 90 (2007) 112905.
[25] P.S. Dobal, A. Dixit, R.S. Katiyar, Z. Yu, R. Guo, A.S. Bhalla, Journal of Applied
Physics 89 (2001) 8085.
[26] S. Miao, J. Pokorny, U.M. Pasha, O.P. Thakur, D.C. Sinclair, I.M. Reaney, Journal
of Applied Physics 106 (2009) 114111.