J Mater Sci (2015) 50:6134–6141
DOI 10.1007/s10853-015-9170-2
Structure and electrical properties of IrO2-doped
0.5Ba0.7Ca0.3TiO3–0.5BaTi0.8Zr0.2O3 ceramics
via low-temperature sintering
Yongshang Tian1 • Yansheng Gong1 • Dawei Meng1 • Yuanjian Li1
Received: 31 March 2015 / Accepted: 9 June 2015 / Published online: 13 June 2015
Ó Springer Science+Business Media New York 2015
Abstract Lead-free ceramics 0.5Ba0.7Ca0.3TiO3–
0.5BaTi0.8Zr0.2O3–xIrO2 (x = 0–1.2 %) were prepared at a
low temperature of 1260 °C via sintering the as-synthe-
sized nanoparticles, which were synthesized by a modified
Pechini polymeric precursor method. All samples featured
high levels of densification under the synthesis conditions;
particularly, the ceramic prepared at IrO2 content of 0.4 %
achieved the highest relative density (*97.4 %). Phase
transition from tetragonal to orthorhombic and a poly-
morphic phase transition (PPT) region were observed,
which were influenced by the IrO2 content. The dielectric
properties, temperature coefficient of capacitance, ferro-
electric properties, and piezoelectric properties as a func-
tion of IrO2 content were thoroughly studied. Optimal
electrical properties (remnant polarization, piezoelectric
constant, and planar electromechanical coupling factors,
i.e., Pr = 6.28 lC/cm2, d33 = 199 pC/N, and kp = 0.258)
were obtained around the PPT region. The findings of the
ceramic electrical properties by IrO2 doping are believed to
be insightful in the development of lead-free dielectric and
ferroelectric materials.
& Yansheng Gong
gongysh@cug.edu.cn
& Dawei Meng
dwmeng@cug.edu.cn
1
Faculty of Material Science and Chemistry, China University
of Geosciences, Wuhan 430074, People’s Republic of China
123
Introduction
Lead-based materials have been conventionally used in
piezoelectric devices that convert mechanical energy to
electrical energy and vice versa for more than 50 years [1].
However, the use of lead-based materials has been pro-
hibited owing to their high toxicity [2]. Consequently, great
efforts have been devoted to the development of eco-
friendly lead-free materials as alternatives. Among the
lead-free candidates studied, BaTiO3 (BT)-based materials
are regarded as promising materials owing to their con-
trollable sinterability, excellent thermostability, and out-
standing electrical properties [3]. However, the application
of BT-based materials is limited by their low Curie tem-
perature (TC) and single functional performance [4]. To
address these issues, many researchers have attempted
modification of BT-based materials by doping/substituting
elements, broadening their performance capabilities by
endowing the materials with optical, electrical, acoustic,
or/and magnetic properties [5–8].
Current research involves the study of BT-based mate-
rials with a perovskite structure (ABO3) via doping rare
elements, and IA, IIA, and VIIB elements in A/B sites for
the multifunctional performance [9, 10]. Among the
research, 0.5Ba0.7Ca0.3TiO3–0.5BaTi0.8Zr0.2O3 (BCT–
BZT) system materials had been received significant
attention for the comparable piezoelectric properties with
the lead-based materials, since the morphotropic phase
boundary region was demonstrated in this system [6].
Moreover, various methods in the preparation and electri-
cal performance research on BCT–BZT system were
developed, which promoted the application of lead-free
materials for the replacement of lead-based materials [11–
16]. As known, platinum group elements, e.g., IrO2 and
RuO2, have potential application in catalysis,
J Mater Sci (2015) 50:6134–6141 6135

electrochemistry, and microelectronic devices [17, 18]. detected by field-emission scanning electron microscopy
However, comprehensive studies on BT-based materials (FESEM; SUV-1080), and the average grain size of the
containing doped platinum group elements are yet to be ceramics was estimated using the linear intercept method.
reported. Such materials are expected to have outstanding The density of the ceramics was determined based on
electrical properties and valuable uses in electrode buffer Archimedes immersion principle using a precision elec-
materials of multilayer ceramic capacitors. tronic balance (ED-124S). The relative permittivity (er),
Our previous studies reported the preparation of BT- loss tangent (tan d), and capacitance values were deter-
based ceramics at a relatively low sintering temperature of mined using a precision LCR meter (TH-2819) at 10 kHz.
1260 °C via sintering the as-synthesized nanoparticles, A Radiant Precision Workstation was used to investigate
which were synthesized by a modified Pechini polymeric polarization–electric field (P–E) hysteresis loops. The
precursor method and showed homogeneous dispersion of resonance and anti-resonance frequencies of the poled
the ingredients, narrow particles size distribution, and samples were measured on a precision impedance analyzer
stable structure [19, 20]. The prepared BT-based ceramics (Agilent 4294A) to calculate the planar and thickness
with the as-synthesized nanoparticles featured high densi- vibration electromechanical coupling factors (kp and kt)
fication, few crystal defects, and enhanced electrical and mechanical quality factor (Qm). The piezoelectric
properties, which had been reported elsewhere [20, 21]. constant (d33) was measured on a quasi-static meter (ZJ-
The properties of platinum group element, iridium (Ir), and 3A) at room temperature.
its compound were also studied in our previous studies [21,
22]. In this work, IrO2-doped BCT–BZT ceramics were
prepared using the above-discussed process. The phase Results and discussion
transition, crystal structure, and electrical properties of the
ceramics as a function of IrO2 content were systematically Figure 1 shows the XRD patterns of the BCT–BZT–xIrO2
studied. ceramics doped with different IrO2 contents (x). All
detected samples featured a pure perovskite (ABO3)
structure with no secondary phases in solid solutions,
Experimental procedure implying that iridium was successfully impregnated into
the ABO3 lattice. As observed in Fig. 1b, the unique
The as-synthesized Ba0.7Ca0.3TiO3 (BCT) and BaTi0.8- splitting of the (002) and (200) diffraction peaks at *45°
Zr0.2O3 (BZT) nanoparticles, which were synthesized by a corresponding to the tetragonal (T) phase (JCPDS #
modified Pechini polymeric precursor method that has been 05-0626) appeared when x \ 0.4 % [15] and merged into
reported elsewhere [19–21], and IrO2 (Ir C 86.0 %) pow- (200) diffraction peak corresponding to the rhombohedral
der were stoichiometric mixed to obtain 0.5BCT–0.5BZT–
xIrO2 powders (abbreviated as BCT–BZT–xIrO2; x = 0,
0.2, 0.4, 0.6, 0.8, 1.0, and 1.2 %). Then, the powders were
dispersed homogeneously and uniaxially pressed into disks
of 20 mm in diameter and *1.5 mm in thickness mixed in
the presence of 2.5 wt% polyvinyl alcohol (PVA) solution
binder at 150 MPa. Following burnt out of PVA at 650 °C,
the green bodies were sintered at 1260 °C for 5 h in air
atmosphere to obtain the BCT–BZT–xIrO2 ceramics. For
the electrode preparation, the ceramics were polished and
both sides of the disks surfaces were silver-painted, then
annealed at 580 °C for 20 min for subsequent dielectric
and ferroelectric measurements. Then, the samples were
poled in a silicone oil bath under a direct-current electric
field of 18 kV/cm at 25 °C for *40 min for the piezo-
electric measurements.
X-ray diffraction (XRD; X’Pert PRO) with Cu Ka
radiation was used to investigate the crystal phase of the
ceramics; the analysis was conducted at room temperature.
The samples were fractured and subjected to a thermal
Fig. 1 a XRD patterns and b corresponding selected enlarged regions
etching process (1050 °C, 15 min, in air atmosphere). (44°–47°) of the BCT–BZT–xIrO2 ceramics prepared with varying
Then, the fractured microstructures of the ceramics were IrO2 contents (x)

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Fig. 2 a Variations in the lattice parameters of the BCT–BZT–xIrO2 ceramics prepared with different IrO2 contents (x) and b crystalline
schematic of the ceramic prepared with x = 1.0 %

(R) phase (JCPDS # 85-1796) when x [ 0.8 % [23]. Both
T and R phases were observed in the intermediate x range
of 0.4–0.6 %. Thus, the results showed the phase transition
of the BCT–BZT–xIrO2 ceramics with increasing x. As
observed in the selected enlarged region (44°–47°) in
Fig. 1b, subtle variations were detected. The diffraction
peaks shifted monotonically to low 2h angles with
increasing x. According to the principles of crystal chem-
istry relating to element doping positions in ABO3 structure
reported by Lee et al. [24] and Morrison et al. [25], iridium
generally occupied the B sites. Thus, the shift in the
position of the diffraction peaks was attributed to the
decreased interplanar spacing owing to the substitution of
Zr4? (ionic radius 0.087 nm) with a smaller Ir4?
(0.072 nm) in the ABO3 structure [26]. Additionally, the
subtle variation in the intensity of diffraction peaks with
increasing x suggested variations in the crystalline prop-
erties of the ceramics including the onset of a distorted
crystal lattice by IrO2 doping.
Figure 2a shows the variations in the average lattice
parameters (a, b, c, and axial angle) of the BCT–BZT–
xIrO2 ceramics doped with varying IrO2 contents. The
average lattice parameters in Table 1 were calculated by
Jade 5.0 after the Rietveld refinement using Fullprof soft-
ware. The dimension of the lattice parameters a, b, and
c decreased slightly at IrO2 content below 0.4 %. More
prominent decreases were observed at IrO2 content above
0.8 %. Variations in the lattice parameters were attributed
to the incorporation Ir4? into the B sites in the ABO3
structure that led to crystal lattice distortion and instigated
phase transition [16]. A schematic of the crystal structure
of BCT–BZT–xIrO2 ceramics (x = 1.0 %), featuring
R phase with average lattice parameters (3.9901(8) Å,
3.9902(1) Å, 3.9901(9) Å, and 89.88°) is shown in Fig. 2b,
which was obtained by Crystal maker software, revealing
the internal crystal structure of the ceramic.
Figure 3 shows the FESEM images of the BCT–BZT–
xIrO2 ceramics doped with different IrO2 contents. All
samples featured a dense microstructure with few cavities
as a result of the sintering process. The average grain size
of the ceramics was *0.7 lm, which was considerably
smaller than that reported in the literature studies [27, 28].
The fine grain size of the ceramics was believed to be
related to the raw material of the as-prepared nanoparticles.

Table 1 Lattice parameters, density and relative densities (DRE), average grain size (GAV) of the BCT–BZT–xIrO2 ceramics prepared with
varying IrO2 contents (x)
x (%) a (Å) b (Å) c (Å) Axial angle (°) Phase Density (g/cm3) DRE (%) GAV (lm)

0 3.9907(7) 3.9907(7) 4.0014(3) 90 T 5.483 96.41 0.713(2)

0.2 3.9905(5) 3.9906(2) 4.0005(3) 90 T 5.514 96.96 0.711(7)
0.4 – – – – T&R 5.537 97.36 0.707(3)
0.6 – – – – T&R 5.502 96.75 0.699(5)
0.8 3.9903(6) 3.9903(9) 3.9904(7) 89.93 R 5.458 95.97 0.690(4)
1.0 3.9901(8) 3.9902(1) 3.9901(9) 89.88 R 5.437 95.61 0.685(6)
1.2 3.9897(7) 3.9898(2) 3.9897(7) 89.84 R 5.413 95.18 0.694(9)

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Fig. 3 FESEM of the fractured morphology of the BCT–BZT–xIrO2 ceramics prepared with different IrO2 contents (x) of a 0 %, b 0.2 %,
c 0.4 %, d 0.6 %, e 0.8 %, f 1.0 %, and g 1.2 %

The average grain size decreased slightly with the distorted, with the formation of some fine grains at the
increasing x. This finding was attributed to the diffusion of grain boundaries, at higher x. This finding was the result of
small Ir4? ions into the matrix of the ABO3 structure. the solubility limit of iridium in the ABO3 structure of the
Additionally, the ceramic crystal lattice was slightly BCT–BZT–xIrO2 ceramics [29].

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densification of the ceramics increased with increases in x,

Fig. 4 Variations in the density and relative density of the BCT–
BZT–xIrO2 ceramics prepared with varying IrO2 contents (x)
Fig. 5 Temperature dependence of the relative permittivity (er) and loss
tangent (tan d) of the BCT–BZT–xIrO2 ceramics measured at 10 kHz.
The inset (a) shows the temperature coefficient of capacitance of the
BCT–BZT–xIrO2 ceramics prepared with different IrO2 contents (x)
The density and relative density values of the BCT–
BZT–xIrO2 ceramics doped with different IrO2 contents are
shown in Fig. 4 and Table 1. As observed, the level of
reaching maximum at x = 0.4 % (density: 5.537 g/cm3;
relative density: 97.36 %), and then decreased with further
increases in x. The enhanced densification was associated
with the replacement of Ti/Zr by iridium with heavier
atomic mass in the ABO3 structure. In contrast, the
decrease in the densification at higher x was due to crystal
lattice distortion [16]. The relative densities of the samples
were all above 95 %, which is indicative of the high den-
sification of the materials featuring few cavities.
Figure 5 shows the temperature dependence of relative
permittivity (er) and loss tangent (tan d) of the BCT–
BZT–xIrO2 ceramics doped with different IrO2 contents
assessed at a frequency of 10 kHz. All samples showed
broadened dielectric peeks banded with a relatively low
permittivity under the testing conditions, which was
attributed to fine grain size, as consistent with the above
analysis [27]. The details of dielectric properties are
shown in Table 2. From the detected results, it can be
seen that tan d first decreased and then increased with
increasing x. This trend was due to the high densification
of the ceramics at x \ 0.6 % and subsequent formation of
fine grains at the grain boundaries. A weak dielectric
relaxation behavior was detected when x [ 0.8 % that
was associated with the disordered crystal structure and
polar nanoregions [26]. Furthermore, phase transition of
the dielectric peaks of the samples was not clearly
detected mainly because of the diffused dielectric char-
acteristic with fine grain size [30]. The inset in Fig. 5
shows the variations in the temperature coefficient of
capacitance (TCC; DC/C) of the BCT–BZT–xIrO2
ceramics as a function of IrO2 content. The TC values of
the samples remained unchanged, indicating that TC was
independent of x. The detected DC/C values (-35 % to 0)
and low tan d satisfied the Y5Y and X7R specifications of
Electronic Industries Association standards at high tem-
peratures ([TC) [31, 32]. Additionally, the subtle change
in the DC/C values was attributed to the large internal
stress [33].

Table 2 The relative permittivity (er) and loss tangent (tan d), remnant polarization (Pr) and coercive field (Ec), piezoelectric constant (d33),
planar electromechanical coupling factors (kp), mechanical quality factor (Qm) of the BCT–BZT–xIrO2 ceramics with different IrO2 contents
(x) at 25 °C
x (%) er tan d (%) Pr (lC/cm2) Ec (kV/cm) d33 (pC/N) kp Qm

0 2849 6.9 6.31 3.57 138 0.213 112.34

0.2 2883 5.8 6.52 3.63 162 0.233 99.01
0.4 2954 5.2 6.28 2.99 184 0.244 78.17
0.6 3013 4.6 5.96 3.85 199 0.258 92.78
0.8 2918 8.7 5.80 5.40 179 0.221 116.89
1.0 2877 9.5 6.21 5.96 171 0.209 117.41
1.2 2797 9.9 6.11 6.08 162 0.207 126.77

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To study the degree of relaxor-like ferroelectric charac-
teristics of the BCT–BZT–xIrO2 ceramics, a modified
Curie–Weiss law (Eq. 1) was used as described below:
1 1 ðT  Tm Þc
 ¼ ; ð1Þ
er em C
where em is the maximum relative permittivity; Tm is the
temperature associated with em; C is the modified Curie–
Weiss constant; and c is the diffuseness exponent. Param-
eter c value ranges from 1 (normal ferroelectric) to 2 (typ-
ical relaxor ferroelectric) [34] and is calculated from the
slope of the graph of ln(1/er - 1/em) versus ln(T - Tm).
Figure 6 shows the variation of c of the BCT–BZT–xIrO2
ceramics doped with different IrO2 contents assessed at a
Fig. 6 Plots of ln(1/er - 1/em) as a function of ln(T - Tm) of the
BCT–BZT–xIrO2 ceramics prepared with different IrO2 contents
(x) assessed at 10 kHz. The inset (a) shows selected enlarged regions
(1.1–1.5)
Fig. 7 Polarization–electric field (P–E) hysteresis loops of the BCT–
BZT–xIrO2 ceramics prepared with different IrO2 contents (x). The
inset (a) shows selected enlarged regions (-6.8 to 0 kV/cm)
6139
frequency of 10 kHz. As observed, c of the samples first
decreased and then increased, which indicated that dif-
fuseness was receded with increasing x (\0.6 %). However,
the diffuseness of the ceramics increased when x [ 0.8 %.
This finding was related to ingredient heterogeneity and
structural disorder/crystal lattice distortion [16]. The higher
relaxor state (c = *1.9) of the ceramics than the literature
reports was believed to be due to the balance between the
altered long-range and short-range forces in the large grain
boundaries volume with fine grain sizes [14, 35].
The P–E hysteresis loops of the BCT–BZT–xIrO2
ceramics doped with different IrO2 contents are shown in
Fig. 7. All hysteresis loops were typically saturated, sug-
gesting good ferroelectric properties. However, the area
associated with the hysteresis loops increased when
x [ 0.6 %, indicating that the electrical loss increased with
excessive IrO2 content. This finding is consistent with the tan
d results in Fig. 5. Variations in the remnant polarization (Pr)
and coercive field (Ec) in the selected enlarged region (-6.8
to 0 kV/cm) can be observed in the inset of Fig. 7 and
Table 2. As observed, Pr first enhanced and then deteriorated
with increasing x. The enhanced Pr was associated with easy
switched domain in the consistence of T and R phases (PPT
region), and the similar results were reported in the literature
[36, 37]. The increased Ec with excessive IrO2 content was
attributed to a high restoring force of domain owing to the
dipole defects in the distorted crystal structure [38].
Figure 8 shows the variations in the piezoelectric con-
stant (d33), planar and thickness vibration electromechani-
cal coupling factors (kp and kt), and mechanical quality
factor (Qm) of the BCT–BZT–xIrO2 ceramics doped with
different IrO2 contents. As observed, d33 reached a maxi-
mum value of 199 pC/N at x = 0.6 % in Table 2 owing to
the substitution of B sites (Ti: 1.54; Zr: 1.33) with higher
electronegative Ir (2.20) in the ABO3 structure of the
Fig. 8 Variations in the piezoelectric constant (d33), planar and
thickness vibration electromechanical coupling factors (kp and kt), and
mechanical quality factor (Qm) of the BCT–BZT–xIrO2 ceramics with
varying IrO2 contents (x)
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6140
ceramics. Substitution resulted in sp3 hybridization of
covalency with more covalent bonds and improved piezo-
electric properties [39]. Moreover, the elevated d33 at
x = 0.6 % was due to the easy polarization in PPT regions in
the presence of an external electric field. However, d33
deteriorated considerably with excessive x, which was
associated with the distorted crystal structure and ingredient
heterogeneity [40]. Likewise to d33, kp and kt featured similar
trend. In contrast, Qm showed an opposite tend. Specifically,
Qm reached a minimum value of 78.17 at x = 0.4 %, and the
relative lower Qm than the literature could enhance the fre-
quency band of the electron component [15, 28]. The
observed trend around PPT regions was attributed to the
relatively low internal stress and weak pinching effects of the
domain wall in the PPT region [36, 37].
Conclusions
0.5Ba0.7Ca0.3TiO3–0.5BaTi0.8Zr0.2O3–xIrO2 ceramics were
prepared via sintering of the as-synthesized nanoparticles
at a temperature of 1260 °C. The ceramic samples featured
high levels of densification with a fine grain size. The XRD
results confirmed the occurrence of phase transition with
increasing IrO2 content and coexisted T and R phases (PPT
region) when x * 0.6 %. Slightly enhanced dielectric
properties and excellent TCC at high temperatures were
obtained that were dependent on the IrO2 content under the
synthesis conditions. The diffuseness dielectric character-
istics were weakened, and the ferroelectric and piezoelec-
tric properties were enhanced in the PPT region, indicating
that the electrical properties were strongly influenced by
IrO2 doping. The deteriorated electrical properties with
excessive x were attributed to the presence of dipole
defects and the distorted crystal structure. The electrical
properties of the ceramics obtained by IrO2 doping sug-
gested that the prepared ceramics are promising candidates
for application as lead-free dielectric and ferroelectric
materials.
Acknowledgements The work was supported by Fundamental
Research Funds for National University (CUG120118), State Key
Laboratory of Advanced Technology for Materials Synthesis Pro-
cessing (Wuhan University of Technology, 2012-KF-3). The authors
express sincere thanks to Dr. Hongquan Wang for FESEM
measurements.
References
1. Cross E (2004) Materials science: lead-free at last. Nature
432:24–25
2. Damjanovic D, Klein N, Li J, Porokhonskyy V (2010) What can
be expected from lead-free piezoelectric materials? Funct Mater
Lett 03:5–13
123
J Mater Sci (2015) 50:6134–6141
3. Chen J, Chen XL, He F, Wang YL, Zhou HF, Fang L (2014)
Thermally stable BaTiO3-Bi(Mg0.75W0.25)O3 solid solutions:
sintering characteristics, phase evolution, Raman spectra, and
dielectric properties. J Electron Mater 43:1112–1118
4. Hennings D, Schreinemacher H (1995) Ca-acceptors in dielectric
ceramics sintered in reductive atmospheres. J Eur Ceram Soc
15:795–800
5. Zhang Q, Sun H, Wang X, Zhang Y, Li X (2014) Strong pho-
toluminescence and piezoelectricity properties in Pr-doped
Ba(Zr0.2Ti0.8)O3-(Ba0.7Ca0.3)TiO3 ceramics: influence of con-
centration and microstructure. J Eur Ceram Soc 34:1439–1444
6. Liu WF, Ren XB (2009) Large piezoelectric effect in Pb-free
ceramics. Phys Rev Lett 103:257602
7. Wu J, Wu W, Xiao D, Wang J, Yang Z, Peng Z, Chen Q, Zhu J
(2012) (Ba, Ca)(Ti, Zr)O3-BiFeO3 lead-free piezoelectric
ceramics. Curr Appl Phys 12:534–538
8. Kaushal A, Olhero S, Singh B, Zamiri R, Saravanan V, Ferreira J
(2014) Successful aqueous processing of a lead free
0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 piezoelectric material
composition. RSC Adv 4:26993–27002
9. Shrout TR, Zhang SJ (2007) Lead-free piezoelectric ceramics:
alternatives for PZT? J Electroceram 19:113–126
10. Zhang L, Ren X (2006) Aging behavior in single-domain Mn-
doped BaTiO3 crystals: implication for a unified microscopic
explanation of ferroelectric aging. Phys Rev B 73:094121
11. Kaushal A, Olhero S, Singh B, Fagg D, Bdikin I, Ferreira J
(2014) Impedance analysis of 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7-
Ca0.3)TiO3 ceramics consolidated from micro-granules. Ceram
Int 40:10593–10600
12. Kaushal A, Olhero S, Ferreira J (2013) Lead-free 0.5Ba(Zr0.2-
Ti0.8)O3-0.5(Ba0.7Ca0.3)TiO3 powder surface treated against
hydrolysis—a key for a successful aqueous processing. J Mater
Chem C 1:4846–4853
13. Wu W, Cheng L, Bai S, Dou W, Xu Q, Wei Z, Qin Y (2013)
Electrospinning lead-free 0.5Ba(Zr0.2Ti0.8)O3-0.5(Ba0.7Ca0.3)-
TiO3 nanowires and their application in energy harvesting.
J Mater Chem A 1:7332–7338
14. Mishra P, Kumar SP (2012) Effect of sintering temperature on
dielectric, piezoelectric and ferroelectric properties of BZT-BCT
50/50 ceramics. J Alloys Compd 545:210–215
15. Srinivas A, Krishnaiah RV, Niranjani VL, Kamat SV, Karthik T,
Asthana S (2015) Ferroelectric, piezoelectric and mechanical
properties in lead free (0.5)Ba(Zr0.2Ti0.8)O3-(0.5)(Ba0.7Ca0.3)-
TiO3 electroceramics. Ceram Int 41:1980–1985
16. Ehmke MC, Daniels J, Glaum J, Hoffman M, Blendell JE,
Bowman KJ (2013) In situ X-ray diffraction of biased ferroelastic
switching in tetragonal lead-free (1 - x)Ba(Zr0.2Ti0.8)O3-
x(Ba0.7Ca0.3)TiO3 piezoelectrics. J Am Ceram Soc 96:2913–2920
17. Liu YX, Masumoto H, Goto T (2005) Structural, electrical and
optical characterization of SrIrO3 thin films prepared by laser-
ablation. Mater Trans 46:100–104
18. Choi KJ, Baek SH, Jang HW, Belenky LJ, Lyubchenko M, Eom
CB (2010) Phase-transition temperatures of strained single-crys-
tal SrRuO3 thin films. Adv Mater 22:759–762
19. Tian YS, Gong YS, Zhang ZL, Meng DW (2014) Phase evolu-
tions and electric properties of BaTiO3 ceramics by a low-tem-
perature sintering process. J Mater Sci Mater Electron 25:5467–
5474
20. Tian YS, Gong YS, Meng DW, Li YJ, Kuang BY (2015)
Dielectric dispersion, diffuse phase transition, and electrical
properties of BCT-BZT ceramics sintered at a low-temperature.
J Electron Mater. doi:10.1007/s11664-015-3727-3
21. Tian YS, Gong YS, Meng DW, Cao SQ (2015) Structure and
electrical properties of Ir4?-doped 0.5Ba0.9Ca0.1TiO3-
0.5BaTi0.88Zr0.12O3-0.12%La ceramics via a modified Pechini
method. Mater Lett 153:44–546
J Mater Sci (2015) 50:6134–6141
22. Tian YS, Gong YS, Wu MY, Meng DW, Jin HY (2014) Study on
the densification of BaIrO3 bulks by spark plasma sintering and
its films deposition. J Electroceram. doi:10.1007/s10832-014-
9961-x
23. Wu J, Xiao D, Wu W, Chen Q, Zhu J, Yang Z, Wang J (2012)
Composition and poling condition-induced electrical behavior of
(Ba0.85Ca0.15)(Ti1-xZrx)O3 lead-free piezoelectric ceramics. J Eur
Ceram Soc 32:891–898
24. Lee YC, Yeh YY, Tsai PR (2012) Effect of microwave sintering on
themicrostructure and electric properties of (Zn, Mg)TiO3-based
multilayer ceramic capacitors. J Eur Ceram Soc 32:1725–1732
25. Morrison FD, Sinclair DC, Skakle JMS, West AR (1998) Novel
doping mechanism for very-high-permittivity barium titanate
ceramics. J Am Ceram Soc 81:1957–1960
26. Dong L, Stone DS, Lakes RS (2012) Enhanced dielectric and
piezoelectric properties of xBaZrO3-(1 - x)BaTiO3 ceramics.
J Appl Phys 111:084107
27. Chen T, Zhang T, Wang G, Zhou J, Zhang J, Liu Y (2012) Effect
of CuO on the microstructure and electrical properties of
Ba0.85Ca0.15Ti0.90Zr0.10O3 piezoceramics. J Mater Sci 47:4612–
4619. doi:10.1007/s10853-012-6326-1
28. Lin W, Fan L, Lin D, Zheng Q, Fan X, Sun H (2013) Phase
transition, ferroelectric and piezoelectric properties of Ba1-x-
CaxTi1-yZryO3 lead-free ceramics. Curr Appl Phys 13:159–164
29. Zhang L, Thakur OP, Feteira A, Keith GM, Mould AG, Sinclair
DC, West AR (2007) Comment on the use of calcium as a dopant
in X8R BaTiO3-based ceramics. Appl Phys Lett 90:142914-
1–142914-3
30. Tang X, Wang J, Wang X, Chan H (2004) Effects of grain size on
the dielectric properties and tunabilities of sol-gel derived
Ba(Zr0.2Ti0.8)O3 ceramics. Solid State Commun 131:163–168
31. Hong JY, Lu HY (2014) Polar nanoregions and dielectric prop-
erties of BaTiO3-based Y5V multilayer ceramic capacitors. J Am
Ceram Soc 97:2256–2263
6141
32. Shen ZB, Wang XH, Gong HL, Wu LW, Li LT (2014) Effect of
MnO2 on the electrical and dielectric properties of Y-doped
Ba0.95Ca0.05Ti0.85Zr0.15O3 ceramics in reducing atmosphere.
Ceram Int 40:13833–13839
33. Maiti T, Guo R, Bhalla A (2008) Structure property phase dia-
gram of BaZrxTi1-xO3 system. J Am Ceram Soc 91:1769–1780
34. Merz WJ (1950) The effect of hydrostatic pressure on the Curie
point of barium titanate single crystals. Phys Rev 77:52–54
35. Jeong IK, Park CY, Ahn JS, Park S, Kim DJ (2010) Ferroelectric-
relaxor crossover in Ba(Ti1-xZrx)O3 studied using neutron total
scattering measurements and reverse Monte Carlo modeling.
Phys Rev B 81:214119-1–214119-5
36. Zhang JL, Zong XJ, Wu L, Gao Y, Zheng P, Shao SF (2009)
Polymorphic phase transition and excellent piezoelectric perfor-
mance of (K0.55Na0.45)0.965Li0.035Nb0.80Ta0.20O3 lead-free
ceramics. Appl Phys Lett 95:022909-1–022909-3
37. Dai YJ, Zhang XW, Chen KP (2009) Morphotropic phase
boundary and electrical properties of K1-xNaxNbO3 lead-free
ceramics. Appl Phys Lett 94:042905-1–042905-3
38. Zhou PF, Zhang BP, Zhao L, Zhao XK, Zhu LF, Cheng LQ, Li JF
(2013) High piezoelectricity due to multiphase coexistence in
low-temperature sintered (Ba, Ca)(Ti, Sn)O3-CuOx ceramics.
Appl Phys Lett 103:172904–1–172904-5
39. Saito Y, Takao H, Tani T, Nonoyama T, Takatori K, Homma T,
Nagaya T, Nakamura M (2004) Lead-free piezoceramics. Nature
432:84–87
40. Coondoo I, Panwar N, Amorı́n H, Alguero M, Kholkin AL (2013)
Synthesis and characterization of lead-free 0.5Ba(Zr0.2Ti0.8)O3-
0.5(Ba0.7Ca0.3)TiO3 ceramic. J Appl Phys 113:214107–1–
214107-6
123