research papers

Journal of
Applied
Evaluating the polymorphic phase transition in
Crystallography calcium-doped Ba(Zr0.05Ti0.95)O3: a lead-free
ISSN 0021-8898
piezoelectric ceramic
Received 28 August 2012
Accepted 7 January 2013 Gurvinderjit Singh,* V. S. Tiwari and P. K. Gupta

Laser Materials Development and Devices Division, Raja Ramanna Centre for Advanced
Technology, Indore 452 013, India. Correspondence e-mail: gjit@rrcat.gov.in

Structural and dielectric investigations were carried out on a perovskite lead-

# 2013 International Union of Crystallography
Printed in Singapore – all rights reserved
free (Ba1xCax)(Zr0.05Ti0.95)O3 ferroelectric ceramic for x = 0.03, 0.05, 0.08, 0.10,
0.12 and 0.15. The room-temperature structural analysis reveals a crossover
from orthorhombic to tetragonal crystal structure near x = 0.10. A coexistence of
tetragonal (P4mm) and orthorhombic (Pmm2) structure is observed in the
composition range 0.05  x  0.10. The fraction of tetragonal phase increases
from 27% for x = 0.05 to 71% for x = 0.10. The dielectric measurements show
that the tetragonal to orthorhombic and rhombohedral to orthorhombic
transition temperatures decrease with an increase in Ca2+ content, while the
cubic to tetragonal transition temperature remains the same. It is also shown
that for the tetragonal to orthorhombic transition a phase coexistence occurs
over a temperature range of about 18 K. The coexistence range covers room
temperature for intermediate compositions: x = 0.05, 0.08 and 0.10. Therefore,
higher dielectric and piezoelectric properties are observed in these composi-
tions.

1. Introduction bohedral transition temperatures (Takahashi et al., 2006). This

Recently, lead-free piezoelectric ceramics have been widely
studied as an alternative to lead-based piezoelectric ceramics
(Takenaka et al., 2008). Among the various possible candi-
dates, barium titanate (BaTiO3)-based materials have received
considerable attention owing to their excellent piezoelectric
properties (Maiwa, 2007; Vijatović et al., 2008; Yu et al., 2007;
Nanakorn et al., 2008; Choi et al., 2010; Li et al., 2010a). The
enhancement in piezoelectric properties in lead-based
compositions has been associated with the existence of the
morphotropic phase boundary (MPB), where two ferroelectric
phases coexist. Near the MPB, the energy barriers of the two
phases are close to each other, making it easy for polarization
to jump from one state to another when an external field is
applied. It has been realized (Chang et al., 2009; Fu et al., 2010)
that coexistence of ferroelectric phases can also be achieved
near room temperature in systems having a polymorphic
phase transition (PPT). It is known that pure BaTiO3 under-
goes polymorphic phase transitions in the temperature range
200–405 K (Jaffe et al., 1971; Lines & Glass, 1977; Clarke,
1976). A phase transformation from the high-temperature
paraelectric cubic phase to a tetragonal phase occurs at 405 K;
further lowering of the temperature leads to an orthorhombic
phase at 273 K, which finally transforms to a rhombohedral
phase at 200 K. The reported (Berlincourt & Krueger, 1957)
piezoelectric charge coefficient (d33) of pure BaTiO3 ceramic
is 190 pC N1 at room temperature. However, this value can
be increased to as high as 420 and 300 pC N1 in the vicinity of
the tetragonal to orthorhombic and orthorhombic to rhom-
information is exploited to achieve a high piezoelectric coef-
ficient at room temperature by bringing the tetragonal to
orthorhombic phase-transition temperature near room
temperature with the help of dopants or the formation of a
solid solution (Yu et al., 2002; Liu & Ren, 2009; Zhang et al.,
2009; Li et al., 2010b; Su et al., 2011). It is known (Chang et al.,
2009) that partial substitution of Zr4+ (or Sn4+) at titanium
(Ti4+) sites shifts the tetragonal to orthorhombic and ortho-
rhombic to rhombohedral phase-transition temperatures
towards the high-temperature side, while lowering the cubic to
tetragonal transition temperature. Thus, a certain amount of
Zr4+ (Sn4+) substitution in BaTiO3 may bring the tetragonal to
orthorhombic transition temperature near to room tempera-
ture, leading to improved piezoelectric properties.
The effect of Zr4+ incorporation on the dielectric and
piezoelectric properties of BaTiO3 has been investigated in
the past (Yu et al., 2002; Li et al., 2010c). It has been observed
that 5 mol% Zr4+ substitution in BaTiO3, i.e. Ba(Zr0.05-
Ti0.95)O3, brings the tetragonal to orthorhombic phase-tran-
sition temperature close to 331 K (Yu et al., 2002; Li et al.,
2010b) and gives optimum piezoelectric properties. Recently,
it has been found (Li et al., 2010b) that the piezoelectric
properties of Ba(Zr0.05Ti0.95)O3 can further be improved by
doping with calcium (Ca2+) and are optimal for 8 mol% of
doping. The enhancement of piezoelectric properties was
attributed to the presence of phase coexistence at room
temperature. Similar results were observed in the (Na0.52-
K0.48)(Nb0.93Sb0.07)O3 (Fu et al., 2009) and (K0.5Na0.5)1x-

324 doi:10.1107/S0021889813000666 J. Appl. Cryst. (2013). 46, 324–331

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LixNbO3 (Ge et al., 2011) systems by bringing the PPT near to out, the diffractometer was aligned with standard silicon
room temperature. However, these studies still lack detailed powder. All the measurements were carried out under similar
analysis of the phase-transition behaviour. The presence of conditions. Fig. 1 shows the powder XRD pattern of the
PPTs can be revealed by detailed structural and dielectric sintered ceramic. The X-ray diffraction patterns revealed the
measurements. In this context, a lot of work has been carried formation of a single perovskite phase. The data were indexed
out on lead-based compositions by means of X-ray diffraction with cubic perovskite as observed in the paraelectric phase.
(Noheda et al., 1999, 2002; Singh & Pandey, 2003; Ye et al.,
2001; Ragini et al., 2002; Mitoseriu et al., 2002; Singh & Tiwari,
2007), and an MPB has been established in the composition 3. Results and discussion
plane. These investigations have established a correlation In order to understand the phase change with composition, the
between structure and the piezoelectric properties. powder X-ray diffraction profiles of the 200, 220 and 222
The present study includes a systematic investigation of the pseudo-cubic reflections of various compositions were
structural and dielectric behaviour of Ca2+-doped Ba(Zr0.05- analysed. It is evident from Fig. 2 that for x = 0.03 and 0.05 the
Ti0.95)O3 ceramic. The effect of calcium content on phase- 200 reflections are broad, but two distinct peaks having almost
transition temperatures and room-temperature crystal struc- equal intensity are present. This suggests the existence of the
ture will be explored with a combination of Rietveld refine- orthorhombic phase with lattice parameters a ’ b 6¼ c in both
ment and dielectric spectroscopy. The outcome of our result the compositions. The 200 diffraction peak splits into 002 and
will provide information about the basic mechanism behind 200/020 peaks with an intensity ratio of 1:2 for compositions
the anomalous behaviour. In addition, it will contribute higher than x  0.08, indicating a tetragonal structure. The 220
further to the contemporary understanding of the nature of set of reflections a show broad single peak for x = 0.03 and
PPTs. 0.05, while for higher compositions this splits into a doublet, as
observed in the tetragonal structure. On the other hand, the
222 reflections show a diffuse hump on the lower-2 side for
2. Experimental the x = 0.05 and 0.08 compositions, indicating the presence of
The (Ba1xCax)(Zr0.05Ti0.95)O3 ceramics for x = 0.03, 0.05, mixed crystallographic phases as observed near the MPB.
0.08, 0.10, 0.12 and 0.15 were prepared by the conventional However, for x = 0.03, 0.10, 0.12 and 0.15 this peak is nearly a
solid-state reaction technique. BaCO3, CaCO3, ZrO2 and TiO2 singlet with asymmetric broadening towards the higher-angle
were mixed in stoichiometric proportion in a 250 ml poly- side. This broadening is due to the K2 contribution, marked
ethylene jar with zirconia balls in ethanol medium for 10 h. All by an arrow in the figure. The X-ray line profile analysis
the starting chemicals were 99.5% pure except ZrO2, which reveals that there is an orthorhombic to tetragonal crossover
had 99% purity. The dried mixture was then calcined twice at
1623 K for 6 h each time, with an intermediate grinding to
ensure the completion of the reaction. Single-phase formation
of the powder was confirmed by X-ray diffraction. Calcined
powders were ground, sieved through a 53 mm mesh, and then
compacted in the form of discs of diameter 15 mm and
thickness 1–2 mm. These discs were sintered in ambient
conditions at 1773 K for 10 h. The density of the sintered
samples was measured by the liquid displacement method and
found to be 95% of the theoretical value. The sintered
specimens were lapped and electroded using a high-
temperature-curing silver paste and subjected to dielectric
measurements at different temperatures and frequencies using
an HP4194A impedance analyser. The sample temperature
was controlled and measured using a Eurotherm 902
programmable temperature controller and a chromel–alumel
thermocouple with an accuracy of 0.1 K.
The sintered ceramic pellets were crushed into fine
powders, sieved through a 53 mm sieve, and annealed at 773 K
for 4 h to remove the residual stresses developed during
crushing and grinding. X-ray diffraction (XRD) analysis of
this powder was carried out using a Rigaku Ultrax-18 powder
diffractometer operated at 50 kV, 150 mA, in Bragg–Brentano
geometry with a curved crystal graphite 224 R mono-
chromator. The XRD data were recorded with Cu K radia-
tion in the 2 range of 20–90 at a step size of 0.01 and a scan Figure 1
rate of 1 min1. Before the XRD measurements were carried Powder X-ray diffraction of (Ba1xCax)(Zr0.05Ti0.95)O3 ceramics.

J. Appl. Cryst. (2013). 46, 324–331 Singh, Tiwari and Gupta  Polymorphic phase transition in (Ba1xCax)(Zr0.05Ti0.95)O3 325
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Table 1 on BaTiO3-based materials. The atomic positions were fixed at
A comparison of R factors obtained after Rietveld refinement of special Wyckoff sites, i.e. the Ba2+/Ca2+ ion occupies the 1a site
(Ba1xCax)(Zr0.05Ti0.95)O3 for Pmm2, P4mm and Pmm2 + P4mm space
groups. at the (0, 0, z) position, Zr4+/Ti4+ occupies the 1b site at ( 12, 12,
z), (O2)1 occupies the 2c site at the ( 12, 0, z) position and
Pmm2 P4mm Pmm2 + P4mm
(O2)11 is at ( 12, 12, z) for the tetragonal phase with space group
x Rp Rwp R B 2 Rp Rwp RB 2 Rp Rwp RB 2 P4mm. For the orthorhombic space group Pmm2 the Ba2+/
0.03 9.72 11.83 3.62 4.29 – – – – 9.75 11.79 4.90 (O) 4.33 Ca2+ ion occupies the 1a site at the (0, 0, z) position, Zr4+/ Ti4+
6.12 (T) occupies the 1d site at ( 12, 12, z), and the three O atoms (O2)I,
0.05 10.60 13.97 6.78 5.07 – – – – 10.10 12.60 4.58 (O) 4.12
5.17 (T)
(O2)II and (O2)III occupy the 1b, 1c and 1d Wyckoff sites,
0.08 – – – – 10.62 13.03 6.11 6.38 9.60 12.15 4.19 (O) 3.80 respectively. Refinements for various compositions were
4.68 (T) carried out in a sequential manner; the refined structural
0.10 – – – – 9.80 12.94 6.38 5.10 9.15 12.50 4.69 (O) 4.78
3.18 (T)
parameters of the lower composition were used as initial input
0.12 – – – – 9.45 12.08 4.01 5.17 9.50 12.03 4.68 (O) 5.20 structural parameters for the next higher composition. On the
4.29 (T) basis of line profile analysis results the diffraction data of x =
0.15 – – – – 9.64 12.81 4.23 4.78 9.60 12.84 4.98 (O) 4.81
4.72 (T)
0.03 and 0.05 were refined for Pmm2 and a mixture of the
P4mm and Pmm2 space groups. Similarly the diffraction data
for x = 0.08, 0.10, 0.12 and 0.15 were refined for P4mm and a
in (Ba1xCax)(Zr0.05Ti0.95)O3. Therefore, further structural mixture of the P4mm and Pmm2 space groups. It has been
analysis was carried out to locate the crossover region. observed, especially for mixed phases, that refinement of peak
Full pattern Rietveld refinement was carried out using width parameters prior to peak profile parameters results in
LHPM-RIETICA (Hunter, 1998; http://www.rietica.org) in nonconvergence of the refinement. Accordingly, the peak
order to analyse the structure of (Ba1xCax)(Zr0.05Ti0.95)O3. In width parameters for all the considered phases were refined
all the refinements, the pseudo-Voigt function was used to after the refinement of peak profile parameters. Insignificant
define the peak profiles, while a fifth-order polynomial was values of isotropic displacement parameters were observed if
used for describing the background. Except for the occupancy atomic positions and displacement parameters were refined
parameter, which was kept fixed at nominal composition, all simultaneously. Therefore, the refinement of displacement
other parameters, i.e. scale factor, zero correction, back- parameters was carried out after fixing the atomic positions.
ground, half-width parameters, positional coordinates and The displacement parameters of O atoms were not refined and
isotropic displacement parameters, were refined. The lattice were kept constant at 0.6. It has been observed that the
parameters were refined using Le Bail fitting prior to the refinement of displacement parameters and atomic positions
structural refinement. The quality of the fit was checked via for mixed phases led to little change in the R factors.
the Rp, Rwp, RB and 2 values (Young, 1993). Tetragonal Fig. 3 depicts the observed, calculated and difference
(P4mm), orthorhombic (Pmm2), and a mixture of tetragonal profiles after the final cycle of refinement for each composi-
and orthorhombic space groups were considered for structural tion. The agreement factors are given in Table 1. This shows
refinement. The choice of space group was decided on the that the x = 0.03, 0.12 and 0.15 compositions have nearly the
basis of our X-ray line profile analysis and available literature same values of Rp, Rwp and 2 for single (Pmm2 for 0.03 and

Figure 2
Evaluation of X-ray diffraction profiles for the 200, 220 and 222 reflections.

326 Singh, Tiwari and Gupta  Polymorphic phase transition in (Ba1xCax)(Zr0.05Ti0.95)O3 J. Appl. Cryst. (2013). 46, 324–331
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Table 2 temperature. The refined structural parameters for the best fit
Lattice parameters, volume and weight fraction of the P4mm phase (Wt) space group are listed in Tables 2 and 3. The weighted frac-
for best fitting space groups for (Ba1xCax)(Zr0.05Ti0.95)O3.
tions of the individual components for mixed phases obtained
Pmm2 P4mm by Rietveld refinement are also listed in Table 2. The weighted
Lattice parameters (Å) Lattice parameters (Å) fractions indicate that the fraction of P4mm increases on
Volume increasing the calcium content. In addition, the volume of the
x a b c a=b c (Å3) Wt unit cell decreases as the calcium content increases. This is
0.03 4.001 (4) 4.010 (3) 4.026 (5) – – 64.59 0.0 expected because of the smaller ionic size of Ca2+ (1.26 Å)
0.05 3.996 (2) 4.004 (2) 4.024 (3) 4.002 (3) 4.000 (4) 64.39 0.27 compared with Ba2+ (1.42 Å). This result further confirms that
0.08 3.992 (3) 3.998 (5) 4.023 (4) 3.996 (5) 4.023 (2) 64.22 0.59
0.10 3.989 (4) 3.998 (3) 4.021 (5) 3.994 (4) 4.019 (6) 64.11 0.71
the calcium ion has entered into the Ba(Zr0.05Ti0.95)O3 matrix.
0.12 – – – 3.990 (4) 4.017 (3) 63.95 1.0 The isotropic displacement parameters of the Ba2+/Ca2+ sites
0.15 – – – 3.984 (3) 4.015 (2) 63.72 1.0 are reasonably lower than those of the lead-based systems
(Table 3), implying strong ordering in the structure (Alonso &
Rasines, 1988; Verbaere et al., 1992; Zhukov et al., 1995;
P4mm for 0.12 and 0.15) as well as a mixture of P4mm and Lampis et al., 1999). Lead-based systems have displacement
Pmm2 phases. However, on the basis of the RB factor, which is parameters as large as 3.2 Å2, which reflects a structural
an indicator of the quality of the fit between observed and disorder. Following from the Rietveld analysis it can be
calculated integrated intensities of Bragg peaks, it is clear that concluded that the introduction of calcium into Ba(Zr0.05-
the x = 0.03 composition has orthorhombic (Pmm2) and the x = Ti0.95) leads to a change in room-temperature crystal structure.
0.12 and 0.15 compositions tetragonal (P4mm) symmetry. All Low calcium content, x = 0.03, results in an orthorhombic
other compositions, x = 0.05, 0.08 and 0.10, have reasonably structure and higher concentration, x = 0.12 and 0.15, in a
low R factors and 2 values for the mixed phase. This fact tetragonal structure. The tetragonal and orthorhombic phases
implies that these compositions exhibit coexistence of coexist for intermediate compositions, i.e. x = 0.05, 0.08 and
orthorhombic (Pmm2) and tetragonal (P4mm) phases at room 0.10.

Figure 3
Observed (dots), calculated (continuous line) and difference (bottom line) profiles obtained from the Rietveld refinement of (Ba1xCax)(Zr0.05Ti0.95)O3.
The data presented are for the best fitting space group, as indicated on each graph.

J. Appl. Cryst. (2013). 46, 324–331 Singh, Tiwari and Gupta  Polymorphic phase transition in (Ba1xCax)(Zr0.05Ti0.95)O3 327
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The temperature dependencies of the dielectric constant
and loss angle (tan ) during cooling for (Ba1xCax)(Zr0.05-
Ti0.95)O3 (x = 0.03, 0.05, 0.08, 0.10, 0.12 and 0.15) ceramics are
shown in Fig. 4. Although we carried out measurements at 20
different frequencies, only data collected at frequencies of 0.1,
10, 50 and 100 kHz are presented for the sake of clarity. The
polymorphic phase transitions corresponding to cubic to
tetragonal, tetragonal to orthorhombic and orthorhombic to
rhombohedral are seen as dielectric anomalies in the figure.
On the basis of earlier investigations on BaTiO3-based cera-
mics (Jaffe et al., 1971; Bao et al., 2010; Hansen et al., 1998; Yu
et al., 2002), the dielectric peak near 383 K has been attributed
to the cubic to tetragonal phase transition. Likewise, the two
dielectric anomalies at lower temperatures are associated with
tetragonal to orthorhombic and orthorhombic to rhombohe-
dral transitions. It may be noted from the figure that dielectric
anomalies associated with tetragonal to orthorhombic and
orthorhombic to rhombohedral transitions are weaker than
that for the cubic to tetragonal transition. Moreover, the
dielectric peak height corresponding to these transitions
decreases with increasing Ca2+ content. It is also clear from the
figure that tan  increases with decreasing temperature. The

Figure 4
Variation of dielectric permittivity with temperature for (Ba1xCax)(Zr0.05Ti0.95)O3.

328 Singh, Tiwari and Gupta  Polymorphic phase transition in (Ba1xCax)(Zr0.05Ti0.95)O3 J. Appl. Cryst. (2013). 46, 324–331
 research papers
Table 3
Structural parameters obtained after Rietveld refinement of (Ba1xCax)(Zr0.05Ti0.95)O3 for Pmm2, P4mm and Pmm2 + P4mm space groups.
0.03 0.05 0.08
Pmm2 Pmm2 P4mm Pmm2 P4mm

Displacement Ba2+/Ca2+ 0.056 (3) 0.126 (4) 0.103 (4) 0.068 (3) 0.15 (2)
parameter (Å2) Zr4+/Ti4+ 0.29 (4) 0.611 (5) 0.81 (7) 0.571 (4) 0.894 (7)

Fractional atomic Ba2+/Ca2+ 0, 0, 0.006 (2) 0, 0, 0.020 (1) 0, 0, 0.013 (3) 0, 0, 0.008 (5) 0, 0, 0.021 (2)
positions (x, y, z) Zr4+/Ti4 0.5, 0.5, 0.487 (3) 0.5, 0.5, 0.479 (7) 0.5, 0.5, 0.477 (1) 0.5, 0.5, 0.486 (5) 0.5, 0.5, 0.505 (5)
OI 0.5, 0, 0.531 (6) 0.5, 0, 0.461 (4) 0.5, 0, 0.481 (5) 0.5, 0, 0.477 (7) 0.5, 0, 0.526 (2)
OII 0.5, 0.5, 0.015 (5) 0.5, 0.5, 0.059 (4) 0.5, 0.5, 0.021 (7) 0.5, 0.5, 0.067 (5) 0.5, 0.5, 0.036 (5)
OIII 0, 0.5, 0.468 (7) 0, 0.5, 0.536 (8) – 0, 0.5, 0.512 (6) –

0.10 0.12 0.15

Pmm2 P4mm P4mm P4mm

Displacement Ba2+/Ca2+ 0.138 (5) 0.169 (3) 0.078 (6) 0.051 (4)
parameter (Å2) Zr4+/Ti4+ 0.345 (3) 0.783 (2) 0.720 (5) 0.602 (3)

Fractional atomic Ba2+/Ca2+ 0, 0, 0.003 (2) 0, 0, 0.011 (1) 0, 0, 0.012 (3) 0, 0, 0.022 (4)
positions (x, y, z) Zr4+/Ti4 0.5, 0.5, 0.472 (6) 0.5, 0.5, 0.488 (3) 0.5, 0.5, 0.501 (3) 0.5, 0.5, 0.489 (4)
OI 0.5, 0, 0.469 (3) 0.5, 0, 0.518 (3) 0.5, 0, 0.512 (7) 0.5, 0, 0.506 (5)
OII 0.5, 0.5, 0.012 (6) 0.5, 0.5, 0.014 (7) 0.5, 0.5, 0.008 (6) 0.5, 0.5, 0.025 (4)
OIII 0, 0.5, 0.532 (8) – – –

peak corresponding to the transition temperature in tan 
appears 4–5 K lower than the corresponding dielectric
constant maximum, but the behaviour of tan  is nearly the
same for all the compositions. The room-temperature value of
tan  = 0.02 is significantly lower, indicating the higher resis-
tivity of the sample. A minute dispersion in the dielectric
constant is observed at the cubic to tetragonal phase-transition
temperature (TC!T). Below and above this temperature the
dielectric constant values are nondispersive. In the ferro-
electric region the evolution of macro-sized ferroelectric
domains is responsible for such nondispersive behaviour (Chu
et al., 1995; Bidault et al., 1996; Dai et al., 1994). In the para-
electric phase, T > TC!T, the absence of any polarization
will also furnish nondispersive behaviour. Fig. 5 shows the
variation of the room-temperature dielectric constant "0RT ,
measured at 1 kHz, as a function of calcium content. As seen
in the figure the dielectric constant increases with increasing
calcium content and attains its maximum at x = 0.08. Beyond
this a gradual decrease in dielectric constant is observed. The
value of "0RT increases from 1830 for x = 0.03 to 2320 for x =
0.08. A similar anomaly was observed in the piezoelectric
charge coefficient (d33) near x = 0.08 (Li et al., 2010b).
The phase-transition temperatures, measured from the peak
position of the dielectric constant during cooling, from cubic
to tetragonal (TC!T), tetragonal to orthorhombic (TT!O) and
orthorhombic to rhombohedral (TO!R) are summarized in
Fig. 6. The points corresponding to x = 0, i.e. Ba(Zr0.05Ti0.95),
have been taken from the literature (Yu et al., 2002). It is seen
from the figure that there is a small shift in the temperature of
the cubic to tetragonal (TC!T) transition towards the higher-
temperature side with increasing calcium content. For x = 0.05
the transition temperature TC!T is 381 K, and it increases to
388 K for x = 0.15. An increase of about 0.7 K per mol% of
calcium content was observed in the cubic to tetragonal
transition temperature. It has been observed in the past that
the Ca2+ ion replaces the Ba2+ ion at the perovskite A site, and
it has been shown that there is a weak dependence of TC!T on
Ca2+ content. The weak increase in TC!T was attributed to the

Figure 5 Figure 6
Variation of dielectric constant with x at room temperature. Variation of TC!T, TT!O and TO!R with Ca concentration (x).

J. Appl. Cryst. (2013). 46, 324–331 Singh, Tiwari and Gupta  Polymorphic phase transition in (Ba1xCax)(Zr0.05Ti0.95)O3 329
research papers
increase in atomic polarizability of the calcium ion, which
stabilizes the distorted oxygen octahedron at higher
temperatures (Mitsui & Westphal, 1961). A similar trend is
observed in the temperature of the dielectric loss maximum.
The transition temperatures corresponding to tetragonal to
orthorhombic and orthorhombic to rhombohedral transitions
show a strong dependence on calcium content. It is clear from
the figure that the temperatures of the tetragonal to ortho-
rhombic (TT!O) and orthorhombic to rhombohedral (TO!R)
phase transitions decrease monotonically with increasing
calcium content. The rate of decrease of TT!O and TO!R is
much sharper than the decrease in TC!T. The approximate
values of dT/dx in the tetragonal to orthorhombic and
orthorhombic to rhombohedral transitions are estimated, on
the basis of a linear fit to the data in Fig. 6, to be 4.35 and
4.75 K per mol%, respectively. The downward shift in the
tetragonal to orthorhombic transition temperature implies
that the tetragonal phase is stabilized in (Ba1xCax)-
(Zr0.05Ti0.95)O3 for a larger temperature range. For instance
for x = 0.03 the tetragonal phase exists in the temperature
range from 378 to 314 K,
T = 64 K, and
T is enhanced to
131 K (temperature range from 388 to 256 K) for x = 0.15. This
enhancement in
T will improve the temperature stability of
the piezoelectric and dielectric properties of these ceramics,
especially for their underwater applications.
It is clear from dielectric measurements of (Ba1xCax)-
(Zr0.05Ti0.95)O3 that the tetragonal to orthorhombic phase-
Figure 7
Heating–cooling dielectric measurements for (Ba1xCax)(Zr0.05Ti0.95)O3 in the vicinity of the tetragonal to orthorhombic transition temperature.
330 Singh, Tiwari and Gupta  Polymorphic phase transition in (Ba1xCax)(Zr0.05Ti0.95)O3
transition temperature decreases from 326 K for x = 0.0 to
275 K for x = 0.12. For x = 0.08 the tetragonal to orthorhombic
phase-transition temperature (292 K) is near to room
temperature (300 K). Thus the X-ray diffraction data analysis
and dielectric measurements suggest that the formation of
phase coexistence in (Ba1xCax)(Zr0.05Ti0.95)O3 is caused by a
shift of the tetragonal to orthorhombic phase-transition
temperature closer to room temperature. In fact, this tetra-
gonal to orthorhombic crossover occurs over a range of
temperature (T1–T2), which corresponds to the phase coex-
istence region. Experimentally it is characterized by thermal
hysteresis of a particular phase transition in dielectric
permittivity measurements. Fig. 7 represents the dielectric
measurements in the vicinity of the tetragonal to ortho-
rhombic transition during the heating–cooling cycle for four
different compositions, i.e. x = 0.05, 0.08, 0.10 and 0.12. It is
evident from the figure that a thermal hysteresis of about 18 K
is observed for the tetragonal to orthorhombic transition. If
this temperature is taken as the span of temperature range for
phase coexistence around the phase-transition temperature
then the coexistence range will be 314–332 K for x = 0.03, 304–
321 K for x = 0.05, 292–310 K for x = 0.08, 286–304 K for x =
0.10, 276–293 K for x = 0.12 and 256–275 K for x = 0.15. This
clearly indicates that compositions x = 0.08 and 0.10 have
coexistence of tetragonal and orthorhombic phases at room
temperature (300 K). The composition x = 0.05 has its coex-
istence range very close to room temperature. A decrease in
J. Appl. Cryst. (2013). 46, 324–331

tetragonal to orthorhombic transition temperature with x
implies that the fraction of the tetragonal phase at room
temperature increases with increasing x. These results are in
concurrence with Rietveld refinement results where a coex-
istence of phases was observed for intermediate compositions
(x = 0.05, 0.08 and 0.10) and an increase in tetragonal phase
fraction with calcium content (x).
Both the dielectric and X-ray diffraction measurements
indicate that the anomaly in dielectric properties is caused by
the presence of a PPT near room temperature. Enhanced
dielectric and piezoelectric coefficients are observed in the
coexistence region of the orthorhombic and tetragonal phases
because the number of possible orientations of spontaneous
polarization are multiplied in this region. In the close vicinity
of the PPT, the two crystallographic phases are in thermal
equilibrium with each other with vanishing polarization
anisotropy. Therefore, a flipping of polarization between the
two phases is possible on application of an electric field. This
will result in higher dielectric and piezoelectric coefficients,
similar to the morphotropic phase boundary in other ferro-
electric systems.
4. Conclusions
Structural and dielectric investigations have been carried out
on a perovskite lead-free (Ba1xCax)(Zr0.05Ti0.95)O3 ferro-
electric ceramic for x = 0.03, 0.05, 0.08, 0.10, 0.12 and 0.15. The
dielectric and piezoelectric properties are found to be most
favourable in the compositions having phase coexistence.
Phase coexistence can be created by bringing the polymorphic
phase transition near to room temperature. Structural and
dielectric measurements on a Ca2+-doped Ba(Zr0.05Ti0.95)O3
ceramic reveal a shift in the tetragonal to orthorhombic
polymorphic phase boundary towards room temperature with
increasing Ca2+ content. A coexistence of tetragonal and
orthorhombic phases has been observed for x = 0.05, 0.08 and
0.10 at room temperature. The fact that the fraction of tetra-
gonal phases increases with increasing calcium content is
attributed to a negative shift in the tetragonal to orthorhombic
transition temperature. The dielectric investigation shows an
anomaly in dielectric constant in (Ba1xCax)(Zr0.05Ti0.95)O3
near x = 0.08. The investigation reveals that the coexistence of
tetragonal and orthorhombic phases at room temperature is
responsible for improved piezoelectric/dielectric properties in
(Ba1xCax)(Zr0.05Ti0.95)O3 because it multiplies the number of
possible orientations of spontaneous polarization. This study
is instructive for composition design of BaTiO3-based lead-
free ceramics to achieve higher piezoelectric/dielectric coef-
ficients.
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