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Acta Materialia 80 (2014) 48–55
www.elsevier.com/locate/actamat

Relationship between electromechanical properties and phase

diagram in the Ba(Zr0.2Ti0.8)O3–x(Ba0.7Ca0.3)TiO3 lead-free
piezoceramic
Matias Acosta a, Nikola Novak a,⇑, Wook Jo b, Jürgen Rödel a
a
Institute of Materials Science, Technische Universität Darmstadt, Darmstadt 64287, Germany
b
School of Materials Science and Engineering, Ulsan National Institute of Science and Technology, Ulsan 689-798, Republic of Korea

Received 7 May 2014; received in revised form 4 July 2014; accepted 26 July 2014
Available online 24 August 2014

Abstract

The Ba(Zr0.2Ti0.8)O3–x(Ba0.7Ca0.3)TiO3 system was synthesized in a wide compositional range in order to study the relationship
between its phase diagram and electromechanical properties. Phase transitions were marked using peaks in temperature-dependent per-
mittivity, providing up to three transitions from the rhombohedral phase to an orthorhombic, tetragonal and finally cubic phase, which
meet in a region that is termed the phase convergence region in this work. In situ small and large signal electromechanical properties were
studied as a function of temperature with specific emphasis on these transitions. A small signal piezoelectric coefficient, d33, presents max-
imized values at the transition from the orthorhombic to the tetragonal phase, while a large signal piezoelectric coefficient, d 33 , does so at
both rhombohedral to orthorhombic and to tetragonal phase transitions. Maximum polarization Pmax was the only quantity determined
that had a clear maximum at the phase convergence region.
Ó 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Electroceramic; Perovskites; Ferroelectric; Piezoelectric; Lead-free piezoceramics

1. Introduction [3,4]. The lead-free (1  x)Ba(Zr0.2Ti0.8)O3 (BZT)–x

Piezoelectric materials are an important class of func-
tional materials. Lead zirconate titanate (Pb(Zr,Ti)O3,
PZT) piezoceramic solid solutions are used in a large variety
of applications, such as actuators, transducers and sensors,
due their superior piezoelectric properties that are adjustable
for each specific application [1]. Recently, new legislation has
been passed prohibiting the use of lead in certain applica-
tions [2]. Therefore, much effort is required to develop
lead-free piezoceramics. To date, it seems that PZT cannot
be replaced on a broad basis, but for certain specific applica-
tions lead-free materials present promising properties, some
of which are even superior to lead-containing piezoceramics
⇑ Corresponding author. Tel.: +49 6151 16 6302.
E-mail address: Novak@ceramics.tu-darmstadt.de (N. Novak).
(Ba0.7Ca0.3)TiO3 (BCT), first reported by Liu and Ren [5],
is one of the key lead-free candidates. At room temperature
the compositionally optimized material presents a
piezoelectric coefficient d33  600 pC N1 and large signal
d 33  1100 pm V1 at 0.5 kV mm1 [5]. These electrome-
chanical responses clearly qualify this material system for
certain applications, outperforming lead-free and even most
PZT materials, albeit only within a limited temperature
range [4].
Liu and Ren [5] reported the phase diagram of the BZT–
BCT system, in which they observed a “tilted morphotrop-
ic phase boundary” (MPB) separating rhombohedral (R)
and tetragonal (T) phases. They also highlighted the pres-
ence of a tricritical point (TCP) between cubic (C)–R–T
phases, similar to that found in lead-containing materials
[6]. Recently, Keeble et al. [7] and Tian et al. [8] proposed

http://dx.doi.org/10.1016/j.actamat.2014.07.058
1359-6454/Ó 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
 M. Acosta et al. / Acta Materialia 80 (2014) 48–55
a bridging orthorhombic (O) phase between the R and T
phases. Keeble et al. [7] proposed the term “convergence
region” instead of TCP, whereas Tian et al. [8] utilized
the term “diffuse phase transition”, since they were unable
to clearly resolve the transition region. Moreover, a third
phase transition in the system was also outlined by pyro-
electric [9], Raman [10] and elastic studies [10], although
it was not recognized as such in those publications. Bjørne-
tun Haugen et al. [11] proposed that the third anomaly in
the system might be related to the coexistence of two differ-
ent symmetries and changes in the different phase fractions,
supporting the work of Ehmke et al. [12]. Hence, the phase
diagram of the system remains controversial. As our dielec-
tric measurements point to an intermediate phase between
the T and R phases, we will refer to it as an orthorhombic
phase and term the narrow regime where the different
phases coexist the phase convergence region [7].
In order to explain the outstanding electromechanical
properties of the system, Liu and Ren [5] rationalized that
the free energy of the MPB composition connected to the
tricritical point is weakly anisotropic and thus almost inde-
pendent of polarization direction [5,13–15]. This property,
accompanied by a softening of the lattice [13,16], results in
an almost negligible energy barrier for polarization rota-
tion [5,17]. In other words, the enhanced response along
the so-called MPB was proposed to result from phase tran-
sition instabilities within a narrow temperature range. If
this is the case, it should be expected that the anisotropy
becomes negligible by approaching the TCP [5,13–15,17].
Therefore, maximized properties at the TCP are expected
due to polarization rotation and extension originating from
the coexistence of ferroelectric and paraelectric phases [18].
A recent quantitative analysis using polarization dynamics
[19] suggests that the energy barrier for domain switching is
minimum at the so-called MPB.
In this study we report a detailed compositional study of
the BZT–BCT system by means of dielectric, small signal
d33 and large signal d 33 properties as functions of tempera-
ture. The methodology employed allows a complete assess-
ment of the role of the convergence region on the
electromechanical properties. Of specific interest, therefore,
is which – if any – of the electromechanical properties peak
at the convergence region. The salient question then is: is
the convergence region responsible for the outstanding
electromechanical properties or is it related to the ferroelec-
tric/ferroelectric phase transitions in the system previously
denominated as MPB?
2. Experimental
The ceramic powders were produced via a mixed oxide
route using reagent grade oxides and carbonates (Alfa
Aesar GmbH & Co. KG). The raw chemicals BaCO3 (pur-
ity 99.8%), TiO2 (purity 99.6%), CaCO3 (purity 99.5%) and
ZrO2 (purity 99.5%) were mixed according to the stoichi-
ometric formula (1  x)Ba(Zr0.2Ti0.8)O3–x(Ba0.7Ca0.3)TiO3
with x = 0.3, 0.32, 0.35, 0.37, 0.4, 0.45, 0.5 and 0.6. The
49
compositions were chosen deliberately, taking into account
representative phase diagrams proposed in the literature
[5,7] with special emphasis on the TCP [5] or phase conver-
gence region [7]. All the powders were added to homemade
nylon milling containers with yttria stabilized zirconia balls
and ethanol. The suspensions were then ball-milled in a
planetary ball mill (Fritsch Pulverisette 5) for 5 h at
250 rpm and dried at 90 °C for 24 h. The powders were cal-
cined at 1300 °C for 2 h with a heating rate of 5 K min1
and subsequently ball-milled for 15 h with the previously
described parameters. Disk-shape samples of 10 mm in
diameter and 1 mm thick (30 mg of powder) were cold
isostatically pressed (KIP 100 E, Weber-Pressen) at
300 MPa for 1.5 min. The green bodies obtained were sin-
tered in covered zirconia crucibles with atmospheric pow-
der at 1500 °C for 2 h and a heating rate of 5 K min1.
Sintered pellets were ground and polished down to
600 lm. Electrodes were painted with a silver paste and
burnt-in at 400 °C for 2 h. The reproducibility of represen-
tative compositions was corroborated with at least two dif-
ferent batches. Specifically, key compositions were
produced two to four times. From each batch at least 16
samples were produced and several of them were tested,
allowing us to choose representative samples on which to
perform further experiments.
The density of all compositions was determined using
the Archimedes method. The microstructure analysis was
performed on polished sample surfaces. To reveal the grain
boundaries, chemical etching was performed for 90 s with
50 vol.% diluted HCl and a few drops of HF. The samples
were imaged using an optical microscope (DMRME, Leica
Mikroskopie und Systeme GmbH). The average grain size
was obtained by the mean intercept length method, with a
numerical multiplication factor of 1.56 [20]. For reliable
statistical information, around 200 grains of at least three
different representative areas of samples were analyzed.
Errors on density measurements were omitted because their
magnitude was not statistically relevant relative to the
reported values. Errors in the mean grain size are reported
as standard deviations in Table 1.
Temperature- and frequency-dependent real e0r and
imaginary e00r relative permittivity were obtained on unp-
oled samples for all compositions. In all cases the complex
relative permittivity was measured in the temperature range
from 100 to 120 °C, with a heating rate of 2 K min1, and
Table 1
Average grain size and relative density of each BZT–BCT composition.
Material Average grain size (lm) Density
BZT–0.3BCT 28 ± 7 98
BZT–0.32BCT 20 ± 3 98
BZT–0.35BCT 36 ± 8 94
BZT–0.37BCT 28 ± 8 97
BZT–0.4BCT 25 ± 5 98
BZT–0.45BCT 36 ± 9 97
BZT–0.5BCT 35 ± 8 97
BZT–0.6BCT 26 ± 6 98
50 M. Acosta et al. / Acta Materialia 80 (2014) 48–55

in the frequency range from 100 Hz to 10 kHz by an
Impedance Analyzer Alpha-A equipped with a cryostat
(Novocontrol Technologies, Germany). The amplitude of
the probing ac electric signal was 1 V for all measurement
frequencies. The standard deviation of the dielectric mea-
surements was minor in comparison to the measurement
error; therefore, the error on the dielectric properties is
expressed as experimental error and is below 1%.
The small signal piezoelectric coefficient d33 was mea-
sured in situ as a function of temperature using a cus-
tom-designed device. The apparatus consists of a furnace
controlled by two thermocouples and a laser vibrometer
(Polytec sensor head OFV-505 and front-end VDD-E-
600). A pinhole was made in the middle of a thermally insu-
lating alumina covering lid, thereby allowing the laser to
pass through. Further details on the measuring machine
are presented elsewhere [21]. A heating rate of 2 K min1
was utilized for the measurement, and points were obtained
in steps of 5 °C. A sinusoidal wave with a frequency of
10 kHz and an amplitude of 10 V (equivalent to a field
strength of less than 20 V mm1) was chosen as the input
voltage. Prior to measurement, all samples were poled at
4 kV mm1 at room temperature for 10 min to ensure a
well-poled initial state. The selection of such high fields
was done based on the results of Wu et al. [22]. Prior to
each measurement, room-temperature d33 values were con-
trasted to values of a commercial Berlincourt meter
(YE2730, Sinocera, Inc.).
Large signal strain and polarization as functions of tem-
properties, it can be concluded that the BZT–BCT system
was successfully synthesized.
3.2. Relative permittivity
Fig. 1 provides the real (e0r ) and imaginary (e00r ) parts of
relative permittivity as functions of temperature and fre-
quency. Three representative compositions were selected
to depict these results, namely x = 0.3, 0.4 and 0.45. The
relative permittivity can be utilized to detect structural
phase transitions [23]. These phase transitions are accom-
panied by a dielectric anomaly independent of the measure-
ment frequency. Therefore, the temperature for phase
transitions can be obtained from the local maxima of e00r
[23]. From the temperature-dependent e00r of all of the com-
positions investigated, a pseudo-binary phase diagram for
the BZT–BCT system can be constructed (Fig. 2). Note
that it is consistent, within experimental error, with the
one recently proposed by Keeble et al. [7], although both
the synthesis route and the techniques utilized to detect
phase transitions differed. Following the work by Keeble
at al. [7], we term the phase between the rhombohedral
and tetragonal phases the orthorhombic phase. A contour
plot of the normalized e0r as a function of temperature and
composition is presented in Fig. 3. For comparison, the
16000 x=0.3 x=0.4 x=0.45
12000
100 Hz
1 kHz
ε r´

perature were obtained using a commercial piezoelectric 8000

10 kHz

system TF analyzer 200 (aixACCT Systems, GmbH). A tri-

4000
angular wave with 5 Hz measurement frequency and
0
3 kV mm1 amplitude was employed in the temperature 600
range from 25 to 125 °C. The high-voltage amplitude was
εr´´

400
chosen deliberately to ensure complete saturation of the
material. All materials were tested from an initially poled 200
state after unipolar cycling at 3 kV mm1 to ensure a
0
reproducible state. For electromechanical measurements, -50 0 50 100
o
-50 0 50 100
o
-50 0
o
50 100
T ( C) T ( C) T( C)
the experimental error was considered. The error in the
large and small signal measurements is in the order of 5– Fig. 1. Relative permittivity real e0r and imaginary e00r parts of represen-
10 microstrain. The error in the polarization measurements tative compositions as functions of temperature and frequency. The peak
is in the order of 1%. Error bars were not utilized in the fig- positions indicating phase transitions are marked with dashed lines.
ures for experimental results because data markers were
selected deliberately in the same length scale as the reported
errors. 100
T R-O
90 T C
O-T

3. Results 80
T c

70
T (°C)

T
3.1. Density and microstructure 60
50
Density and mean grain size measurements are pre-
40 R O
sented in Table 1. The grain size varies non-monotonically
30
from 20 ± 3 lm at x = 0.32 to 36 ± 9 lm at x = 0.45. All
the materials present relative densities above 94%. Varia- 0.30 0.35 0.40 0.45 0.50 0.55 0.60
BZT-xBCT
tions in grain size and density are comparable to prior
reports [22]. The X-ray analysis of the samples revealed a Fig. 2. Phase diagram obtained from the imaginary part of the relative
single phase for all materials. Considering the mentioned permittivity e00r peaks at 1 kHz.
 M. Acosta et al. / Acta Materialia 80 (2014) 48–55
Fig. 3. Contour plot of normalized real relative permittivity e0r at 1 kHz as
a function of temperature and composition.
phase transitions previously discussed in Fig. 2 are super-
imposed. In the normalized figure, local maxima appear
insignificant. Maximum e0r values should occur, as
observed, at temperatures slightly higher than the Tc
obtained from the local maxima of e00r . This is because its
maximum coincides with the inflection point of e0r [24]. It
is seen that the maximum value of e0r is given at around
x = 0.3 and 65 °C instead of the convergence region, which
is consistent with the literature [5].
3.3. Small signal piezoelectric properties
The small signal piezoelectric coefficient d33 was mea-
sured in situ in all compositions as a function of tempera-
ture. These curves, together with the phase transitions
obtained from dielectric properties, are depicted in Fig. 4.
All phase transitions in the system are accompanied by
local maxima in d33. Interestingly, the d33 does not present
the highest values for all compositions at the Tc but only
for x < 0.4. For the range of 0.4 < x < 0.5, d33 is observed
to peak at the O–T phase boundary. For all compositions
d33 retains significant values of 100 pC N1 even up to
10 °C above the Tc. Residual piezoelectricity above the Tc
was also observed in other studies [10,25,26]. Meanwhile,
on the tetragonal side (x = 0.6), the BZT–BCT system
exhibits an almost temperature-insensitive d33 value of
300 pC N1 in the temperature range from room
600 x=0.3
d33 (pC/N)
400
200
0
600 x=0.4
d33 (pC/N)
400
200
0
50 100 50
T (°C) T (°C)
Fig. 4. In situ small signal piezoelectric coefficient d33 as a function of temperature. The peak positions indicating phase transitions are marked with
dashed lines.
51
Fig. 5. Contour plot of the small signal piezoelectric coefficient d33 as a
function of temperature and composition.
temperature up to 95 °C, making this composition attrac-
tive for certain low-temperature applications.
The curves displayed in Fig. 4 were combined to pro-
duce a contour plot of d33 as a function of temperature
and composition (Fig. 5). The series of phase transitions
identified from the dielectric properties is superimposed
for comparison. Fig. 5 clearly reveals that the overall max-
imum piezoelectric response of the BZT–BCT system
occurs along the O–T phase boundary, which is consistent
with the literature [8,27,28]. It is noted that the piezoelec-
tric coefficient exhibits local maxima at the convergence
region, but overall it is not as high as near to the O–T phase
boundary.
3.4. Large signal electromechanical response
Fig. 6 provides temperature-dependent unipolar strain
values at 3 kV mm1 for the three selected representative
compositions. It is apparent that at certain temperatures
the strain output of the system is enhanced. Therefore,
the d 33 was monitored as a function of temperature for
all eight compositions to facilitate comparison with the
small signal d33. In order to ensure saturation of the
BZT–BCT system, the d 33 values are presented at
3 kV mm1, i.e. a field strength 30 times larger than the
coercive field Ec utilized. This reflects the reduced d 33 in
comparison to the values reported in the literature, which
x=0.32 x=0.35 x=0.37
x=0.45 x=0.5 x=0.6
100 50 100 50 100
T (°C) T (°C)
52 M. Acosta et al. / Acta Materialia 80 (2014) 48–55

0.20 25 °C
x=0.3 x=0.4 x=0.45 35 °C
45 °C
0.15 55 °C
65 °C

Strain (% )
0.10 75 °C
85 °C

0.05

0.00
0 1 2 3 0 1 2 3 0 1 2 3
E (kV/mm) E (kV/mm) E (kV/mm)

Fig. 6. Large signal electromechanical response of representative compositions as a function of temperature measured at 5 Hz.

x=0.3 x=0.32 x=0.35 x=0.37

d33* (pm/V)

400

200

0
d33* (pm/V)

x=0.4 x=0.45 x=0.5 x=0.6

400

200

0
50 100 50 100 50 100 50 100
T (°C) T (°C) T (°C) T (°C)

Fig. 7. The large signal coefficient d 33 as a function of temperature calculated at 3 kV mm1. The peak positions indicating phase transitions are marked
with dashed lines.

were mostly obtained at around 0.5–1 kV mm1 [5]. It is

noted that the d 33 of the currently studied materials
obtained at the optimum driving field of 1 kV mm1 at
room temperature reaches 1000 ± 200 pm V1 (depend-
ing on the composition), consistent with literature values
[5]. Again, obtained d 33 values are presented in context to
the phase transitions obtained from dielectric properties
in Fig. 7. In contrast to the d33 curves (Fig. 4), the correla-
tion between the large signal d 33 and the phase transitions
is rather weak, with only smooth changes in the strain
obtained around the transitions. In all cases, a d 33 of
200 pm V1 persists even at 10 °C above the Tc, consis-
tent with the non-zero residual d33 (Fig. 4). The composi-
tion on the tetragonal side (x = 0.6) presents the highest
temperature stability; nevertheless, the temperature depen-
dence is more pronounced than for the small signal d33. In
this case, a decay of d 33 from 350 to 250 pm V1 is
observed from room temperature up to 95 °C.
The d 33 values from Fig. 7 are summarized in a contour
plot to visualize the electromechanical response of the
BZT–BCT system as a function of temperature and com-
position at high fields. This data is presented in Fig. 8,
together with the phase diagram obtained from the dielec-
tric properties. Interestingly, contrary to the small signal
d33, there is a broad region in which the system presents
a high electromechanical response. Nevertheless, the maxi-
mum values still follow the phase transitions. Both phase
transitions from R–O and O–T present the highest d 33 val-
ues. This indicates a different electromechanical output to
the small signal d33, which peaked only at the O–T phase
Fig. 8. Contour plot of the large signal coefficient d 33 as a function of
temperature and composition calculated at 3 kV mm1.
transition (Fig. 5). As observed in the dielectric properties
and also in the small signal d33, the large signal d 33 is not
maximized at the phase convergence region.
Polarization values at 3 kV mm1, designated as maxi-
mum polarization Pmax and the remanent polarization
Prem, were also monitored as functions of temperature
and composition. No clear trends in the Prem values could
be detected, within experimental error, regardless of tem-
perature and composition. Pmax is introduced in Fig. 9
together with the phase diagram obtained from the dielec-
tric properties. In contrast to the other electromechanical
properties, Pmax remains relatively constant around all fer-
roelectric/ferroelectric phase transitions. Nevertheless, it is
maximized in the proximity of the convergence region.
Pmax acquires considerably high values (Pmax  13–
14 lC cm2), which are 45% higher than those at room
 M. Acosta et al. / Acta Materialia 80 (2014) 48–55
Fig. 9. Contour plot of Pmax as a function of temperature and compo-
sition calculated at 3 kV mm1.
temperature (Pmax  8–9 lC cm2). Therefore, the peak of
Pmax does not coincide with the response of either dielectric
or large and small signal electromechanical properties.
4. Discussion
4.1. Density and microstructure
Based on the results from Hao et al. [26], the grain size
and density values (higher than 20 lm and 94%, respec-
tively) of the samples under the current investigation are
large enough to correlate the measured functional proper-
ties with the composition and temperature (i.e. the presence
of phase transitions). Therefore, both grain size and density
are considered as secondary parameters influencing the
electromechanical properties of the system under the stud-
ied synthesis conditions.
4.2. Dielectric properties
As previously mentioned, the local maxima of the e00r
were attributed to the phase transitions of the system,
which is in good agreement with the phase diagram from
Keeble et al. [7]. Contrary to the frequency-dependent local
maxima commonly observed in relaxors [29], it was
observed that the local maxima did not present frequency
dispersion consistent with the dielectric response of classi-
cal ferroelectrics [1].
The highest values of relative permittivity do not occur
at the convergence region but at x = 0.3 and 65 °C, consis-
tent with the literature [5]. The domain morphology of
BZT–BCT near x = 0.5 has already been revealed by
Gao et al. [30] using TEM. They observed that a hierarchi-
cal nanodomain structure arises around the O–T phase
boundary. These results could be rationalized within a clas-
sical domain theory, in which domain size is proportional
to the domain wall energy, leading to minimized domains
near phase transitions. It is further consistent with theoret-
ical predictions [31] indicating that domain miniaturization
is also expected near phase instabilities in general. This
leads to an increased domain wall density and therefore
53
an increase relative permittivity. Nevertheless, the
5 mol.% BCT discrepancy between the maximized proper-
ties and the triple points gives an indication that a more
complicated physical behavior may arise [5]. We are cur-
rently performing in situ field-dependent TEM to better
correlate the domain morphology near triple points to
the presented phenomenological approach. Hence, domain
wall mobility, size and morphology are all expected to play
a key role, as recently shown in the dielectric and piezoelec-
tric response of BT [32].
4.3. Small signal piezoelectric properties
For BT, it was shown that reversible and irreversible
domain wall movement contribute to the small signal prop-
erties at fields above 5 V mm1 and at 20 Hz [33], giving
rise to a Rayleigh behavior. Regardless of the fact that
BZT–BCT is a very soft system [16], we assume, as a first
approximation, a negligible contribution of reversible and
irreversible domain wall movement with our chosen exper-
imental conditions of 0.2 V mm1 and 10 kHz. There-
fore, extrinsic contributions to d33 will not be considered
in this section. The Rayleigh analysis of the system is
beyond the scope of the present study, but should be car-
ried out for better clarification of the Rayleigh threshold
field of the system.
For further insight, we ignore the polycrystalline and
multi-domain nature of the system and instead consider a
Landau phenomenological approach [14,15,34,35] to
describe the d33, as previously proposed for the BZT–
BCT system [5,30]. For a material with a high-temperature
cubic phase, the intrinsic electric-field-induced strain can be
obtained with Eq. (1)
S ij ¼ Qijkl  P k  P l ð1Þ
where Qijkl is the electrostrictive coefficient and P k;l the
spontaneous polarization. Based on the general definition
@S
of the small signal piezoelectric coefficient d mij ¼ @Eijm , the
piezoelectric coefficient can be deduced, as demonstrated
in Eq. (1), by ignoring the temperature dependence of the
electrostrictive coefficient Qijkl [36]:
 
@P k @P l
d mij ¼ Qijkl  P l  þ Pk 
@Em @Em
¼ Qijkl  ðP l  ekm þ P k  elm Þ ð2Þ
where ekm;lm is the relative permittivity. From Eq. (2) the
piezoelectric coefficient d mij is proportional to the electro-
strictive coefficient Qijkl, the spontaneous polarization P l;k
and the relative permittivity ekm;lm . We stress that this result
is independent of the symmetry of the material, the crystal-
lographic direction and the flattening or isotropization of
the free energy. Since the electrostrictive coefficients Qijkl
are not known for BZT–BCT and are normally considered
to be temperature independent [34], we ignore their contri-
bution to temperature dependence. The maxima observed
54 M. Acosta et al. / Acta Materialia 80 (2014) 48–55
from the piezoelectric coefficients in Fig. 4 at the first phase
transition (namely R–C, R–O, O–T or T–C) are due to a
softening of the lattice [16], which is also accompanied by
local maxima in the e0r and thus in d33, as predicted in
Eq. (2). For compositions with more than one phase tran-
sition in Fig. 4, we observed that either the second phase
transition (O–C, O–T or T–C) or third phase transition
(T–C) present only local maxima of d33, indicating that
polarization extension [13] may not play a major role in
the electromechanical properties of the system. This has
recently been verified by in situ high-energy X-ray diffrac-
tion, comparing lattice extension and domain switching
as functions of the electric field [37]. Since maximized prop-
erties are not observed at high-temperature phase transi-
tions, a continuous loss of spontaneous polarization of
the system should be responsible for the non-maximized
properties in Fig. 5 based on Eq. (2). This phenomenon
was demonstrated, specifically at compositions next to
the phase transitions, by Benabdallah et al. [9]. Interest-
ingly, Benabdallah et al. [9] observed a continuous decay
of the spontaneous polarization Ps with increasing temper-
ature. Hence, the convergence region is not able to provide
maximized small signal piezoelectric coefficients due to the
already low spontaneous polarization.
Instead, the maximum values of d33 are observed at and
slightly above the O–T phase boundary (Fig. 5). The ability
of the system to retain the spontaneous polarization is
therefore critical in determining the high d33 values. It
remains an open question for future investigations why
the R–O phase transition does not yield a high piezoelectric
coefficient d33. Since the composition with x = 0.6 is com-
positionally away from all phase transitions, it presents a
much more stable spontaneous polarization, which is
reflected in its almost temperature-insensitive small signal
d33 (Fig. 4).
4.4. Large signal electromechanical response
The large signal strain measurements and calculation of
d 33 were done deliberately at very high fields (more than
one order of magnitude higher than the Ec for all compo-
sitions) in order to avoid unsaturated loops. Since intrinsic
contributions to strain are known from the previous sec-
tion and non-saturation can be discarded, so d 33 can be uti-
lized to study the large signal properties and the extrinsic
contributions on them. It is already known that domain
wall contributions can account for more than 50% of the
total strain output in d 33 , due to non-180° domain wall
switching [38].
The domain size, morphology, mobility and activation
barrier all play a major role in determining the ease of
switching and thus the electromechanical output of BZT–
BCT [19,30]. Moreover, all these contributions are
expected to be highly dependent on the crystal structure
[10,19,30]. As previously shown [19] based on an inhomo-
geneous field mechanism model [39], there is a broad
energy barrier minimum for switching from around
x = 0.4 to x = 0.5 at room temperature. This is due to a
balance between the activation barrier per unit volume
and the critical volume of nucleating domains, which is a
parameter governed by the domain morphology and size.
Fig. 8 verifies that a large contribution of the switching
around the ferroelectric phase transitions should originate
from non-180° domain wall motion, leading to high d 33 val-
ues. Moreover, the broad minimum for switching, rational-
ized as a switching energy barrier, also occurs at higher
temperatures around both phase transitions, as depicted
from the maximized d 33 . The broad switching minimum
can be attributed to the hierarchical domain structure
observed by Gao et al. [30] due to the proximity to the
phase transitions, which aids non-180° domain wall switch-
ing [37]. On the other hand, the d33 was found to peak only
at the O–T phase transition. This leads to a complex sce-
nario in which small signal and large signal properties are
not fully coupled. Although switching should also be aided
at the convergence region and Tc due to both hierarchical
domain structures and the minimum switching energy bar-
rier, high d 33 values are not observed – probably due to the
small contribution to the strain per switching event. This
could be rationalized based on the results by Keeble
et al. [7], in which local distortions from a cubic symmetry
are very small at such temperatures. This strain per switch-
ing event can be quantified using a figure of non-cubic dis-
tortion for the tetragonal symmetry as c/a  1. For the
tetragonal side of the BZT–BCT phase diagram, an
increased switching contribution was found with decreased
distance to ferroelectric/ferroelectric phase transitions [37].
In general, there is a maximum in d33 as well as in d 33 for an
intermediate non-cubic distortion [40]. A high distortion
provides a high strain per switching event, but only few
domains switch, whereas a low distortion provides many
switching events with small contributions per domain wall
[40].
Fig. 9 demonstrates that the maximum polarization
Pmax peaks at around the Tc and presents maximized values
at the convergence region. Since high strain is not involved
in this composition and temperature regime (Fig. 8), we
attribute the high Pmax values mostly to 180° domain
switching, which is known to be an extrinsic contribution
to polarization that does not involve remanence in the
strain [1]. This contribution to Pmax is more substantial
than that of non-180° domain switching, since we do not
observe maximized values of Pmax along the phase
transitions.
Figs. 8 and 9 reveal that non-zero values of d 33 and Pmax
occur even at 10 °C above the Tc. Hence, a considerable
amount of 180° domain switching may give rise to the high
values of Pmax around the convergence region and to a les-
ser amount of non-180°, giving rise to non-zero electrome-
chanical output [41]. Moreover, it has already been verified
in the BZT–BCT system that an electric field induces phase
changes and an increased Tc [42].
 M. Acosta et al. / Acta Materialia 80 (2014) 48–55
5. Conclusions
It is suggested that the existence of a triple point or a
general phase convergence region is not the cause of the
high electromechanical properties in the BZT–BCT system.
Instead, the highest small and large signal piezoelectric
coefficients occur at ferroelectric–ferroelectric phase transi-
tions and are rather small at the phase convergence region.
This behavior is attributed to the low spontaneous polari-
zation related to the small non-cubic distortion at the phase
convergence region. The phase convergence region leads
only to a maximum in only one property, polarization.
This is suggested to be due to high 180° domain switching
and an increase in transition temperature with electric field.
Acknowledgment
This work was supported by the AdRIA Hesse state
center for Adaptronics.
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