Journal of Alloys and Compounds 862 (2021) 158488

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Journal of Alloys and Compounds

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

Temperature dependence of polarization and strain in

Bi0.5Na0.5TiO3-SrTiO3 multilayer composites ]]
]]]]]]
]]

⁎
Soon-Jong Jeong a, , Dong-Hwan Lim a, Dong-Jin Shin a, Mohsin Saleem b, Bo-Geun Koo a,
In-Sung Kim a, Min-Soo Kim a
a
Energy Conversion Research Center, Korea Electrotechnology Research Institute (KERI), Changwon 51543, Republic of Korea
b
School of Chemical and Material Engineering (SCME), National University of Science and Technology (NUST), Islamabad, Pakistan

a r t i cl e i nfo a bstr ac t

Article history: Relaxor-ferroelectric phase transition materials exhibit excellent strain behavior under applied electric
Received 22 September 2020 fields for utilization in actuator applications. However, the large strain of relaxor-ferroelectric phase tran­
Received in revised form 10 December 2020 sition materials can only be achieved in a narrow temperature range. Hence, in this study, composition-
Accepted 21 December 2020
based multilayer samples and compositional gradient composite (CGC) samples were designed and fabri­
Available online 12 January 2021
cated to extend the usable temperature range of relaxor-ferroelectric materials. The raw materials used
were 0.78(Bi0.5Na0.5TiO3)–0.22SrTiO3 and 0.72(Bi0.5Na0.5TiO3)–0.28SrTiO3. The multilayered sample con­
Keywords:
Lead-free piezoelectrics taining two ceramics showed higher temperature-dependent strain and polarization than those of the
BiNaTiO3-SrTiO3 single-composition ceramic. In addition, phase transition was observed in the CGC in the low- and high-
Relaxor-ferroelectric phase transition temperature ranges. In the CGC sample, the compositional gradient characteristics of Sr were observed
Compositional gradient composite along the vertical direction owing to diffusion. This reduced the temperature-dependent unipolar strain of
the sample (0.148–0.175%) in the range of −20 °C < T < 100 °C. This behavior can be attributed to the
combined effect of the relaxor-ferroelectric phase transition and ferroelectric domain reorientation, as well
as the relaxor electrostriction. The sintering temperature had a significant effect on the compositional
gradient of Sr and the performance of the layered composites.
© 2020 Elsevier B.V. All rights reserved.

1. Introduction the phase transition and its corresponding strain in relaxor-ferro­

Materials that undergo phase transition under applied electric
fields such as lead-based perovskite compounds are widely used as
actuation elements in solid-state actuator applications [1,2]. Re­
cently, lead-free ceramics have attracted considerable attention as
promising alternatives to lead-containing ceramics [3–8]. Bismuth-
based perovskite compounds [9,10] have emerged as one of the most
promising candidates to replace lead-based perovskite oxides owing
to their large strain behavior with potential applications as actuator
materials. However, despite their excellent properties, the effects of
frequency and temperature on the strain of bismuth-based per­
ovskite compounds limit their practical application in actuator de­
vices [11–13].
Relaxor-ferroelectric phase transition materials such as Na1/2Bi1/
2TiO3-based materials can exhibit a relatively large strain (> 0.2%),
which improves the phase transition of these materials. In addition,
⁎ bulk materials at the sub-millimeter scale and are mostly incapable
Corresponding author.
E-mail address: sjjeong@keri.re.kr (S.-J. Jeong).
electric phase transition materials occur in a narrow temperature
range (< 50 °C), which enables their utilization in actuator appli­
cations [14–16]. Several methods have been introduced to tailor the
properties of Na1/2Bi1/2TiO3-based materials such as chemical con­
trol (chemical doping, nonstoichiometry), microstructure control
(composite formation), and process control (quenching) to extend
the temperature range where deformation can occur [17–21]. An­
other method involves the construction of heterogeneous geometric
structures [22–24], in which the electrical performance of Na1/2Bi1/
2TiO3-based materials is based on the average properties of each
discrete component. The composite structures fabricated using this
method exhibit discrete component stacking and functional gradient
characteristics.
Since the introduction of artificial functionally graded materials
(FGMs), various processing techniques including layer-by-layer de­
position, centrifugal casting, inkjet printing, and electrospinning
have been developed for structural metals and ceramics to fabricate
FGMs [25–27]. However, these techniques can only be applied to
of generating a continuous gradient without sharp transitions [28].

https://doi.org/10.1016/j.jallcom.2020.158488
0925-8388/© 2020 Elsevier B.V. All rights reserved.
S.-J. Jeong, D.-H. Lim, D.-J. Shin et al.
Fig. 1. Concept geometry of the layered composites: (a) Multilayer and (b) CGC samples.
Functional gradients are fundamentally associated with the varia­
tions in the local chemical compositions/constituents and structural
characteristics involved in the arrangement, distribution, dimen­
sions, and orientation of the building units [29].
Studies on structural composites have reported that mixtures
containing high- and low-temperature materials show stable prop­
erties in a wide temperature range [26,27]. In this study, two com­
posite samples, namely a composition-based multilayer sample and
compositional gradient composite (CGC) sample were prepared for
applying the FGM concept to ceramics. The geometric structures of
the samples are shown in Fig. 1(a). The two composites were pre­
pared using different methods. First, two materials with varying
compositions were prepared and stacked alternately along the ver­
tical direction using the conventional tape casting and multilayer
device fabrication process. The second process involved the gra­
dient-change method. For this process, two materials with varying
compositions were placed vertically, and the diffusion of some ele­
ments between the two materials produced an FGM structure, thus
controlling their properties over a wide temperature range. In ad­
dition, depending on the heat treatment conditions such as the
sintering temperature, the region of the two-composition mixture
zone was divided into the following regions: the discrete line,
stepwise, and FGM regions. This enabled the observation of inter­
esting properties in these materials.
In this study, composition-based multilayer and CGC samples were
fabricated to extend their usable temperature range up to ~ 100 °C. The
composite consisted of two compositions, wherein phase transition in
one composition occurred in the high-temperature range, whereas that
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Journal of Alloys and Compounds 862 (2021) 158488
of the other composition occurred in the low-temperature
range. Consequently, the phase transition in the composite occurred
in the low- and high- temperature ranges. The compositions
used in this study were 0.78(Bi0.5Na0.5TiO3)–0.22SrTiO3 and
0.72(Bi0.5Na0.5TiO3)–0.28SrTiO3, and their high field-induced polariza­
tion and strain were investigated as functions of temperature. The
temperature-dependent properties were evaluated using the polar­
ization–strain (P–S) relationship.
2. Experimental procedure
2.1. Materials and fabrication
2.1.1. Materials
The materials used in this study included
0.78Bi0.5Na0.5TiO3–0.22SrTiO3 (BNST22), 0.76Bi0.5Na0.5TiO3–0.24SrTiO3
(BNST24), 0.74Bi0.5Na0.5TiO3–0.26SrTiO3 (BNST26), and
0.72Bi0.5Na0.5TiO3–0.28SrTiO3 (BNST28). The materials were classified
based on the temperature corresponding to the relaxor-to-ferroelectric
phase transition temperature range of 60–100 °C or lower. The phase
transition of BNST22 and BNST24 occurred in the high-temperature
range (60–100 °C), whereas that of BNST26 and BNST28 occurred in the
low-temperature range (−20 to 40 °C).
2.1.2. Multilayer device fabrication using two ceramics
The geometries of the multilayer devices fabricated using two
ceramic materials and the CGC are depicted in Fig. 1. The multilayer
devices with two ceramic materials were fabricated using a
S.-J. Jeong, D.-H. Lim, D.-J. Shin et al.
conventional doctor blade method. First, the BNST ceramic tape was
fabricated using the doctor blade method. Then, a 5-μm-thick AgPd
electrode was printed on the BNST ceramic tape, after which the
printed tapes were laminated. Subsequently, heat treatment was
performed at 150 °C for 2 h to remove the organic materials, fol­
lowed by heating at 450 °C for 4 h, and then heating at 550 °C for 6 h.
Then, sintering was performed at 1150 °C at a rate of 3 °C/min under
air, and the temperature was maintained at 1150 °C for 4 h. The as-
fabricated multilayer device had a size of 25 × 2 × (0.25–0.3) mm3.
2.1.3. Multilayer devices fabricated using CGC
BNST22 and BNST28 were used for fabricating the multilayer
devices containing the CGC. These compositions mainly exhibit re­
laxor phases and undergo a relaxor-to-ferroelectric phase transition
accompanied by strain under an applied electric field. BNST22 and
BNST28 were compacted with two layers in a sequential compaction
process. The resulting compacted body was 6 × 10 × 50 mm in size.
Next, the compacted body was sintered at 1175, 1200, and 1250 °C
for 4 h. Then, the sintered body was cut to a size of 5 × 5 × 1 mm.
Finally, AgPd electrodes were printed on both surfaces of the sin­
tered cuts.
2.2. Measurements (Small- and large-signal measurements)
Field-emission scanning electron microscopy (Hitachi FE-SEM
S4800, Japan) was used for microstructural investigation. A Precision
LCR Meter 4192 A (Hewlett Packard Corporation, Palo Alto, CA) was
used to measure the dielectric constants as functions of tempera­
ture. X-ray diffraction (XRD) patterns were measured from 20° to 80°
(step interval of 0.01°) with a Panalytical X′ pert PROMPD system
equipped with an X′ celerator detector using monochromatic (Cu Kα)
radiation (λ = 1.54056 Å) from graphite. Rietveld refinement of the
XRD patterns was performed using the HighScore Plus software.
Fitting was conducted by comparing the experimental data with the
reference data (stored in the ICSD structure database). The space
group of each phase was selected with a minimum value of the
goodness of fit ( χ2) from the reference data of the space groups.
The electrical coupling factor was measured using an IEEE stan­
dard. Polarization–electric field (P–E) hysteresis loops and field-in­
duced strains were measured using a piezoelectric evaluation
system (AixaccT 2000, Germany).
3. Results
3.1. Performance of the single-composition ceramic and its
multilayer device
BNT and ST exhibited ferroelectric rhombohedral (R) and cubic (C)
phases, respectively, near room temperature. Previous studies have
reported that the solid solutions of BNT and ST at certain ratios tran­
sition from the R phase to the C phase [30,31]. In this study, phase
transitions from the R and T (tetragonal) phases to the C phase were
observed between BNST20 and BNST30 near room temperature.
Among these composition ranges, BNST22, enriched with BNT, ex­
hibited non-ergodic (or ferroelectric) and ergodic relaxor transitions in
the temperature range of 40–100 °C. The relaxor phase, characterized
by nanodomains, was transformed to a ferroelectric (F) phase, char­
acterized by microdomains under an applied electric field, thus re­
sulting in large deformation (strain). With an increase in the SrTiO3
content in BNST22, the relaxor phase became more stable, thus de­
creasing the relaxor-ferroelectric phase transition temperature.
Fig. 2 shows the polarization characteristics of BNST22–BNST28.
The BNST22 and BNST24 samples show a typical ferroelectric pat­
tern in the low-temperature range (−20 to 20 °C), a double clinch
loop in the high-temperature range (60–100 °C), and an inter­
mediate pattern between these temperature ranges. The
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Journal of Alloys and Compounds 862 (2021) 158488
ferroelectric domain boundary movement in the low-temperature
range and the relaxor-to-ferroelectric phase transition in the high-
temperature range can be attributed to the polarization in the
BNST22 and BNST24 samples. Furthermore, the BNST26 and BNST28
samples show slim hysteretic loops in the high-temperature range
and double clinch loops in the low-temperature range. These can be
attributed to the distortion of the relaxor phase and the relaxor-to-
ferroelectric phase transition, respectively. These polarization char­
acteristics can also be identified using the remnant polarization (Pr),
saturation polarization (Ps), and Ps/Pr with respect to temperature
(T) (see Fig. 2(b)). The Pr is a measure of the interplay between the
relaxor and ferroelectric phases; this interplay determines the
boundary between the relaxor and ferroelectric phases with respect
to temperature [32]. An increase in SrTiO3 decreased the transition
between the relaxor and ferroelectric phases, as shown in the Pr–T
relationship in Fig. 2. In addition, according to the Pr–T relationship,
the relaxor and ferroelectric phases coexist in the temperature range
of 40–80 °C for BNST22, 0–60 °C for BNST24, −20–40 °C for BNST26,
and −40–20 °C for BNST28.
Furthermore, the unipolar and bipolar strains of the samples
showed similar behaviors with respect to temperature. The largest
strain for BNST22 and BNST24 was observed in the high- temperature
range. In addition, the temperature required for the largest strain to
occur decreased with an increase in the ST content. Interestingly, the
largest value was observed at temperatures corresponding to a point
between R and R + F in the Pr–T relationship curve (80 °C for BNST22,
60 °C for BNST24, 40 °C for BNST26, and 20 °C for BNST28). This is a
common phase transformation phenomenon observed in many solid
materials, indicating large strains resulting from field application
(electric field, magnetic field, or external mechanical stress) at the in­
itial temperature between the high- and low-temperature phases. In
addition, the strain (> 30%) significantly varied with temperature,
which is important for utilizing these materials in actuator applica­
tions. Considering the importance of deformation for using ceramics in
actuator applications (0.1–0.15%), the deformation of the ceramic
samples investigated in this study occurred at the appropriate tem­
perature range. This indicates that these ceramic compositions can be
utilized for developing low-temperature actuator materials.
3.2. Two-material multilayer device
To reduce temperature-dependent strain in a relatively broad
temperature range, composites with multilayer and CGC structures
were fabricated using two BNST ceramics. The multilayer samples
were prepared using two compositions. In the composites with one
composition, the phase transition occurred at high temperatures
(BNST22 and BNST24), and in the other composition, the phase
transition occurred at low temperatures (BNST26 and BNST28).
Fig. 3 shows the polarization and strain of the BNST22–BNST26
(BNST22/26), BNST22–BNST28 (BNST22/28), BNST24–BNST26
(BNST24/26), and BNST24–BNST28 (BNST24/28) multilayer samples
with respect to the applied electric field. These samples exhibited
the characteristics and average performance corresponding to each
ceramic layer. In the P–E measurements, all the multilayer samples
showed considerable changes with temperature. In the high-tem­
perature range of 80–100 °C, shallow curves were observed (see
yellow and pink curves), whereas double clinch curves were ob­
tained for the low-temperature range of −20–20 °C (see black, red,
and green curves). Particularly, the Pr measurements indicated that
the relaxor and ferroelectric phases coexisted in a broader tem­
perature range compared to that observed for the single-composi­
tion samples (BNST22–BNST28) (as shown in Fig. 3(b)). In addition,
the bipolar strain curves showed tendencies similar to those of the
single-composition samples. Furthermore, a butterfly strain shape
was obtained between −20–20 °C, and a parabolic strain shape was
obtained at 80–100 °C. In the unipolar strain measurements, the
S.-J. Jeong, D.-H. Lim, D.-J. Shin et al. Journal of Alloys and Compounds 862 (2021) 158488

Fig. 2. Polarization and strain properties of BNST22–BNST28 ceramics, (a) Polarization–electric field curves, (b) Remnant polarization (Pr), Saturation polarization (Ps), and Ps/
Pr–temperature curves, (c) Bipolar strain–electric field curves, (d) Unipolar stain–electric field curves.,.

strain (with 4 kV/mm application) in the multilayer samples varied
to a lesser extent compared to that observed for the single-compo­
sition samples. This can be attributed to the combined ceramic
characteristics of the samples. However, the variation in strain with
temperature (> 20% at −20 to 100 °C) requires further improvement
for practical utilization of these materials in actuator applications.
3.3. Functional gradient composite multilayer device
The multilayer device using the CGC structure was successfully
fabricated, and the fabrication process is presented in Figs. 1 and 4.
The two ceramics used for this device were BNST22 and BNST28.
Each layer had a thickness of 100 µm and an area of 5 × 5 mm. The
degree of diffusion of the composites during sintering was evaluated
by examining the SEM images and EDX profiles. Fig. 4(a) shows the
SEM images and Sr EDX line profiles of the composite samples sin­
tered at 1175–1250 °C. In the sample sintered at 1175 °C, a distinct
interface is observed, with a discontinuous stepwise Sr distribution
along the distance between the BNST22 and BNST28 layers. In con­
trast, on increasing the sintering temperature to 1200 °C, a con­
tinuous Sr composition gradient formed at the interface between the
BNST22 and BNST28 layers. This can be attributed to the diffusion of
Sr, which resulted in the formation of BNST22 + x with 0 < x < 6.
Furthermore, when the sintering temperature was increased to

4
S.-J. Jeong, D.-H. Lim, D.-J. Shin et al. Journal of Alloys and Compounds 862 (2021) 158488

Fig. 2. (continued)

5
S.-J. Jeong, D.-H. Lim, D.-J. Shin et al. Journal of Alloys and Compounds 862 (2021) 158488

Fig. 3. Properties of the multilayer device comprising BNST22/26, BNST22/28, BNST24/26, and BNST24/28, (a) Polarization–electric field curves, (b) Remnant polarization (Pr),
Saturation polarization (Ps), and (Ps/Pr)–temperature curves, (c) Bipolar strain–electric field curves, (d) Unipolar stain–electric field curves (For interpretation of the references to
colour in this figure legend, the reader is referred to the web version of this article).

1250 °C, a gradual change in the Sr content was observed. This in­
dicates that complete diffusion of Sr produces a uniform composi­
tion in the layers of the sample. The diffusion distance is an
important parameter in determining the various physical properties
of FGC structures (the distance was ~ 35 µm for a layer thickness of
100 µm). This induced different electrical properties in the compo­
site sample, which are discussed below. The samples sintered at
1200 °C were analyzed to understand the relationship between the
composites with different layer thicknesses and their electrical
properties.
As indicated in previous studies [31,32], rhombohedral and tet­
ragonal structures are observed in BNT-ST with ST < 20%; a mixed
phase comprising tetragonal and cubic structures exists in the range
corresponding to 20% < ST < 30%, and a cubic structure exists for

6
S.-J. Jeong, D.-H. Lim, D.-J. Shin et al. Journal of Alloys and Compounds 862 (2021) 158488

Fig. 3. (continued)

7
S.-J. Jeong, D.-H. Lim, D.-J. Shin et al. Journal of Alloys and Compounds 862 (2021) 158488

Fig. 4. Microstructures, EDX profiles, polarization, and strain of BNST22/28 CGC composite samples sintered at 1175, 1200, and 1250 °C with respect to the applied electric field, (a)
SEM images and EDX line profile for Sr, (b) XRD patterns of BNST22/28 CGC samples sintered at 1175, 1200, and 1250 °C, (c) Dielectric constant and loss versus temperature, (d) P
Polarization–electric field curves, (e) Remnant polarization (Pr), Saturation polarization (Ps), and (Ps/Pr)–temperature curves, (f) Bipolar strain–electric field curves, (g) Unipolar
strain–electric field curves.

ST > 30%. The addition of ST to BNT weakens the long-range ferro­
electric ordering of BNT. Based on the Rietveld refinement of the
XRD patterns shown in Fig. 4(b), the space group of pm3m (cubic)
was used to index the hkl value of SrTiO3 (cubic) with BNT (tetra­
gonal). For this analysis, CGC samples without the AgPd electrode
were prepared with the same procedure used for multilayer device
fabrication. The peaks indicate that all ceramics crystallized into a
single-phase perovskite structure without any impurity peaks
(measurable by the normal XRD instrument used in this study).
BNST22 exhibited a mixture of ferroelectric (tetragonal (p4mm)) and
relaxor phases (cubic (pm3m)), and BNST28 mainly exhibited a re­
laxor phase. To confirm the coexistence of the relaxor and ferro­
electric phases, a detailed analysis was performed in the range of
45–48° corresponding to the (200) peak. Separation of the ferro­
electric tetragonal (T) and relaxor pseudo-cubic (C) phases was ob­
served. BNST28 comprised the C phase whereas BNST22 included
the T phase. The CGC samples exhibited different combinations of
the T and C phases with varying sintering temperatures. The samples
sintered at 1175 and 1200 °C showed mixed phases, but the sample
sintered at 1250 °C mainly showed the C phase. These phase com­
positions may be related to the diffusion of Sr, which induces the
formation of phases with a single composition. This was also con­
firmed by the change in lattice parameters of the samples with
varying sintering temperatures. The lattice parameters of the C
phase were equal for the samples sintered at 1175 and 1200 °C.
When the temperature was increased to 1250 °C, the cubic and
tetragonal phases merged. The lattice parameters of the cubic phase
were as follows: a = 0.391 nm (1175 ℃), a = 0.391 nm (1200 ℃), and
a = 0.389 nm (1250 ℃) for the C phase; and a = 0.393 nm and
c = 0.390 nm (1175 and 1200 ℃) for the T phase.
Fig. 4(c) shows the dielectric constant (εr) and loss (tanδ) as
functions of temperature (T). BNST22 exhibits a peak near 60 °C,
whereas BNST28 exhibits a peak near 120 °C. In addition, the CGC
samples sintered at 1175 °C show convoluted and minor peaks near
60 °C, and a major peak near 120 °C. With respect to the dielectric
loss, the CGC samples sintered at 1175 °C exhibit the characteristics
of both the ceramics (BNST22 and BNST28). In addition, double
peaks are observed for the CGC samples sintered at 1175 °C, which
correspond to those of BNST22 and BNST28. For the CGC samples
sintered at 1200 °C, the double peaks narrow and merge into one
peak. This indicates that the composition normalized via the diffu­
sion of Sr. Similar behaviors were also observed in the samples
sintered at 1250 °C.
Fig. 4(d) shows the P–E curves of the three CGC samples at
−20–100 °C. The polarization curves of the CGC samples are similar
to those of the multilayer samples. In the low-temperature range

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Fig. 4. (continued)

9
S.-J. Jeong, D.-H. Lim, D.-J. Shin et al.
Fig. 4. (continued)
(−20 to 20 °C), the polarization curve shows a typical ferroelectric
loop, whereas double kink-like loops are observed in the tempera­
ture range of 60–100 °C. However, the Pr–T relationship indicated
that the F and R phases coexisted over a wide temperature range in
the CGC sample sintered at 1200 °C.
In the bipolar strain–electric field curves of the composite sin­
tered at 1175 °C, a typical butterfly pattern is observed at −20 °C.
However, at 40 °C, the strain curve changes to a parabolic shape,
indicating the relaxor-to-ferroelectric transition. On further in­
creasing temperature to 100 °C, a narrow hysteresis curve is ob­
served, indicating the distortion of the relaxor phase under the
applied electric field. In the CGC sample sintered at 1200 °C, the
strain behavior showed the butterfly pattern with a small negative
strain at −20 °C. In addition, the positive strains were almost similar
for the samples at −20–100 °C. Furthermore, the hysteresis nar­
rowed with an increase in the test temperature. For the CGC sample
sintered at 1250 °C, the strain curve changed from a butterfly pat­
tern to a parabolic pattern with an increase in temperature. This
indicates that reorientation of the ferroelectric domain occurred
under electric field application at −20 °C, and the relaxor-to-ferro­
electric phase transition occurred at 20–100 °C. The effect of the
electric field on the unipolar strain curves of the samples at
−20–100 °C is shown in Fig. 4(d). The CGC samples show different
10
Journal of Alloys and Compounds 862 (2021) 158488
strain behaviors at different sintering temperatures. The CGC
sample sintered at 1250 °C exhibits the maximum strain at 20 °C
and the strain decreases with increasing temperatures. This change
in strain is similar to that of the single-composition BNST24
sample. This indicates that Sr diffusion ensures uniform mixing of
BNST22 and BNST28. Furthermore, the CGC sample sintered at
1200 °C exhibited unipolar strain, which was almost constant at all
the test temperatures used in this study. A strain of 0.148–0.175%
with less than 10% variation in the temperature range of −20 °C <
T < 100 °C was observed in the CGC sample sintered at 1200 °C.
This can be attributed to the combined effect of the relaxor-ferro­
electric phase transition, ferroelectric domain reorientation, and
relaxor electrostriction, along with the compositional gradient
characteristics of Sr along the thickness direction owing to diffu­
sion. The BNST22/BNST28 composition was evenly distributed in
the vertical direction; the composite exhibited the properties of
both the ceramic layers. For the sample sintered at 1175 °C, the
maximum strain was observed at 80 °C. This indicates that the
sample has the characteristics of BNST22 and BNST28.
According to the polarization and strain behaviors observed for
the CGC samples, depending on the sintering temperatures, the
sample sintered at 1200 °C exhibited the characteristics of BNST 22
and BNST28 at −20–100 °C, including phase transition and
S.-J. Jeong, D.-H. Lim, D.-J. Shin et al.
Fig. 4. (continued)
ferroelectric domain motion. In the temperature range of
60 °C < T < 100 °C, the phase transition corresponding to the char­
acteristics of BNST22 was observed along with the electrostriction
behavior of BNST28. In addition, the sample sintered at 1250 °C had
no Sr gradient, but it exhibited a homogeneous Sr distribution along
the layer direction. The sample sintered at 1175 °C showed the
characteristics of BNST22 and BNST28.
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Journal of Alloys and Compounds 862 (2021) 158488
4. Discussion
The performances of two-material multilayer and CGC samples
were evaluated by analyzing the P–E and strain–polarization (S–P)
relationships with respect to temperature. These relationships were
mainly examined for the BNST22–BNST28 multilayer and CGC
samples, as distinct differences in their strain behaviors were
S.-J. Jeong, D.-H. Lim, D.-J. Shin et al. Journal of Alloys and Compounds 862 (2021) 158488

Fig. 4. (continued)

T
observed at 0 and 80 °C. These samples were selected for analyses in where < P33 > represents the average polarization in the samples
the low-, intermediate- and high-temperature ranges. with applied Eo; t1 and t2 are the thickness ratios the first (BNST22)
and second (BNST28) phases, respectively. The calculation results
(dotted lines in Fig. 5(b)) could be obtained using the above equa­
tion. The calculated values based on averaging the thicknesses of
4.1. Polarization with respect to temperature in two-material
BNST22 and BNST28 (each layer is 0.5 times the total thickness)
multilayer and CGC devices
coincide with the experimental data.
Meanwhile, compositional variations were observed in the
The two-composition multilayer samples and CGC samples were
BNST22–BNST28 CGC samples sintered at 1175 and 1200 °C. The
similar in geometry, owing to their layered structures. However, they
interface zones could be divided into two layers (BNST22 and
completely differed in their electrical characteristics, which could be
BNST28) for the sample sintered at 1175 °C and four layers (BNST22,
observed using equivalent circuit designs. The single-composition
BNST24, BNST26, and BNST28 compositions) for the sample sintered
sample was examined using a circuit with one capacitor. The two-
at 1200 °C. The calculations were performed using the ferroelectric
material multilayer sample was examined considering a circuit with
composite model proposed in earlier studies based on the electro­
two capacitors connected in parallel. For simplicity, in the CGC
static coupling mechanism [40]. For the samples sintered at 1200 °C,
sample, two and four capacitors were connected in series, depending
the calculation results almost coincide with the experimental re­
on the sintering temperatures, namely 1175 and 1200 °C, as shown in
sults. Moreover, the experimental and calculated results are almost
Fig. 5(a). The capacitance can represent polarization (P), as C ~ P.
identical at 0, 40, and 80 °C, as shown in Fig. 5(c). As various com­
From the P–E curves, the change in polarization can be regarded
positions with BNST22 and BNST28 coexist in the layers, the tran­
as a function of the excitation electric field (Eo). P could be plotted as
sition from the relaxor to the ferroelectric phase, domain
a function of Eo with the bold lines obtained by plotting P from the
reorientation of the ferroelectric phase, and relaxor electrostriction
minor P–E curves [39]. The bold lines for the multilayer and CGC
simultaneously influence the polarization behavior of these mate­
samples measured at 0, 40, and 80 °C are presented in Fig. 5(b). For
rials under the applied electric field. This might have resulted in the
comparison, those (short dashed lines) of BNST22, BNST24, BNST26,
reduced temperature dependence of polarization in the entire
and BNST28 are included in the figures.
temperature range (−20 to 100 °C). These CGC samples have
In the BNST22–BNST28 multilayer samples, the lines account for
similar polarization behaviors. Polarization in turn affects the strain
the average of BNST22 and BNST28. This follows the simple mixture
behavior of these materials, leading to fewer variations in the
rule for two capacitors.
strain–temperature relationships, which are described below.
The calculated results for the CGC samples sintered at 1175 °C
< P33T (Eo) > = t1 [P(33,1)
T (Eo) + t2 [ P33,2T (Eo)] (1) differed from the experimental results. The CGC samples showed

12
S.-J. Jeong, D.-H. Lim, D.-J. Shin et al. Journal of Alloys and Compounds 862 (2021) 158488

Fig. 5. Equivalent circuit models and polarization curves of BNST22/28 multilayer and CGC samples, (a) Equivalent circuit models and polarization–electric field curves, (b)
Polarization behavior of BNST22–28 multilayer and CGC samples with respect to excitation electric field at 0, 40, and 80 °C, (c) Polarization behavior of BNST22/28 CGC samples
sintered at 1175 and 1200 °C with respect to excitation electric field at 0, 40, and 80 °C.

polarization lines corresponding to those indicating the highest
polarization in BNST22 and BNST28. At 0 °C, the CGC sample was
identical to BNST28, showing a higher polarization than BNST22
when E < 3 kV/mm. When E > 3 kV/mm, the polarization of the CGs
sample approached that of BNST22 (The crossover of polarization in
BNST22 and BNST28 takes place at 3 kV/mm). We inferred that the
polarization of the CGC sample is close to largest value of BNST22
and BNST28, which may be related to the induced polarization ob­
served in bilayered ferroelectric materials. At 40 and 80 °C, similar
polarizations were observed. Accordingly, as the CGC sample is a
vertically stacked structure comprising BNST22 and BNST28, the
polarization of this sample approached that of a single BNST com­
position. The diffusion distances were limited and the interface was
distinct. According to investigations [36–38] on multilayered ferro­
electric materials, bilayered ferroelectric composites, with different
ferroelectrics and dielectrics, show a ferroelectric anomaly, which
can be explained using the concept of electrostatic coupling. BaTiO3
(BT) and SrTiO3 (ST) were stacked serially. ST exhibited considerably
less polarization compared to BT. However, with field application, ST
showed induced polarization, which was almost equal to that of BT
in samples having compositions below specific S/T ratios. Our CGC
samples sintered at 1175 °C showed similar polarization behaviors.
4.2. Polarization–strain relationship and electrostriction coefficient
The strain results were evaluated by plotting the P–S curves. To
understand the polarization and strain behaviors of the multilayer
and CGC samples, the P–S relationship was investigated using the
following electrostriction equation [33,34]. The results obtained at
−20–100 °C are shown in Fig. 6.
S = Q 33 P 2 (2)
where Q33 is the electrostriction coefficient. The P–S relationships of
the BNST22/28 CGC samples varied with the test temperatures.
Different P–S relationships and their resulting electrostrictive
coefficients for various ferroelectric phases are reported in literature

13
S.-J. Jeong, D.-H. Lim, D.-J. Shin et al.
Fig. 5. (continued)
[34,35]. Based on the P–S relationships, the major polarization me­
chanism and the resultant strain behavior in the multilayer and CGC
samples were assessed. At low temperatures (0 °C), the P–S re­
lationship showed a large hysteresis pattern with a negative slope at
small P and a positive slope at high P. This can be attributed to the
ferroelectric domain reorientation. In the intermediate temperature
range (40 °C), the P–S curves exhibited a shadow hysteresis loop at
low P, which corresponds to the relaxor-to-ferroelectric phase
transition (or nano-to-macrodomain phase transition), whereas a
reversible loop, originating from the distortion in the domain of the
relaxor phase, was observed at large P. The shallow hysteresis part
had a positive P/S slope. In addition, at a high temperature (80 °C),
only the reversible S/P slope was observed, which can be attributed
to the distortion of the nanodomains in the relaxor phase under
electric field application. With further increases in the temperature,
the slope decreased owing to the distortion of the nanodomains in
the relaxor phase. These behaviors were also observed in BNST22.
BNST24 and BNST26 also showed similar P–S relationships, except
14
Journal of Alloys and Compounds 862 (2021) 158488
for the large hysteresis loop corresponding to the ferroelectric do­
main reorientation. In contrast, only the reversible loop was ob­
served in BNST28.
The P–S relationships of the four multilayer samples (BNST22/26,
BNST22/28, BNST24/26, and BNST24/28) were investigated, and the
results are shown in Fig. 4(b). At 0 °C, a hysteresis loop is observed
for the BNST22/26 and BNST22/28 multilayer samples, corre­
sponding to the ferroelectric domain boundary movement and
phase transition. Based on the extremely thin hysteresis and re­
versible loops, the phase transition and electrostriction mainly oc­
curred at 40 °C. However, when the temperature increased to 80 °C, a
shallow hysteresis loop were observed, originating from the phase
transition of BNST22. For the BNST24/26 and BNST24/28 samples,
shallow loops were observed, which were related to the phase
transition of BNST24. When the test temperatures were increased to
40 and 80 °C, the electrostriction of the relaxor phase had a sig­
nificant effect on the polarization and strain behaviors, resulting in
the formation of a reversible loop.
S.-J. Jeong, D.-H. Lim, D.-J. Shin et al. Journal of Alloys and Compounds 862 (2021) 158488

Fig. 5. (continued)

Fig. 6. Polarization (P)–electric field (E) curves of the BNST22–BNST28 single composition samples, BNST22/26–BNST24/28 multilayer samples, and BNST22/28 CGC samples, (a)
P–E relationships of the BNST22, BNST24, BNST26, and BNST28 samples, (b) P–E relationships of the BNST22/26, BNST22/28, BNST24/26, and BNST24/28 multilayer samples, (c)
S–P relationships of the BNST22/28 CGC multilayer samples.,.

15
S.-J. Jeong, D.-H. Lim, D.-J. Shin et al. Journal of Alloys and Compounds 862 (2021) 158488

Fig. 6. (continued)

The CGC samples exhibited complicated behaviors. At 0 °C, a on the polarization behavior of these samples. This was probably
large hysteresis loop at low P and shallow hysteresis loop at high P owing to the coexistence of various compositions via the diffusion of
were observed. This indicates that the ferroelectric domain Sr. This behavior was maintained even when the test temperature
boundary movement and phase transition have a significant effect was increased to 40 °C. At 80 °C, a shallow loop was observed, which

16
S.-J. Jeong, D.-H. Lim, D.-J. Shin et al.
can be attributed to the phase transition. In addition, the slopes at
high P are almost the same. The phase transition plays a major role
in the polarization occurring at −20–100 °C. According to the above
explanation, the 22–28 CGC samples show less temperature-de­
pendent polarization and have the same values for the electro­
strictive coefficient Qij (= S/P) within the test temperature range. This
leads to less strain variations with respect to temperature compared
to those observed for the multilayer samples. This behavior can be
attributed to the compositional variation characteristics of BNST in
the samples owing to Sr diffusion during sintering.
A piezoelectric strain change was observed in the multilayer
samples with respect to temperature at −20–100 °C, where two
composite layers stabilized the electromechanical conversion per­
formance of the ceramic material with temperature to within 10%.
This property makes it possible to obtain the desired piezoelectric
properties in piezoelectric ceramic devices. Hence, we concluded
that temperature stabilization of these characteristics can be
achieved by improving the geometric structures rather than the
properties of the ceramic materials.
5. Conclusion
Mixtures of high- and low-temperature materials showed stable
properties in a wide temperature range. In addition, phase transitions
in the CGC samples were observed in the low- and high-temperature
ranges. To verify these transitions, a BNST22–BNST28 single-composi­
tion sample, multilayer samples comprising two ceramics, and CGC
samples containing BNST22 and BNST28 were prepared and evaluated
as actuator materials under electric field applications. The layer thick­
ness and sintering temperature had a significant effect on the com­
positional gradient of Sr and the performance of the layered composite.
Owing to the appropriate Sr diffusion during sintering, the BNST22–28
layered composite samples exhibited temperature-dependent unipolar
strain in the range of −20–100 °C.
CRediT authorship contribution statement
Soon-Jong Jeong: Conceptualization, Writing - original draft. Dong-
Hwan Lim: Resources, Formal analysis. Mohsin Saleem: Methodology,
Writing - review & editing. Dong-Jin Shin: Conceptualization,
Methodology, Investigation. Bo-Kun Koo: Visualization, Investigation,
Formal analysis, Data curation. In-Sung Kim: Project administration.
Min-Soo Kim: Writing - review & editing, Validation.
Declaration of Competing Interest
The authors declare that they have no known competing fi­
nancial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
This research was supported by a grant from the basic research
program of Korea Electrotechnology Research Institute in Republic of
Korea.
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