DR.

RAHUL KAMBALE (Orcid ID : 0000-0001-5625-0664)

Accepted Article
Article type : Article

Ferroelectric, Piezoelectric and Electrostrictive Properties of Sn4+ Modified

Ba0.7Ca0.3TiO3 Lead-Free Electroceramics

Bharat G. Baraskar1, Rahul C. Kambale1*, A. R. James2, M.L.V. Mahesh2, C.V.

Ramana3 and Y. D. Kolekar1

1
Department of Physics, Savitribai Phule Pune University, Ganeshkhind, Pune 411007,
Maharashtra, India

2
Defence Metallurgical Research Laboratory, Hyderabad 500058, India
3
Department of Mechanical Engineering, University of Texas at El Paso, El Paso, Texas

79968, USA

*
E-mail: rckambale@gmail.com

Abstract

Lead-free Ba0.7Ca0.3Ti1-xSnxO3 (x = 0.00, 0.025, 0.050, 0.075, and 0.1, abbreviated as BCST)

electroceramic system was prepared by solid state reaction method and investigated its

ferroelectric, piezoelectric and electrostrictive properties. X-ray diffraction shows that the

compositions with x ≤ 0.05 exhibit a tetragonal crystal structure having P4mm symmetry;

while the compositions x = 0.075 and 0.1 exhibit a mixed P4mm + Amm2 phase coexistence

of tetragonal and orthorhombic and P4mm + Pm m pseudo-cubic lattice symmetries,

respectively at room temperature. The dense microstructure having relative density ~90-92%

and average grain size in the range ~2.36 µm to 8.56 µm was observed for BCST ceramics.

Temperature dependent dielectric measurements support the presence of phase coexistence

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 and show the decrease in Curie temperature (TC) with Sn4+ substitution. The dielectric loss

(tan δ) values in the temperature range (-100 ᵒC to 150 ᵒC) was observed to be less than 4%,
Accepted Article
for all BCST ceramics. The BCST compositions exhibit typical polarization-electric field (P-

E) hysteresis and electric field induced strain (S-E) butterfly loop, which confirms the

ferroelectric and piezoelectric character. The compositions x = 0.025, 0.05 and 0.075 show

the peaking behavior of displacement current density ( ) to an applied electric field ( ) (J-E)

which implies the saturation state of polarization. The maximum electrostrictive coefficient

(Q33) value of 0.0667 m4/C2 was observed for x = 0.075 and it is higher than some of the

significant lead based electrostrictive materials. The compositions x = 0.05 and 0.075 exhibit

the notable electrostrictive properties that may be useful for piezoelectric Ac device

applications. The observed results are discussed and correlated with the structure-property-

composition.

Keywords: Lead-free piezoelectric; BaTiO3; Dielectric and Ferroelectric; Curie temperature.

I. INTRODUCTION

Smart technology, i.e. mobile consumer electronics and automobile industry trusts only on

the PbTiO3-PbZrO3 (PZT) and Pb(Mg1/3Nb2/3)O3-PbTiO3 (PMN-PT) based piezoelectric

materials. This is not only because of the superior piezoelectric properties viz. piezoelectric

charge coefficient (d33), electromechanical coupling factor (Kp), dielectric constant (εr), and

dielectric loss (tanδ) of PZT and PMN-PT but also due to the absence of any other alternative

lead-free piezoelectric ceramics which can compete with Pb-based materials. However, PZT

and lead-based oxide materials are not environmental friendly due to the toxicity of lead

oxide. Furthermore, nowadays with increasing the levels of electronic equipment being

manufactured, used and discarded, it has been well noticed that the level of hazardous

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 substances in the environment has been rising day-to-day life due to the use of lead based

materials like PZT. Thus, there is an increasing demand of global environmental protection
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and accordingly all over the world, many researchers have greatly engaged in developing the

lead-free ceramics to replace the lead-based ceramics.1-3 Among the lead-free piezoelectric

ceramics, (K,Na)NbO3 (KNN), (Bi0.5Na0.5)TiO3 (BNT), and (Bi0.5K0.5)TiO3 (BKT) ceramics

have drawn great attention of researchers in the past few years. However, these lead-free

piezoelectric ceramics possess some major issues which are still being unsolved; 1) The

processing of KNN ceramics has some unsafe issues such as volatility of alkali-oxides,

compositional inhomogeneity, poor densification, and phase stability; 2) BaTiO3 (BT) based

piezoelectric i.e. BZT-BCT shows stable piezoelectric properties. However, the main issue of

BZT-BCT is its lower Curie temperature (Tc) ~ < 100 oC and low coercive field and these

lead to temperature dependent properties more and polarization stability less as well as the

difficulties in poling treatments; and 3) BNT based ceramic contains heavy metal as bismuth,

which is toxic and hence it cannot be considered.

Barium titanate, BaTiO3 (BT), exhibits the stable piezoelectric and dielectric

properties; hence considered it as a promising lead-free ferroelectric ceramic material with

perovskite ABO3 structure.4 The dielectric and piezoelectric properties of BaTiO3 ceramics

have been well documented by Jaffe et al. .5 The present scenario of BT based

electroceramics is to bring the polymorphic phase transition (PPT) close to room temperature

and to achieve the phase coexistence at 300 K and hence shows the enhanced piezoelectric

properties.6 It is known that the Zr4+, Sn4+, and Hf4+ substitution at Ti4+ site in BaTiO3

increases PPT temperatures from low temperatures (0 oC and -90 oC) to room temperature.6

Recently, high performance BT-based ceramics such as (Ba,Ca)(Ti,Zr)O3 and

(Ba,Ca)(Ti,Sn)O3 prepared by substitution of Ca2+ at A-site and Zr4+/Sn4+ at B-site exhibits

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 the properties comparable to the lead based soft PZT materials.3, 7-11
Furthermore, the

substitution of Ca2+at Ba2+ in BaTiO3-CaTiO3 system (i.e. to form Ba1-xCaxTiO3 (BCT)

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ceramics) results in a slight increase in the Curie temperature (TC) and on the other hand

suppresses the orthorhombic to tetragonal (TO-T) transition temperature. This is one of the

important considerations in developing the temperature stability of piezoelectric properties

for various practical applications.12

Modified BT based electroceramics i.e. a binary solid solution system composed of

ferroelectric BT and non-ferroelectric barium stannate (BaSnO3) i.e. BaTi1-xSnxO3 (BTS) has

attracted a considerable attention due to the presence of diffused type phase transition.13-17

Moreover, the Curie temperature of BT based electroceramics are sensitive to Sn4+content

which obeys the structure-property correlation.13-22 In this context, many research groups

have reported the dielectric, diffused phase transition, ferroelectric and piezoelectric

properties of BCST ceramics.12-21 However, there is a scarcity of the detailed investigation of

electrostrictive properties of BT based lead free electroceramics which are correlated with the

structure-property-composition having the phase coexistence of orthorhombic-tetragonal (O-

T) lattice symmetry, at room temperature. Thus, in view of the above, we have investigated

the structural, ferroelectric, piezoelectric and electrostrictive properties of Sn4+ modified BCT

ceramics and tried to correlate the measured properties with the phase coexistence achieved

at room temperature.

II. EXPERIMENTAL DETAILS

Ba0.7Ca0.3Ti1-xSnxO3 (BCST) ceramics with x = 0.00, 0.025, 0.050, 0.075, 0.1 were prepared

by solid state reaction method. Stoichiometric amounts of AR grade raw materials of BaCO3

(99%), CaCO3 (99%), TiO2 (99%) and SnO2 (99.9%) (all are from Sigma Aldrich) were

mixed with the addition of ethanol, and dried, then calcined at 1130 oC for 10 h. Thereafter,

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 they were remixed and pressed into pellets having 10 mm diameter and 0.6-1 mm in

thickness and sintered for two times first at 1260 oC for 10 h and secondly at 1400 oC for 5h
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in an air atmosphere. The post-calcination at 1260 oC for 10 h was carried out to achieve

proper diffusion to assist the homogenization and avoid the phase segregation of CaTiO3.

The phase formation, crystal lattice symmetry and microstructural features of the

samples were examined using the X- ray diffraction (XRD) with a CuKα radiation (λ =

1.5406 Å; D8 Advance, Bruker Inc., Germany) and the scanning electron microscopy (JEOL-

JSM 6306A, Japan). Since poling gives an information about the effective intrinsic direction

of polarization of the existing crystallographic symmetries inside the material therefore to

check the crystallographic phase transformation, (due to Sn4+ substitution in BCT), all the

samples were poled electrically at Dc bias of 800-1000 V for 30 minutes at room temperature

and then recorded the XRD pattern. The relative density of sintered (at 1400 oC) pellets was

estimated from the ratio of the apparent density measured by Archimedes’ principle and the

theoretical density calculated using crystal cell parameters. For electrical property

measurements, silver paste was applied on both sides of the polished surfaces of pellet and

then the sample was cured at 200 oC for overnight to dry out the moisture prior to any

measurements. Dielectric constant (εr) and loss tangent (tanδ) were measured as a function of

temperature from -100 oC to 150 oC at 100 kHz using inductance-capacitance-resistance

(LCR) meter (HIOKI- 3532-50, Japan), connected to a computer-controlled furnace.

Polarization (P) versus electric field (E) i.e. P-E hysteresis loops and the electric field

induced strain i.e. S-E curves for BCST ceramics were recorded on virgin (unpoled) samples

at an applied electric field of ~ 50-60 kV/cm at 0.1 Hz, using a ferroelectric test system (TF

Analyzer 2000 of M/s. aixAcct Systems, GmbH, Germany).

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 III. RESULTS AND DISCUSSION
A. Phase formation and microstructural analysis
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Figure 1 shows the Rietveld refined X-ray diffraction (XRD) patterns of Ba0.7Ca0.3Ti1-

xSnxO3 (BCST) ceramics with x = 0.00, 0.025, 0.05, 0.075 and 0.1 compositions recorded at

room temperature. All the BCST ceramics were crystallized into a perovskite structure,

signifying the Ca2+ and Sn4+ are well diffused into the BaTiO3 lattice to form a solid solution.

Rietveld analyzed XRD data of the compositions with x = 0.00, 0.025 and 0.05 show good

agreement with tetragonal structure of P4mm (ICSD#245946) symmetry. The composition x

= 0.075 diffraction pattern shows the best refinement fit to a combination of P4mm (72%)

and Amm2 (28%) (ICSD#186460) symmetries. Thus, the diffraction data of the compositions

x = 0.075 showing P4mm + Amm2 phase coexistence of tetragonal and orthorhombic lattice

symmetries. However, the composition x = 0.10 shows the best refinement fit to a

combination P4mm (60%) and cubic Pm m (40%) (ICSD# 99736) lattice symmetries. Hence,

the composition x = 0.10 exhibits the pseudo-cubic (PC) lattice symmetry.

It is observed that, with increasing Sn4+ content, there is a systematic shift of (002)/

(200) and (103)/ (301) peaks toward lower 2θ except for x = 0.025 as shown in figure

S1(Supplemental material). The anomalous peak shift to higher 2θ side is observed for x =

0.025. This might be due to initial incorporation of Sn4+ into BCT lattice, where the Sn4+ ions

are inhibited to diffuse completely into the host BCT lattice. However, the ions may be

situated very close to the grain boundaries. The observed values of lattice constants i.e., a, b

and c are shown in Table 1, which reveals the increase in the volume of the unit cell upon

increasing the concentration of Sn4+ in the lattice of BaTiO3- CaTiO3 16-17,23

(except

negligible decrease of unit cell volume for x = 0.1). This refers to a larger unit cell constant

induced by the partial replacement of Ti4+ (ionic radius 0.605 Å) by Sn4+ (ionic radius 0.69

Å) in octahedral sites which increases the d spacing and obeys the Vegards law. 24 The overall

tetragonality (axial ratio c/a) decreases with increasing Sn4+ content and becomes 1.0017 for

the partially transformed lattice symmetry from tetragonal to pseudo-cubic phase, when x =

0.1. Therefore, it is proposed that the orthorhombic-tetragonal phase coexistence occurs for x

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 = 0.075 composition at room temperature. Thus, the BCST compositions with x ≤ 0.05

exhibit a tetragonal crystal structure having P4mm symmetry of the unit cell whereas the
Accepted Article
BCST composition with x = 0.075 exhibit a mixed P4mm + Amm2 phase coexistence of

tetragonal and orthorhombic lattice symmetries that can tune the ferroelectric and

piezoelectric responses of lead-free BCST ceramics. To make sure about the phase

coexistence and tetragonal lattice symmetry of BCST ceramics, the compositions were

electrically poled at room temperature for Dc bias of 800-1000 V for 30 minutes and

recorded the XRD pattern for poled samples, shown in figure S2 (Supplemental material). It

is clearly seen that the compositions with x = 0.00 to 0.05 retains the tetragonal lattice

symmetry with higher intensity (002) reflection than the (200) reflection.9,15 On the other

hand, the compositions x = 0.075 and x = 0.1 exhibits the orthorhombic-tetragonal and

pseudo-cubic lattice symmetries having higher intensity (200) reflection than the (002) and a

single (200) reflection, respectively. 9,15

The SEM micrographs as shown in figure S3 (Supplemental material) of the polished

surfaces of BCST ceramics sintered at 1400 oC for 5h reveals the well-densified coarse-

grained and pore-free microstructure, consisting of irregular grains. The relative density and

porosity were found to be in the range of 90-92% and ~10%, respectively (Table 1). It is seen

from SEM images that the compositions x = 0.05, 0.075 and 0.1 exhibit the higher density

which indicates that Sn4+ has a significant role in tailoring the microstructure of BCST

ceramics. The average grain size of BCST ceramics with Sn4+ content was calculated by

using the line intercept method and the obtained values are shown in figure S3(f)

(Supplemental material). As Sn4+ content increases from 0.0 to 0.1, the average grain size of

BCST ceramics decreases from 8.56 µm to 2.36 µm (Table 1) and thus higher the Sn4+

content, the more substantial is the decrease of average grain size. This decrease of average

grain size with Sn4+ content may be attributed to the lower grain-growth rates of slowly

diffusing Sn4+ due to its higher ionic radii compared to Ti4+. This may also be interpreted as,

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 during the solid-state reaction, Sn4+ takes longer time to get diffuse due to its higher ionic

radii. This is because the coalescence process takes place and forms the non-uniform
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microstructure having the grains of irregular shapes and undefined boundaries. This

composition-dependent evolution of microstructure is demonstrating the inhibiting effect of

solute on the grain growth process. 17, 25-26

B. Dielectric properties
Temperature dependent dielectric parameters viz. dielectric constant (εr) and dielectric loss

(tanδ) were measured from -100 oC to 150 oC, at 100 kHz shown in figure 2. From figure2(a-

b) it is seen that for x = 0.00 and 0.025; there is only one phase transition was observed in the

studied temperature range, which corresponds to the ferroelectric-paraelectric phase transition

i.e. Curie temperature (TC). This revealed that the TC remains almost unchanged for x = 0.00

and x = 0.025, whereas the orthorhombic-tetragonal (TO-T) and rhombohedra-orthorhombic

(TR-O) may be shifted below -100 oC. This suggests that the off-centering nature of Ca2+

stabilizes the tetragonal phase of BCT. In this context, Xio et.al have investigated the phase

diagram of Ca2+ substituted polycrystalline Ba1-xCaxTiO3 (BCT) ceramics and reported that

the Ca2+ substitution lowers the TR-O and TO-T phase transition temperatures; considerably

broaden the tetragonal temperature range of BT ceramics, without disturbing TC.12 The peaks

correspond to TO-T and TR-O are observed below (εr)max for x = 0.05 and x = 0.075 (Figure

2(c-d)). Furthermore, for composition x = 0.10 (figure 2e), the TO-T and TR-O phase transitions

were disappeared, and (TR-T) is observed at -25 oC in addition to the TC. It is known that for

BaTiO3 based ceramics with Zr, Hf, and Sn substitutions, there is an increase of the

orthorhombic-tetragonal (TO-T) and the rhombohedral-orthorhombic (TR-O) transition

temperatures, whereas decrease of the tetragonal-cubic transition (Tc) temperature.6 Similar

trends are observed in the present study for Sn4+ modified BCT ceramics. Thus, the

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 compositions with x = 0.05 and 0.075 exhibit a sequence of three ferroelectric phase

transitions as from rhombohedral to orthorhombic (R-O), orthorhombic to tetragonal (O-T)

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and the tetragonal to cubic (T-C) phase with heating cycle. Figure 2f illustrates that, with

increasing Sn4+ content, (εr)max increases initially for x ≤ 0.05; thereafter decreases for the

remaining samples. Furthermore, the dielectric maxima of BCST ceramics shows the

systematic broadening of peak at TC with increasing Sn4+ content. This suggests the diffused

phase transition (DPT) type of behavior present for Sn4+ modified BCT ceramics.27-29 This is

attributed to the coalescence of low temperature phase transformations such as rhombohedral

to orthorhombic and orthorhombic to tetragonal.9,18,29 The Curie temperature of BCT

ceramics is found to be decreases with Sn4+ content whereas the R-O and O-T transition

temperature increases with increasing Sn4+ content; for higher Sn4+content (x = 0.1) the R-O

and O-T transitions get merged into rhombohedral to tetragonal (R-T). Therefore, based on

the dielectric anomaly observed at different temperatures with Sn4+ content in BCST

ceramics, a phase diagram has been constructed and is shown in figure 3. Thus, the observed

dielectric results are in good agreement with the XRD results which show the phase

coexistence of orthorhombic-tetragonal lattice symmetry for x = 0.075 of BCST ceramics.

Furthermore, it is known in electroceramics as the grain size decreases, the Curie

temperature of BaTiO3 and BT based materials decreases. 16, 30-31 In this connection, Uchino,

et al. have suggested that with decreasing grain size, the TC was shifted to lower temperature

side through the room temperature and thus eventually tending toward 0K at some critical

grain size.32 In the present study, in accordance with the SEM micrographs, the grain size of

BCST ceramics is found to be decreased with increasing Sn4+ content (figure S3 (f)

(Supplemental material)). Hence, the TC of BCST ceramics decreases with increasing Sn4+

content. Moreover, the decrease of TC with increasing Sn4+ content may be attributed to the

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 formation of defects in the form of non-ferroelectric SnO6 octahedra which would disturb the

cooperative linking between the ferroelectric active TiO6 octahedra,33 like Zr4+ doping .34-35
Accepted Article
The measured dielectric loss (tanδ) values as shown in figure S4 (Supplemental

material) also show the maximum around the phase transitions. The maxima observed in tanδ

at TC; can be ascribed to an increase of the mobility of ions and imperfections in the material.

However, it is important to note that with Sn4+ modification, the lower dielectric loss

observed to be very small (< 4%) in the measured temperature range.

C. Ferroelectric Properties
Figure 4(a-e), shows the polarization-electric field (P-E) hysteresis loop and displacement

current density - electric field (J-E) curves measured with an applied electric field up to 50-

60 kV/cm at 0.1 Hz. Both the P-E and J-E measurements were performed on virgin (unpoled)

composition. All BCST ceramics exhibit a typical electric-field induced ferroelectric

polarization hysteresis loop, which confirms the ferroelectric nature of investigated samples.

In the present work, some of BCST compositions do not show the well-saturated P-E

hysteresis loops. Because to achieve the saturation state of polarization in electroceramics is

rather quite difficult due to the dielectric strength of the electroceramics which limits the

electric field value. Moreover, the saturation state of polarization as well as the proper values

of coercive field (Ec) and remnant polarization (Pr) can be reported by measuring the electric

field induced displacement current density that reveals the sharp peaking behavior during

positive and negative cycles.36-37 The presence of J-E peak corresponds to the Ec value i.e. a

field responsible for domain switching for a saturated loop.36-38 It is important to note that,

most of the time, the reported values of Pr and Ec values are estimated from the observed P-E

hysteresis loop which is not well saturated; thus, in principles they are not proper values as
36-37
they are measured from the pre-saturated P-E loops. Therefore, the peak value of

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 displacement current density (J) shown in figure 4(a-e) for the forward and reverse cycles

indicate the presence of a cyclic and uniform in both the directions, a typical characteristic of
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ferroelectric materials.

An observation made from figure 4 a-e reveals that the compositions with x = 0.00

and x = 0.1 does not exhibit the sharp peaking behavior hence they are said to be not the

completely saturated, whereas the compositions with x = 0.025, 0.05 and 0.075 show the

sharp peaking behavior of displacement current density. Thus, the compositions with x =

0.025, 0.05 and 0.075 are said to be completely saturated with respect to an applied electric

field. The observed values of Jmax for positive cycle are tabulated in Table 1. The

compositions x = 0.05 and 0.075 show the maximum values of Jmax as 4.71 10-5 A/cm2 and

3.61 10-5 A/cm2, respectively. Another important observation is made from figure 4 that for

compositions with x = 0.025, 0.05 and 0.075, both the P-E and J-E curves are intersecting at a

value of electric field which is approximately corresponds to the coercive field Ec. On the

other hand, the compositions with x = 0.00 and 0.1 does not show any intersection of P-E and

J-E plots. Furthermore, the compositions with x = 0.025, 0.05 and 0.075 exhibit the

symmetric nature during positive and negative cycle of an applied electric field i.e. there is no

imprint behavior of polarization state. This means that the compositions with x = 0.025, 0.05

and 0.075 may be useful for piezoelectric Ac device i.e. vibrational energy harvesting

applications

The ferroelectric parameters namely remnant polarization (Pr), maximum polarization

(Pmax) and coercive electric field (Ec), with Sn4+ content is presented in figure (4f) and the

values are tabulated in Table 1. For x = 0.00 the observed values of Pr, Pmax and Ec are 5.75

µC/cm2, 12.70 µC/cm2 and 7.12 kV/cm, respectively. Here, the BCT showed high value of Ec

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 which indicates that the ferroelectric domains are stabilized and thus the larger electric field

is required to reverse the domains. 12 Further, as Sn4+ content increases from x = 0.025 to 0.1,
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the observed Ec values are in the range, 5.77 kV/cm - 4.34 kV/cm, which indicates that these

ceramics are relatively easy to pole and hence it may be possible to achieve better

piezoelectric and electrostrictive properties. The possible reason for decrease of Ec with Sn4+

is ascribed to the decrease of c/a ratio with Sn4+ content, because the stress resulted from the

domain switching gets reduced with decrease of c/a ratio; hence the domain switches easily
39
under a lower electric field. With Sn4+ content increases, the Pr increases up to 7.05

µm/cm2 (for x = 0.05) and then decreases to 3.97 µm/cm2, for x = 0.1. This increase of Pr

values with increasing Sn4+ content is quite reliable, as it is known that the Sn4+ are not

ferroelectric active where as Ti4+ are ferroelectric active.15,16,18 Thus, the incorporation of Sn4+

into BaTiO3 may dilute the ferroelectricity and suppresses the piezoelectric/electrostrictive

properties. However, in the present study, we have noticed the increasing trend of Pr with

Sn4+ content up to x = 0.05 which could show the promising piezoelectric/electrostrictive

properties. The increase in Pr and Pmax for x = 0.05 may be attributed to the tetragonal crystal

lattice symmetry retained in the composition. However, the compositions x = 0.075 and 0.1

exhibit the crystallographic phase coexistence of orthorhombic-tetragonal and pseudo-cubic

lattice symmetries respectively which gives rise to the instability of ferroelectric domain and

thus the Pr and Pmax decreases. 40 Furthermore, there are some reports which states that when

Sn4+ content in BaTiO3 increases (> 0.075), the system gets transformed from ferroelectric to

paraelectric state and exhibit the cubic lattice symmetry. 15-18,23 However, in the present case,

the composition x = 0.1 shows the well hysteretic nature which means that it is a ferroelectric

at room temperature and exhibit the non-cubic/non-centrosymmetric lattice symmetry i.e.

pseudo-cubic. The observed results also support the results obtained from XRD and dielectric

studies. The observed non-linear behavior of Pmax for BCST ceramics may be ascribed to the

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 phase coexistence and partial transformation of orthorhombic-tetragonal phase to pseudo-

cubic phase as evidenced from XRD and dielectric studies

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.

D. Piezoelectric and electrostrictive properties

The bipolar strain (S) versus electric field (E) behavior was investigated for all the BCST

samples and is shown in figure 5 (a-e). They exhibit a typical butterfly loop, which is a

feature of piezoelectric system for biaxial field. It is well-known that the butterfly loop is

observed due to the normal converse piezoelectric effect of the lattice along with the

switching and movement of domain walls. Here, all the BCST ceramics show the hysteretic

strain behavior which may be associated with the domain reorientation. The converse

piezoelectric constant is defined as = Smax/Emax, where Smax is the maximum strain at

maximum electric field (Emax); accordingly, it is calculated and shown in figure (5f). A

careful observation made on S-E plots reveals that the butterfly shape for x = 0.00 is not

symmetric for positive and negative electric field cycle. This type of asymmetric strain

behavior is not suitable for Ac applications where the electric field cycles get continuously

changed and hence will not work properly as desired. Therefore, an effort should be made to

tailor the materials composition to get the symmetric butterfly loop with as small as deviation

in values for positive and negative cycles. Interestingly, in the present work, we have

observed that, with Sn4+ content increases, the asymmetric butterfly observed for x = 0.00,

tends to transform towards the symmetric butterfly loop for x = 0.1 having small deviations in

values for positive and negative cycles.

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 The average value of i.e ( )ave, is calculated and plotted as a function of Sn4+

content for BCST ceramics (shown in figure 5f). It is observed that, as Sn4+ content increases
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the ( )ave value increases linearly from 133 pm/V (for x = 0.00) to 199 pm/V (for x = 0.075)

and thereafter decreases to 185 pm/V (for x = 0.1). The observed values of ( )ave are lower

compared to the reported values for Sn4+ modified BaTiO3-CaTiO3 and BaTiO3 ceramics, 9,15-
18,23,41-42
but it is remarkable to understand the observed symmetric and asymmetric nature of

S-E butterfly loop having smaller hysteresis area. Furthermore, it can be seen from figure 5

(a-e) that the bipolar strain level increases from 0·097% at -56 kV/cm, 0.052 % at +56 kV/cm

(for x = 0·00) to 0·12% at -56 kV/cm, 0.105 % at +56 kV/cm (for x = 0·075). The observed

values of strain 0·115% at 56 kV/cm and 0.1 % at 56 kV/cm for x = 0.075 and x = 0.05,

respectively, are quite remarkable and comparable to the lead-based piezoelectric materials.43

Thus, the present BCST ceramics with x = 0.05 and 0.075 possess the reasonably high strain

level ~ 0·10% (with sprout shape rather than the usual butterfly loop) and consistently

smaller area of hysteresis loop, suitable candidate for piezoelectric Ac devices. 44 The higher

value of strain observed for x = 0.075 may be attributed to the ferroelectric orthorhombic-

tetragonal phase coexistence at room temperature as evidenced from XRD and dielectric

measurements. The strain as well as ( )ave values observed to be decreases for x = 0.1 and

this may be because at this composition, the system gets transformed from non-

centrosymmetric to less symmetric crystal structure i.e. pseudo-cubic structure as confirmed

from XRD data. A careful observation of Table 1 reveals that the composition x = 0.05 shows

better ferroelectric properties than x = 0.075 composition; in contrast, the composition x =

0.075 shows better piezoelectric properties than x = 0.05 composition. This result may be

attributed to the crystallographic lattice symmetries retained by x = 0.05 and 0.075

compositions. The composition x = 0.05 exhibit a pure tetragonal lattice symmetry having six

possible directions of the spontaneous polarization without any instability of ferroelectric

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 17
domains/switching; hence it possesses an easy axis polarization property. But, the

composition x = 0.075 shows the phase coexistence of orthorhombic-tetragonal lattice

Accepted Article
symmetry (near room temperature) having instability of ferroelectric domains which may

results into the more distorted i.e. non-centrosymmetric lattice symmetry and hence it shows

the better piezoelectric response.

The results of electromechanical investigations for BCST ceramics obtained at an

applied electric field up to 50-60 kV/cm at a frequency of 0.1 Hz. The strain curves follow

the square of the polarization i.e. S-P2 as shown in figure S5 (Supplemental material), and the

corresponding averaged (Q33)ave value was calculated and shown in figure S5 (f)

(Supplemental material) . The observed S-P2 hysteresis loop suggests that the strain and

polarization are not in phase. The estimated (Q33)ave values are presented in Table 1. The

(Q33)ave value of lead-based electrostrictive material, such as PbMgNbO3-PbTiO3(PMN-PT),

is reported to be about 0.017 m4/C2. 45 This means that the (Q33)ave values of BCST materials

are notably larger than that of the lead-based and other known lead-free electrostrictors.46-18

Thus, the Sn4+ modified BCT ceramics with x = 0.05, 0.075 and 0.1 having (Q33)ave ~ 0.0469,

0.0667 and 0.0543 m4/C2, respectively, exhibiting the non-linear strain-polarization relation,

can be registered as a promising candidate for electrostrictive actuator applications.

CONCLUSIONS

Ba0.7Ca0.3Ti1-xSnxO3 (BCST) with x = 0.00, 0.025, 0.050, 0.075, 0.1 lead-free electroceramic

system was prepared by solid state reaction method. The studied properties are found to be

structure-composition sensitive. The composition x = 0.075 revealed the phase coexistence of

P4mm + Amm2 i.e. orthorhombic-tetragonal lattice symmetries at room temperature. The J-E

measurements show the peaking characteristic for compositions x = 0.025, 0.05 and 0.075;

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 which reveals that the complete saturation state of polarization along with the proper Ec and

Pr values. The minimum deviation in strain % values, during both the positive and negative
Accepted Article
electric field cycles can be obtained for Sn4+ substitution in BCST ceramics with x = 0.05 and

0.075 compositions. The moderate electrostrictive coefficient (Q33)ave values as 0.0469,

0.0667, 0.0543 m4/C2 were observed for x = 0.05, 0.075 and 0.1, compositions, respectively

and they are higher than the lead-based and lead-free electroceramics. The x = 0.05 and 0.075

compositions showed the notable electrostrictive properties which are useful for piezoelectric

Ac devices namely vibrational energy harvester.

ACKNOWLEDGMENTS

YDK thankfully acknowledges the financial assistance from Department of Science and

Technology (Govt. of India) (Grant No.: SR/FTP/PS-040/2010). RCK thankfully

acknowledge the University Grants Commission (UGC), Government of India (Grant No.

F.30-26/2014 (BSR)) and BCUD Savitribai Phule Pune University for providing start-up

grant and Research grant (RG-31) respectively.

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SUPPORTING INFORMATION

Additional Supporting Information may be found online in the supporting information tab for

this article.

Figure Captions

Figure 1: (Color Online) Rietveld fitted X-ray diffraction pattern of BCST ceramics for x =
0.00, 0.025, 0.050 using P4mm model, for x = 0.075 P4mm+Amm2 model and for x = 0.10
P4mm+ Pm m model.
Figure 2(a-e): Temperature dependent dielectric constant (εr) measured at 100 kHz and (f)
Variation of temperature dependent dielectric maxima with Sn4+ content BCST ceramics
measured at 100 kHz.

Figure 3: Phase diagram for Ba0.7Ca0.3Ti1-xSnxO3 ceramics

Figure 4(a-e): Variation of polarization and displacement current density with applied electric
field at 0.1 Hz for BCST ceramics (f) Variation of coercive field (Ec), remnant polarization
(Pr) and maximum polarization (Pmax) with Sn4+ content in BCST ceramics.

Figure 5(a-e): Variation of bipolar electric field induced strain hysteresis loops measured at
0.1Hz for BCST ceramics (f) Variation of effective piezoelectric coefficient(d*33)ave with
respect to Sn4+ content in BCST ceramics.

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 Table 1: Structural, microstructural, dielectric, ferroelectric, piezoelectric and
electrostrictive
properties of Ba0.7Ca0.3Ti1-xSnxO3 ceramics.
Accepted Article
Parameters x = 0.00 x = 0.025 x = 0.05 x = 0.075 x = 0.1
Lattice constant a, (Å) 3.9596 3.9680 3.9766 3.9819 (T) 3.9805 (T)
3.9797 (O) 3.9830 (C)
Lattice constant b, (Å) - - - 5.6421 (O) -
Lattice constant c, (Å) 3.9939 3.9940 3.9878 3.9896 3.9897
Axial ratio c/a (Tetragonality) 1.0086 1.0065 1.0028 1.0019 1.0017
Volume of unit cell (Å3) 62.619 62.887 63.063 63.260 (T) 63.181 (T)
126.51 (O) 63.186 (C)
Theoretical density (g/cm3) 5.36 5.45 5.52 5.54 5.59
Apparent density (g/cm3) 4.87 4.90 5.09 5.06 5.11
Relative density (%) 90.86 89.91 92.22 91.34 91.42
Porosity (%) 9.14 10.09 7.78 8.66 8.58
Average grain size (µm) 8.56 5.37 4.09 3.89 2.36
Curie temperature (oC) 136 114 94 72 44
εr (100 kHz, 25 oC) 709 790 1193 1496 2343
εr (100 kHz, at Tc) 3030 3189 3270 3105 2652
Pr (µC/cm2) 5.75 6.55 7.05 5.56 3.97
Pmax(µC/cm2) 12.70 12.50 15.20 12.60 12.89
Ec( kV/cm) 7.12 5.77 4.98 4.22 4.34
J ( 10-5A/cm2) 1.70 3.42 4.71 3.61 1.76
( )ave (pm/V) 149 161 186 199 185
4 2
(Q33)ave(m /C ) 0.0524 0.0445 0.0469 0.0667 0.0543

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Accepted Article

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Accepted Article

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Accepted Article

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Accepted Article

This article is protected by copyright. All rights reserved.