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Ferroelectric and Piezoelectric

Studies on MoSubstituted SrBi2Ta2O9
Ferroelectric Ceramics
a b c b
Indrani Coondoo , Neeraj Panwar , Venkata S. Puli & R. S.
b
Katiyar
a
National Physical Laboratory, Dr. K. S. Krishnan Road, New Delhi,
110012, India
b
Department of Physics, University of Puerto Rico, San Juan, 00931,
Puerto Rico
c
DECV & CICECO, University of Aveiro, Portugal

Available online: 27 Jun 2011

To cite this article: Indrani Coondoo, Neeraj Panwar, Venkata S. Puli & R. S. Katiyar (2011):
Ferroelectric and Piezoelectric Studies on MoSubstituted SrBi2Ta2O9 Ferroelectric Ceramics,
Integrated Ferroelectrics, 124:1, 1-9

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 Integrated Ferroelectrics, 125:19, 2011
Copyright Taylor & Francis Group, LLC
ISSN: 1058-4587 print / 1607-8489 online
DOI: 10.1080/10584587.2011.573711

Ferroelectric and Piezoelectric Studies on

MoSubstituted SrBi2 Ta2 O9 Ferroelectric Ceramics

INDRANI COONDOO,1,, NEERAJ PANWAR,2,

VENKATA S. PULI,2 AND R. S. KATIYAR2
Downloaded by [University of Aveiro], [Indrani Coondoo] at 03:54 28 June 2011

1
National Physical Laboratory, Dr. K. S. Krishnan Road,
New Delhi - 110012, India
2
Department of Physics, University of Puerto Rico, San Juan 00931, Puerto Rico

Samples of compositions SrBi2 Mox Ta2-x O9 (SBMT), with x = 0.0, 0.025, 0.050, 0.075,
0.10 have been synthesized by solid-state reaction method taking SrCO3 , Bi2 O3 , Ta2 O5
and MoO3 in their stoichiometric ratios. X-ray diffraction patterns of the samples
confirm the formation of single phase layered perovskite structure in the samples with
x up to 0.05. The effect of Mo+6 substitution on the dielectric behavior of SBT was
studied by measuring the capacitance and tangential loss using an impedance analyzer
(HP 4294A). The temperature dependence of dc conductivity vis-a-vis molybdenum
content shows a decrease in conductivity, which is attributed to the suppression of
oxygen vacancies. The ferroelectric and piezoelectric studies of the Mo substituted SBT
ceramics show that the remanent polarization and d33 values increase with increasing
concentration of molybdenum.

Introduction
In recent years, there has been a tremendous interest in ferroelectric materials from the
perspective of their potential applications in electronic devices such as non-volatile random
access memories (NvRAMs) pyroelectric infrared detectors and optical switches [13]. On
account of their read-write speed, non volatility, low operating power and radiation hard-
ness, NvFRAMs are promising candidates for substituting silicon based electrically erasable
programmable read-only memories (EEPROMs) and flash EEPROMs. The materials for
the memory applications are required to possess the following properties: a large remanent
polarization (Pr ), a low coercive field (Ec ), sufficient fatigue endurance against repetitive
polarization switching etc. [4]. Among ferroelectrics, lead zirconate titanate PbZr1-x Tix O3
(PZT) has been investigated extensively and found to be the most promising material for
NvFRAM applications. However, apart from Pb toxicity, PZT suffers from serious degrad-
ing problems such as fatigue, ageing and leakage current that hinder the usability of this
material in devices [57]. Among them fatigue (a decrease in switchable polarization with
increasing number of polarization reversals) is an important reliability issue for NvRAM
devices [8].
During the search for alternate Pb-free ferroelectric materials for the aforementioned
applications, it was realized that bismuth oxide layered structures (BLSFs), originally

Received August 15, 2010; in final form November 4, 2010.

Corresponding author. E-mail: indrani coondoo@yahoo.com. Present address: DECV &
CICECO, University of Aveiro, Portugal
1
 2 I. Coondoo et al.

synthesized by Aurivillius [9], are the most suitable ones due to their relatively high Curie
temperature, Tc , low dielectric dissipation and anisotropic nature originating from their
layered structure [1011].
SrBi2 Ta2 O9 (SBT) is one of the important BLSF ferroelectric materials for NvRAM
applications. In SBT, orthorhombic structural distortions with non-centrosymmetric space
group A21 am causes spontaneous ferroelectric polarization (Ps ) along a axis. A non-
stoichiometry in the SBT composition by introducing excess Bi or cation vacancies at
Sr sites is known to result in improved ferroelectric properties [1213]. In a related sys-
tem, SBN, partial substitution of pentavalent niobium ions (Nb5+) with smaller pentavalent
vanadium ions (V5+) resulted in enhanced dielectric and ferroelectric properties includ-
ing both dielectric constant and remanent polarization attributed to an increased rattling
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space inside the NbO6 octahedra [1415]. The addition of soft ions (ions with higher
valency than the substituting ion) results in the generation of cation vacancies [16]. Gener-
ally, soft ferroelectrics are characterized by a lower coercive field (Ec ) and higher remanent
polarization (Pr ) [1718].
Hexavalent substitution has recently been investigated as an important substituent and
enhanced remanent polarization has been reported only with small substitution [1922].
Therefore, with the objective to improve structural, dielectric and ferroelectric properties,
molybdenum (Mo+6) has been chosen as a donor cation for partial replacement of the
pentavalent tantalum (Ta+5) in SBT. In this report, the effect of molybdenum substitution in
SBT (SBMT), on the micro-structural, dielectric, ferroelectric and piezoelectric properties
is reported.

Experimental
Samples of compositions SrBi2 Mox Ta2-x O9 (SBMT), with x = 0.0, 0.025, 0.050, 0.075,
0.10 have been synthesized by solid-state reaction method taking SrCO3 , Bi2 O3 , Ta2 O5
and MoO3 in their stoichiometric ratios. The powders were thoroughly mixed, ground and
calcined at 850 C in air for 8h. The calcined mixtures were reground and admixed with
about 11.5 wt% polyvinyl alcohol as a binder and then pressed into disk shaped pellets.
The pellets were sintered at 1150 C for 2 h in air. X-ray diffractograms of the sintered
samples were recorded using a Siemens, D5000 diffractometer in the range 10 -2 -70
with Cu K radiation. The sintered pellets were polished to a thickness of 1 mm and
coated with silver paste on both sides for use as electrodes and cured at 550 C for half
an hour. DC electrical conductivity measurement was carried out using Keithleys 6517A
Electrometer. The polarization-electric field (P-E) hysteresis measurements were done at
room temperature using a ferroelectric tester (RT 500 V, Radiant Tech.) at virtual ground
mode. Piezoelectric charge co-efficient d33 was measured using a Berlincourt d33 meter
after poling the samples in silicone-oil bath at 200 C for half an hour under a dc electric
field of 6070 kV/cm.

Results and Discussions

i. X-ray Diffraction Studies

Figure 1 shows the XRD patterns of the studied samples of composition SrBi2 Mox
Ta2-x O9 sintered at 1150 C. Since no unidentified peaks are observed it can be concluded
that the single phase layered perovskite structure is maintained all the samples. The peaks
have been indexed using the observed interplanar spacing d and the peaks in the Mo
 Mo-Substituted SrBi2 Ta2 O9 Ferroelectric Ceramics 3
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Figure 1. XRD patterns for SrBi2 Mox Ta2-x O9 samples.

substituted samples are observed to shift towards higher diffraction angle suggesting the
incorporation of Mo+6 ions at Ta+5-sites.

ii. Microstructural Studies

The SEM images of the surface of the Mo-substituted samples are shown in Fig. 2. It
is observed from the figure that Mo substitution has an influence on the microstructural
feature.
The sample with x = 0.0 exhibits a microstructure with porosity, however, with increase
in molybdenum content, a comparatively packed microstructure with reduced porosity is
observed. This implies an improved densification in the doped samples.

iii. Dielectric Studies

Figure 3 (a-b) shows the temperature dependence of dielectric permittivity (r ) and tan-
gential loss, respectively at a selected frequency of 100 kHz in SBMT samples sintered

Figure 2. SEM micrographs of surfaces of SrBi2 Mox Ta2-x O9 samples with (a) x = 0.0, (b) x = 0.05,
(c) x = 0.075 and (d) x = 0.10.
 4 I. Coondoo et al.
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Figure 3. Temperature dependence of (a) r and (b) tangent loss measured at 100 kHz in
SrBi2 Mox Ta2-x O9 samples sintered at 1150 C.

at 1150 C. The samples exhibit transition at their respective Curie temperatures (Tc ). It is
observed that peak dielectric permittivity increases from 210 (x = 0.0) to 450 (x =
0.10) while loss reduces with increasing molybdenum concentration in SBT.
The observed variation in Tc and peak-permittivity (r ) with concentration is due to the
substitution of parent cation (Ta5+) by a smaller and higher valent cation Mo6+. Generally
in perovskite ferroelectrics, doping at B-site (located inside an oxygen octahedron) with
smaller ion results in the shift of the Curie point to a higher temperature, leading to a
larger polarization due to the enlarged rattling space available for smaller B-site ions
[15]. On similar argument, the substitution of smaller cation causes Tc to increase in the
present study. The high Tc is indicative of enhanced polarizability [23] and that explains the
increase in peak-r as observed in the studied samples. Moreover, since the valency of the

substitutional cation (Mo6+) is higher than Ta5+, it creates cationic vacancies at Sr-site (VSr )
to maintain electrical neutrality of the lattice structure [24]. The process can be represented
 Mo-Substituted SrBi2 Ta2 O9 Ferroelectric Ceramics 5

as:
1 
Null = MoT a + VSr (1)
2
where MoT a represents molybdenum replacing tantalum site and VSr 
denotes the Sr-vacant
site. It has been reported that the cation vacancies make the domain motion easier and
increase the dielectric permittivity [2526] and thus an increase in r with increasing Mo
content is observed. The dissipation behavior in the studied samples can be explained in
terms of the oxygen vacancy contribution. It has been reported that the presence of inherent
oxygen vacancies Vo in SBT (formed due to Bi2 O3 volatilization) act as space charge and
contribute to the dielectric loss [2728], which explains the high tangential loss observed
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for pure SBT. Substitution of Mo6+ for Ta5+ in SBT results in the formation of cation
vacancies. This effectively reduces the concentration of oxygen vacancies which in turn
reduce the tangent loss.

iv. Bulk Conductivity

Figure 4 shows the temperature dependence of bulk conductivity (bulk ) as obtained for
the studied samples from the impedance data. For all the samples, the conductivity is
observed to increase with the increase in temperature. The activation energy Ea associated
with the bulk conduction has been calculated using Arrhenius equation and is shown in
the figure. The observed high conductivity value of the pure sample (x = 0.0) can be
attributed to the presence of inherent oxygen vacancies which are the most mobile charged
species in such layered ferroelectric ceramics [2829]. However, in the Mo-substituted
samples, to achieve charge neutrality, the substitution of Mo6+ onto Ta5+ is accompanied
by the formation of cation vacancies which are effectively negatively charged. The cation
vacancies thus suppress the formation of anionic oxygen vacancies (effectively positively
charged) resulting in a significant decrease of vacancy complexes. As the concentration
of cation vacancies increases, more and more oxygen vacancies are compensated for. The

Figure 4. Variation of bulk conductivity with temperature in SrBi2 Mox Ta2-x O9 samples.
 6 I. Coondoo et al.

energy needed for migration of the combined vacancies also increases, leading to higher
activation energy [3031]. As a result, the conductivity decreases because there are fewer
oxygen vacancies available with sufficient energy to move around [3132]. Therefore the
observed decrease in bulk conductivity with increase in Mo content can be understood.

v. P E Studies
The primary feature distinguishing ferroelectrics from other pyroelectrics is that the spon-
taneous polarization can be reversed with an applied electric field. Fig. 5 shows the P-E
plots of the studied samples. On comparing the loops in Fig. 5 it is observed that all the
Mo-substituted samples show better loops as compared to the loop observed in the samples
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with x = 0.0. The 2Pr value increases from 5 C/cm2 (x = 0.0) to 18 C/cm2 (x =
0.10).
It is known that ferroelectric properties are affected by compositional modification,
microstructure and lattice defects like oxygen vacancies within the structure of the mate-
rials [3334]. The ferroelectric domains are locked by the defects and their polarization
switching is difficult, leading to a decrease in Pr . It has been reported that with higher-valent
substituents the significant decrease in the defects (oxygen vacancies) reduces the domain
pinning and leads to high Pr [3536]. It has also been reported that cation vacancies gener-
ated by donor doping make domain motion easier and enhance the ferroelectric properties
[37]. Based on the obtained results and above discussion, it can be understood that in pure

Figure 5. P-E hysteresis loops at room temperature of SrBi2 Mox Ta2-x O9 samples.
 Mo-Substituted SrBi2 Ta2 O9 Ferroelectric Ceramics 7

20

18

16

d33 ( pC/N)
14

12

10
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8
0.000 0.025 0.050 0.075 0.100
x in SrBi 2Ta 2-xMo xO9

Figure 6. Variation of d33 in SrBi2 Mox Ta2-x O9 samples.

SBT, the oxygen vacancies assemble at sites like domain boundaries leading to a strong
domain pinning. Hence well-saturated P-E loops for pure SBT are not obtained. Whereas,
in the Mo-substituted samples the associated cation vacancy formation suppresses the con-
centration of oxygen vacancies reducing the pinning effect on the domain walls, leading to
enhanced remnant polarization and lower coercive field. Another possible reason could be
attributed to the fact that ferroelectric oxides with a higher Tc have a larger Ps (or Pr ) [23].

A. d33 studies
Figure 6 shows the variation of piezoelectric charge coefficient d33 with Mo concentration
in the SrBi2 Mox Ta2-x O9 samples. The d33 values are observed to increase with x however,
d33 did not improve significantly. For the studied samples the piezoelectric coefficient, d33 ,
increases from 9 pC/N in the sample with x = 0.0 to 18 pC/N in the sample with x = 0.10.
Since BLSF generally have high Curie temperature and high coercive field at room
temperature, it is necessary to perform poling at high temperature [38]. However, relatively
high conductivity often prevents the application of high electrical field during the high-
temperature poling treatment [3839]. The conductivity, therefore, should be reduced in
BLSFs to increase the
poling efficiency. As observed in Fig. 4, the Mo-substituted SBT samples show an
electrical conductivity value 23 order of magnitude lower than that of pure samples.
The decrease in conductivity upon donor doping improve the poling efficiency and thus
higher d33 values are obtained. It has been reported that the incorporation of higher valent
ions accompanied with cation vacancies at the A site in BLSFs, improves not only the
ferroelectric property but also the piezoelectric one [4041]. The report that the vacancies
at A sites improve the piezoelectric properties due to increased wall mobility supports the
present observation [41].

Conclusions
Single phase layered perovskite structure is maintained in the samples with molybdenum
substitution in SBT in the range 0.0 x 0.10 as confirmed from X-ray. Molybdenum
 8 I. Coondoo et al.

substitution is effective in enhancing the dielectric constant (r ) and the Curie temperature
(Tc ). The dielectric loss reduces with increase in Mo concentration. The maximum Tc of
330 C is observed in the sample with x = 0.10 as compared to 295 C for the pure
sample when sintered at 1150 C. The peak r increases from 210 in the sample with
x = 0.0 to 450 for the composition with x = 0.10. The temperature dependence of the
electrical conductivity shows that Mo doping results in the decrease of conductivity by as
much as two orders of magnitude compared to pure SBT. The Mo substitution is effective
in enhancing the Pr values. The reduced conductivity allow high-temperature poling of the
doped samples. The d33 values are observed to increase with increasing Mo content.

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