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PROPERTIES OF Sr1x
LA2x/3Bi4Ti4O15 FERROELECTRIC
CERAMICS
a

WEI WANG , SHI-PU GU , JUN ZHU & XIAO-BING

CHEN

College of Physics Science and Technology,

Yangzhou University, Yangzhou, P. R. China
Published online: 14 Feb 2007.

To cite this article: WEI WANG , SHI-PU GU , JUN ZHU & XIAO-BING CHEN (2006):
PROPERTIES OF Sr1x LA2x/3Bi4Ti4O15 FERROELECTRIC CERAMICS, Integrated
Ferroelectrics: An International Journal, 85:1, 85-92
To link to this article: http://dx.doi.org/10.1080/10584580601085727

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Integrated Ferroelectrics, 85: 8592, 2006

Copyright Taylor & Francis Group, LLC
ISSN 1058-4587 print / 1607-8489 online
DOI: 10.1080/10584580601085727

Properties of Sr1x La2x/3 Bi4 Ti4 O15

Ferroelectric Ceramics

Downloaded by [Seoul National University] at 01:40 28 June 2013

Wei Wang, Shi-pu Gu, Jun Zhu, and Xiao-Bing Chen

College of Physics Science and Technology, Yangzhou University,
Yangzhou P. R. China

ABSTRACT
Dielectric and ferroelectric properties of La-doped Sr1x La2x/3 Bi4 Ti4 O15 ( SLBT-x,
x = 0.000.75) ceramics were investigated. A single phase is achieved up to x = 0.30.
The temperature dependence of dielectric permittivity () for SLBT-x shows the Curie
temperature (Tc ) decreases with increasing La content, implying the relaxation of lattice
distortion, meanwhile the peak of the -T curve decreases and broadens, indicating the
dispersion of phase transition. The A-site vacancies induced by the substitution of La3+
for Sr2+ weakened the coupling between the neighboring TiO6 octahedra and gave rise
to the relief of lattice distortion. The broadening of dielectric peak may be attributed to
the difference of ionic radii between La3+ and Sr2+ as well as the exchange of La3+ at
A-site and Bi3+ at bismuth oxide layer. The hysteresis loops of SLBT-x shows the Lasubstitution increased the 2Pr up to 23.1 C/cm2 and lowered E c down to 79.6 kV/cm.
It may be related to the dipole defects induced by higher-valence-doping at A-site.
Keywords: Ceramics; dielectric properties; ferroelectricity

1. INTRODUCTION
Bismuth layer-structured ferroelectrics (BLSFs) have received much attention for device application due to their advantageous nature such as being
fatigue-free, relatively high Curie temperature (Tc ), low dielectric dissipation
and anisotropic characteristics [13]. However, the ferroelectric and piezoelectric properties are found much lower compared to those of Pb(Zr,Ti)O3 materials because the spontaneous polarization movements are confined to the
a(b) plane of the unit cell. Aurivillius compounds have as general fomula

Received May 31, 2006.

Corresponding author. E-mail: xbchen@yzu.edu.cn

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(Bi2 O2 )2+ (Am1 Bm O3m+1 )2 , built up by m (ABO3 )2 layers that alternates

with (Bi2 O2 )2+ layers. The ferroelectric and piezoelectric properties of BLSFs
vary not only with crystallographic direction but with the number of m. Great
efforts have been made to explore ways aimed to enhance their ferroelectric
and piezoelectric properties and many exciting findings including doping and
forming intergrowth have already been reported [46]. Noguchi et al. detailed
the doping influence on the ferroelectric and dielectric properties of SrBi2 Ta2 O9
(m = 2) by substituting trivalent La3+ for divalent Sr2+ and found a larger remanent polarization (2Pr ) as well as much smaller coercive field (E c ) [7, 8].
As for Bi4 Ti3 O12 (m = 3), an increased 2Pr was also reported in both ceramic
and thin film forms when modified by La at A-site [3, 9]. Another promising
BLSFs, SrBi4 Ti4 O15 (m = 4, SBTi), has been intensively investigated due to its
better fatigue-endurance property and high Tc [10]. The SBTi single crystal has
a 2Pr as high as 58 C/cm2 along the a(b)-axis under an electric field of 59
kV/cm [11]. However, SBTi still has some problems to be addressed such as
small 2Pr (6.2 13 C/cm2 ) and high E c in the thin film forms. The fatigue
property deteriorates with increasing pulse width and decreasing operating frequency [10]. It was reported that the 2Pr of SBTi increases to as high as 24.2
C/cm2 while its E c drops to 60 kV/cm when appropriate La ions enter into
the Bi sites of the perovskite layer [12].
Considering the A-sites in perovskite unit of SBTi are occupied by two
kinds of cations, trivalent Bi3+ and divalent Sr2+ , and the pronounced Ladoping effect on the ferroelectric properties, we are interested in substituting
trivalent La3+ for divalent Sr2+ . It was not reported previously to the best of our
knowledge. The 2Pr was found in our experiment increased to 23.1 C/cm2
and the E c decreased to 79.6 kV/cm when the La content was 0.3. The possible
mechanism responsible for such improvement was discussed.

2. EXPERIMENTAL
The La-doped Sr1x La2x/3 Bi4 Ti4 O15 (SLBT-x, x = 00.75) ceramic samples
were synthesized using the conventional solid-state reaction. Starting metal
oxide SrCO3 , Bi2 O3 , TiO2 and La2 O3 of analytic purity were mixed in ethanol
and ball milled for 24 h, then calcined at 800 C for 8 h. Excess Bi2 O3 of
10 at.% of the stoichiometric composition was added to compensate for the
volatilization of bismuth during sintering. The powders were pressed into pellets
with a diameter of 12 mm and thickness of about 1.5 mm. These pellets were
fired at 11801210 C for 4 h in air followed by furnace cooling.
The crystal structure of each species was characterized by X-ray diffraction
(XRD) using M03XHF22 diffractometry with Cu K radiation. These pellets
were filed and polished to a thickness of about 0.2 mm, then coated with silver electrode (1.0 mm in diameter) for ferroelectric property measurements.

Properties of Sr1x La2x/3 Bi4 Ti4 O15 Ferroelectric Ceramics

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The ferroelectric hysteresis loops were measured by a standard ferroelectric

analyzer (Radiant Technologies, Precision LC). The dielectric properties were
measured with a low-frequency impedance analyzer (HP-4192A). The pellets
for dielectric property measurements have a typical thickness of 0.5 mm and
an electrode diameter of about 2.5 mm.

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3. RESULTS AND DISCUSSION

As shown in Fig. 1, a single phase of randomly-oriented bismuth layered structure was maintained with increasing La content up to 0.3 and a secondary
phase was found with further doping. In case of La3+ substitution for Bi3+ ions
(SrBi4x Lax Ti4 O15 , SBLT-x), the phase purity could be kept with x as high
as 1.00 [12]. In the pseudo-perovskite layer of SBTi, there is only one Sr2+
ion coupled with two Bi3+ ions to be substituted, so it is understandable that
the solubility of La3+ in our experiment, 30%, is lower than that of SBLT-x,
50%. But taking into account the fact that some La3+ ions started to enter into
(Bi2 O2 )2+ layers in higher doping level in SBLT-x, the percentages of solubility
in both cases are comparable.
Figure shows the dielectric permittivity () of SLBT-x ceramics as a function of temperature measured at a frequency of 116 kHz and the inset gives
the dependence of Tc on the doping content. It can be seen that the peak of the
-T curve decreases and broadens and Tc presents a rough linear decreasing

Figure 1. XRD patterns of SLBT-x.

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W. Wang et al.

Figure 2. Temperature dependence of of SLBT-x, inset is Tc dependence on La

content.

tendency as the doping content increases up to 0.30. In terms of the generallyaccepted relation rule between the Tc and lattice structure [13], it can be deduced
that the introduction of La3+ ions in SLBT-x caused the relief of lattice distortion, which is analogous to SBLT-x [12]. It runs against experimental fact
if we merely take Coulomb interaction into account which prefers tightened
lattice distortion when La3+ ions with higher positive charge and smaller radius
(0.117 nm for La3+ , 0.132 nm for Sr2+ [17]) were substituted for Sr2+ . So we
tend to believe that such crystal relaxation may be related to the A-site vacancies
rather than the ion charge and radius induced by the substitution of trivalent
La3+ ion for divalent Sr2+ ion under the restriction of charge neutrality [16],
which can be expressed more explicitly via the Kroger-Vink notation shown
below:

La2 O3 2LaSr + 3OX
O + VSr

(1)

In this equation, LaSr is La ion at the A (Sr) site with +1 effective charge,
denotes O ion and VSr indicates the A site vacancy.
Figure presents the comparison of Tc dependence on La content between
SLBT-x and SBLT-x. Obviously the Tc drops more drastically in equivalentvalence-doping case. What responsible for this faster decrease of Tc about SBLTx may come from the following two aspects. For one thing, the ion radius of
Bi3+ is smaller than that of Sr2+ (0.117 nm for Bi3+ , 0.132 nm for Sr2+ [17]) and
Bi3+ has +3 positive charge while Sr2+ only +2, so the Coulomb interaction

O OX

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Properties of Sr1x La2x/3 Bi4 Ti4 O15 Ferroelectric Ceramics

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Figure 3. Dependence of Curie temperature on La content about SLBT-x and SBLT-x.

between Bi3+ and O2 should be more strong than that between Sr2+ and
O2 . Moreover, the Bi3+ ions with lone-pair 6s electrons tend to be covalently
bonded with O2 ions, leading to a drastic distortion of the pseudo-perovskite
blocks while Sr2+ ions do not have this kind of lone-pair electrons [14, 15].
In other words, when certain La3+ ions without 6s electrons occupy the Bi3+
site, they will expel the same amount strongly-bonded Bi3+ ions thus relieve
the distortion; when the same amount of La3+ ions enter into the Sr2+ site, they
will expel the same amount of Sr2+ ions together with half the amount of Asite vacancies. Though the A-site vacancies help weaken the coupling between
neighboring TiO6 octahedra and result in the distortion relaxation, the La3+
ions sitting at Sr2+ site might tighten the distortion.
Raman study of equivalent-valence La-doped Bi4 Ti3 O12 , SrBi4 Ti4 O15 , and
mixed-layer Bi4 Ti3 O12 -SrBi4 Ti4 O15 had confirmed the site selectivity between
perovskite layer and bismuth oxide layer [1820]. The La ions prefer to occupy
the A-sites with low doping content and start to be incorporated into (Bi2 O2 )2+
layers at a critical doping value which is 0.1 for SBLT-x. Given that the dielectric permittivity peak of SLBT-x exhibits a similar broadening tendency with
increasing La content to that of SBLT-x, it is acceptable that a small amount
of La ions in our samples may likely enter into (Bi2 O2 )2+ layer at somewhere
below 0.3. Therefore, with increasing La content, the Bi3+ in Bi2 O2 layers
and La3+ in A-sites will exchange to counteract the size mismatch between
Bi2 O2 layers and perovskite blocks [21]. So, cations at A-site distributed in a
microscopic scale are inhomogeneous, which leads to microscopic ferroelectric domains with slightly different Tc values. The distribution of Tc induces

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W. Wang et al.

Figure 4. (a) Polarization-electric hysteresis loops of SBTi and SLBT-0.3; (b) The 2Pr
and E c variation with the La content.

the dispersion of the phase-transition, causing the broadening of the dielectric

peaks as can be seen in the -T curves of both SLBT-xand SBLT-x [21].
Figure 4(a) shows the polarization-electric hysteresis loops of SBTi and
SLBT-0.30 under an applied electric field of about 190 kV/cm and Fig. 4(b)
gives the variation of 2Pr and E c of SLBT-x with x = 00.3. It can be found that
La-substitution improves the rectangularity of hysteresis loops and increases
the 2Pr from 17.3 C/cm2 of non-doped SBTi to 23.1 C/cm2 of SLBT-0.3, a
34% increase in 2Pr . Meanwhile the E c is decreased from 87.1 kV/cm to 79.6
kV/cm. As for the SBLT-0.25, the 2Pr increases roughly 50%, higher than that
in our case. It might be related to the different mechanism presiding over the
increase of 2Pr . Table lists the 2Pr and E c data of SLBT-0.3 and SBLT-0.25.
In SLBT-xseries, when La3+ ion is incorporated into the Sr site, LaSr and VSr
can form dipolar defects which exhibit extremely low mobility below Tc . The
random field around such defects would exert influence upon the polarization
switching process and likely facilitate the switching of those pinned domains,
leading to the increase in 2Pr . On the other hand, the random field lowers
the activation potential required for nucleation of new domains and therefore
resulted in a lower E c [7]. In SLBT-x case, the 2Pr increases monotonically until
x = 0.3 and impure phase is detected with further doping. It might result from
Table 1
The comparison of 2Pr and E c data between SLBT-0.3 and SBLT-0.25

SBTi/SLBT-0.3
SBTi/SBLT-0.25

Applied electric field (kV/cm)

2Pr (C/cm2 )

E c ( kV/cm)

190
150

17.3/23.1
12.5/24.2

87.1/79.6
80.9/60.8

(The data of SBLT-0.25 was cited from reference 12).

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the fact that the excess A-site vacancies deteriorate the integrality of the unit
cell. While in SBLT-x samples, the main factor contributing to the improvement
of 2Pr is the restraint of oxygen vacancies [12]. By the comparison, it can be
found that the restraint of oxygen vacancies plays a more dominant role than
that of dipolar defects in determining the ferroelectric properties.

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4. CONCLUSIONS
In summary, several La-doped Sr1x La2x/3 Bi4 Ti4 O15 samples were prepared
and their dielectric and ferroelectric properties were investigated. It was found
that substituting La3+ for Sr2+ ion can enhance the remanent polarization and
lower the coercive field due to the dipole defects induced by nonequivalent
substitution. The dielectric peak lowers and broadens with increasing La content
and the Curie temperature decreases simultaneously, which may be attributed
to the ions exchange between Bi2 O2 layer and perovskite layer.
ACKNOWLEDGMENTS
This work was supported by the financial support from the National Natural Science Foundation of China (Grant No. 10274066) and the Natural Science Foundation of Education Bureau of Jiangsu Province, China (Grant No.
GK0410181). Partial support was also provided by the Natural Science Foundation of Jiangsu Province, China (Grant No. BK2005052).
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