Dielectric and ferroelectric properties of SrBi4Ti4O15 single crystals

Hiroshi Irie and Masaru Miyayama

Citation: Appl. Phys. Lett. 79, 251 (2001); doi: 10.1063/1.1384480
View online: http://dx.doi.org/10.1063/1.1384480
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APPLIED PHYSICS LETTERS

VOLUME 79, NUMBER 2

9 JULY 2001

Dielectric and ferroelectric properties of SrBi4Ti4O15 single crystals

Hiroshi Iriea)
Research Center for Advanced Science and Technology (RCAST), The University of Tokyo, 4-6-1 Komaba,
Meguro-ku, Tokyo 153-8904, Japan

Masaru Miyayama
Institute of Industrial Science, The University of Tokyo, 4-6-1 Komaba, Meguro-ku, Tokyo 153-8904, Japan

Received 19 January 2001; accepted for publication 17 May 2001

SrBi4Ti4O15 single crystals were grown, and their dielectric and ferroelectric properties were
investigated along the a(b) axis and c axis, separately. The dielectric permittivity at 1 MHz was
1900 along the a(b) axis at the Curie temperature of 520 C. This value was ten times higher than
that along the c axis. With respect to the ferroelectricity, the saturated remanent polarization was 29
C/cm2 and the saturated coercive field was 26 kV/cm along the a(b) axis under an electric field
of 59 kV/cm, and ferroelectricity was not observed along the c axis. 2001 American Institute of
Physics. DOI: 10.1063/1.1384480

Bismuth layer-structured ferroelectrics BLSFs are considered to be excellent candidates for application in ferroelectric random access memories FeRAMs. Their coercive
fields are lower than those of other ferroelectrics1 4 and domain configuration in them is the 180 domains, which
makes them potentially useful for FeRAMs available with
low power and operated without degradation of performance
fatigue free.5 Among them, SrBi2Ta2O9 is now studied
extensively for the application to FeRAMs. It has been reported that Sr-deficient and Bi-excess SrBi2Ta2O9 shows an
increase in Curie temperature T C with increasing compositional deviation and a marked increase in remanent
polarization.6,7 Generally, the displacive ferroelectrics with a
higher T C have a larger remanent polarization. Since the T C
of SrBi4Ti4O15 520 C is higher than that of SrBi2Ta2O9
335 C, a high remanent polarization can be expected.
However, there has been no report on ferroelectric properties
of SrBi4Ti4O15 single crystals, but for dielectric properties of
SrBi4Ti4O15 bulk ceramics.8 Therefore, the authors have
grown SrBi4Ti4O15 single crystals and measured their dielectric and ferroelectric properties along the a(b)-axis and
c-axis directions independently, which could not be obtained
using bulk ceramics. In addition to that, the measured remanent polarization and coercive field were compared with
those of other BLSF single crystals8 and their dependences
on T C and m number the number of BO6 octahedra were
evaluated.
SrBi4Ti4O15 single crystals were grown from the melt of
stoichiometric mixtures of Bi2O3, SrCO3, and TiO2 by slow
cooling with the vertical temperature gradient of
23 C/mm.915 Plate-like thin sheets, with a thickness of
approximately 0.2 mm and transverse dimensions of approximately 1 mm2 mm, were obtained by this method.
Figure 1 shows the measured x-ray powder diffraction
pattern and the result of Rietveld analysis using the program
16
RIETAN
for powders prepared by pulverizing the
SrBi4Ti4O15 single crystals. In Fig. 1, a dotted line indicates
the measured pattern, a solid line the calculated pattern, and

delta the difference between them. The vertical lines in the

middle of Fig. 1 show the positions of the peak. As the
refined structural parameters for SrBi4Ti4O15, the space
group A2 1 am(36) and lattice parameters, a0.5445 nm, b
0.5437 nm, c4.095 nm, Z4, were obtained. The
SrBi4Ti4O15 single crystal was identified to be a single phase
from the quite small delta. As the agreement factors, the
R-weighted pattern R wp of 10.3 and the goodness of fit S
(R wp /R exp), of 1.70 were also obtained.
Figure 2a shows the dielectric permittivity and dielectric loss of the SrBi4Ti4O15 single crystal along the a(b) axis
from room temperature to 680 C at 1 MHz, Fig. 2b along
the c axis. As the samples were electroded with Pt paste by
heat treatment at 800 C for 1 h, there should be no effects on
the dielectric permittivity at high temperatures. As shown in
Figs. 2a and 2b, T C was found to be 520 C and the
dielectric permittivity along the a(b) axis to be about ten
times higher than that along the c axis. The value of dielectric loss at T C , which is due to the motion of domain walls,
was below 10% along both a(b) axis and c axis. The increased dielectric loss at high temperature is assumed to be
caused by an increase in conductivity.
Samples for hysteresis loops were electroded with Ag
conductive resin dried in air. Figures 3a and 3b show a
coercive field E c and a remanent polarization P r as a function of applied electric field E m , respectively, along the a(b)
axis. Both plots tended to saturate and the saturation points
were defined as the saturated coercive field E c 0 and the satu-

FIG. 1. Measured and calculated x-ray diffraction patterns for powders prepared by crushing SrBi4Ti4O15 single crystal; dotted line for the measured
pattern and solid line for the calculated pattern. Cu K , wavelength:
0.1541 nm.

Electronic mail: irie-hrs@fchem.chem.t.u-tokyo.ac.jp

0003-6951/2001/79(2)/251/3/$18.00

251

2001 American Institute of Physics

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252

Appl. Phys. Lett., Vol. 79, No. 2, 9 July 2001

H. Irie and M. Miyayama

FIG. 2. Temperature dependence of dielectric permittivity and dielectric loss

in the SrBi4Ti4O15 single crystal. a a(b)-axis direction, b c-axis direction.

FIG. 6. E c 0 and E m 0 as a function of m in various BLSF single crystals

along the a(b) axis Ref. 12. Abbreviations are the same with those in Fig.
5.

FIG. 3. a Coercive field E c and b remanent polarization P r as a function

of applied electric field E m in the SrBi4Ti4O15 single crystal along the a(b)
axis.

FIG. 4. Saturated hysteresis loops in the SrBi4Ti4O15 single crystal along the
a(b) axis and c axis.

rated remanent polarization P r 0 , respectively. E m 0 corresponds to the minimum applied electric field necessary for
obtaining those saturated values. From Figs. 3a and 3b,
E c 0 , P r 0 , and E m 0 were found to be 26 kV/cm, 29 C/cm2,
and 59 kV/cm, respectively. Figure 4 shows the saturated
P E hysteresis loops along the a(b) axis and c axis, applying the electric field of 59 kV/cm (E m 0 ). Ferroelectricity was
not observed along the c axis.
Figure 5 shows the P r 0 , E c 0 , and E m 0 as a function of
T C in various BLSF single crystals along the a(b) axis.9 The
P r 0 in BLSFs, including SrBi4Ti4O15, showed linear increase
with increasing T C , as shown in Fig. 5. This relationship
holds true not only in BLSFs but also typical perovskite type
compounds, if they are displacive ferroelectrics.17 In general,
the stoichiometric displacive ferroelectrics with large P r 0
have large E c 0 and E m 0 . However, this relationship does not
hold true strictly for all BLSFs, and SrBi4Ti4O15 showed a
relatively small E c 0 , as shown in Fig. 5. Figure 6 shows the
m number dependence of E c 0 and E m 0 in various BLSF
single crystals along the a(b) axis.9 As shown in Fig. 6, our
finding is that the E c 0 and E m 0 in BLSFs, including
SrBi4Ti4O15, decreased with increasing m number.
In summary, SrBi4Ti4O15 m4, T C 520 C single
crystals were grown, and their dielectric and ferroelectric
properties were examined along a(b)-axis and c-axis directions separately. The dielectric permittivity at 1 MHz was
1900 along the a(b) axis at the Curie temperature of 520 C.
This value was ten times higher than that along the c axis.
With respect to the ferroelectricity, the P r 0 was 29 C/cm2
and the E c 0 was 26 kV/cm along the a(b) axis, applying E m 0
of 59 kV/cm. The P r 0 is larger in BLSFs with a higher T C ,
and the E c 0 and E m 0 are smaller in BLSFs with a larger m
number. Ferroelectricity was not observed along the c axis.

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FIG. 5. P r 0 , E c 0 , and E m 0 as a function of T C in various BLSF single

crystals along the a(b) axis Ref. 12. BIT:Bi4Ti3O12, SrBT:SrBi4Ti4O15,
BBT:BaBi4Ti4O15, B2BT:Ba2Bi4Ti5O18, and P2BT:Pb2Bi4Ti5O18.

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