Ferroelectric properties of intergrowth Bi4Ti3O12SrBi4Ti4O15 ceramics

Yuji Noguchi, Masaru Miyayama, and Tetsuichi Kudo

Citation: Appl. Phys. Lett. 77, 3639 (2000); doi: 10.1063/1.1328366
View online: http://dx.doi.org/10.1063/1.1328366
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APPLIED PHYSICS LETTERS

VOLUME 77, NUMBER 22

27 NOVEMBER 2000

Ferroelectric properties of intergrowth Bi4Ti3O12 SrBi4Ti4O15 ceramics

Yuji Noguchia)
Department of Applied Chemistry, School of Engineering, The University of Tokyo, 7-3-1 Hongo,
Bunkyo-ku, Tokyo 113-8656, Japan

Masaru Miyayama and Tetsuichi Kudo

Institute of Industrial Science, The University of Tokyo, 7-22-1, Roppongi, Minato-ku,
Tokyo 106-8558, Japan

Received 20 January 2000; accepted for publication 5 October 2000

Ferroelectric intergrowth Bi4Ti3O12 SrBi4Ti4O15 has been demonstrated to have a large remanent
polarization (2 P r ) of 30 C/cm2 and a high Curie temperature of 610 C using bulk ceramics. The
Rietveld analysis of the powder x-ray diffraction patterns showed that there are two kinds of Bi ions
in Bi2O2 layers. One Bi ion in the Bi2O2 layers was displaced to the other Bi ion along the
polarization direction by about 2% of parameter a, which would contribute to the large 2 P r .
2000 American Institute of Physics. S0003-69510000548-9

3) and SrBi4Ti4O15 SBTi; m4), as shown in Fig. 1.7

The crystal structure is an intergrowth made up of one-half
of the unit cells of BIT and SBTi.8 The perovskite blocks of
BIT and SBTi are in turn sandwiched between (Bi2O2) 2
layers, and the BO6 octahedra in BIT-SBTi are all TiO6.
Two Bi ions occupy the A-site of BIT blocks, while two Bi
ions and one Sr ion compose that of SBTi blocks.
Ceramic samples of BIT, SBTi, and BIT-SBTi were prepared by the standard solid-state reaction. Powders of

Ferroelectric materials have been intensively studied for

their application to nonvolatile random access memory
NvRAM. Ferroelectric SrBi2Ta2O9 SBT, one of the bismuth layer-structured ferroelectrics BLSFs, is received as a
leading candidate because of its excellent fatigue endurance
against repetitive switching of polarization even when in the
form of thin films with Pt electrodes.1 However, the remanent polarization ( P r ) of SBT thin films is not sufficient for
high-density integration of NvRAM, and the ferroelectric
properties of SBT exhibit a temperature drift2 because of its
low Curie temperature. To improve P r and to raise Curie
temperature (T C ), thin films with compositions deviating
from the stoichiometry of SBT have been studied.35 Noguchi et al.3 reported that the SBT thin films with Sr deficient
and Bi-excess composition showed a larger 2 P r of 23
C/cm2, and this improvement has been confirmed by several groups.4,5 Recently, thin films of lanthanum-substitued
bismuth titanate (Bi3.25La0.75Ti3O12) was reported to show a
relatively large 2 P r of 24 C/cm2.6 However, there is no
report on ferroelectrics with striking progress of P r , and an
alternative material with a large P r and a high T C is desired
to emerge.
In this letter, we report the ferroelectric properties of a
regular intergrowth BLSF, Bi4Ti3O12 SrBi4Ti4O15, measured using sintered ceramics, and show that this intergrowth
oxide would be a promising candidate for ferroelectric materials without the drawbacks described above.
The crystal structure of BLSFs is generally formulated
as (Bi2O2) 2 (A m1 B m O3m1 ) 2 , where A is mono-, di-, or
trivalent ions, B is tetra-, penta-, or hexavalent ions with
appropriate size and valency, and m is the number of BO6
octahedra in the perovskite blocks (m1, 2, 3, 4, and 5.
The perovskite blocks, (A m1 B m O3m1 ) 2 , are sandwiched
between bismuth oxide layers, (Bi2O2) 2 , along the c axis.
On the other hand, the intergrowth Bi4Ti3O12 SrBi4Ti4O15
BIT-SBTi is composed of two BLSFs, Bi4Ti3O12 BIT; m
a

Present address: University of Tokyo, RCAST Intelligent Materials Lab.,

4-6-1 Komaba, Meguro-ku, Tokyo 153-8904, Japan; electronic mail:
ynoguchi@iis.u-tokyo.ac.jp

0003-6951/2000/77(22)/3639/3/$17.00

FIG. 1. Schematic representation of the crystal structure of intergrowth

BIT-SBTi.
3639

2000 American Institute of Physics

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3640

Appl. Phys. Lett., Vol. 77, No. 22, 27 November 2000

Noguchi, Miyayama, and Kudo

FIG. 2. Result of the Rietveld analysis for the powder XRD pattern of
intergrowth BIT-SBTi. The indicates the difference of the observed data
plus and the calculated solid line pattern.

SrCO3, Bi2O3, and TiO2 of 99.99% purity were mixed for

12 h. Mixed powder was calcined at 800 C for 7 h, and then
fired at 1100 C for 4 h for x-ray diffraction XRD measurements. To obtain dense samples and to compensate Bi vaporization during sintering process, excess Bi2O3 of 3 at. % for
BIT, 2 at. % for SBTi, and 1.5 at. % for BIT-SBTi, was
added to the starting powder. The final sintering of pellets
was performed at 830 C BIT and 1200 C SBTi and BITSBTi for 1 h. The density of the samples obtained was over
90% of their theoretical density. Powder XRD patterns of
BIT-SBTi were analyzed by the Rietveld method the RI9
ETAN program on the basis of the space group P2 1 am.
Figure 2 shows the results of the Rietveld analysis for
BIT-SBTi. The calculated pattern fits fairly well to the observed data (R wp7.0% and S (R wp /R e )1.33). These results demonstrate that the regular intergrowth structure
spreads through the crystal and that the single phase of
BIT-SBTi was obtained.
Figure 3 indicates the temperature dependence of dielectric constant. While T C of BIT and SBTi was 675 and
520 C, respectively, the intergrowth BIT-SBTi had a T C of
610 C. This T C for BIT-SBTi is almost the middle of those

FIG. 3. Temperature dependence of dielectric constant at 1 MHz.

FIG. 4. a Polarization hysteresis loops and b the relation between 2 P r

and maximum applied electric field (E m ) measured at 25 C.

of BIT and SBTi, and much higher than that of SrBi2T2O9

300 C.10,11 For further investigations of ferroelectric phase
transitions, differential thermal analysis DTA measurements were performed using the broken pieces of the
samples during heating and cooling. The phase-transition
temperature of BIT estimated from endo- and exothermic
peaks were 675 C, which indicates that the ferroelectric
paraelectric transition of BIT is of the first-order type. On the
other hand, any peak was not detected for SBTi. In the case
of BIT-SBTi, the DTA signal caused by both endo- and exothermic structural change appeared at around 610 C, which
is direct evidence of the first-order-type ferroelectric phase
transition at 610 C. While parameter b 0.54459 nm and c
3.6926 nm of BIT-SBTi became the average of those for
BIT and SBTi, parameter a 0.54269 nm is shorter than
those of the constituent BLSFs 0.54473 nm for BIT and
0.5451 nm for SBTi. The ferroelectricity of BLSFs mainly
originates from the displacements of A- and B-site ions along
the a axis,12 and parameter a is closely related to the ferroelectricity. The shorter a and T C of BIT-SBTi could be the
result of the strong ferroelectric interaction between two
kinds of perovskite blocks in the intergrowth structure.
Figure 4 shows a polarization hysteresis loops and b
maximum electric field (E m ) dependence of 2 P r measured at

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Appl. Phys. Lett., Vol. 77, No. 22, 27 November 2000

25 C. Note that the 2 P r of BIT-SBTi is larger than those of

the constituent BIT and SBTi, and reached 30 C/cm2. This
2 P r value is twice as large as that of SrBi2T2O9. 1 For the
relation between 2 P r and E m shown in Fig. 4b, while the
saturation tendency of 2 P r can be observed for SBTi and
BIT-SBTi, the 2 P r of BIT linearly increased with E m and
did not begin to saturate. These results show that the spontaneous polarization of BIT-SBTi is larger than that of SBTi.
As a result of the Rietveld analysis, the (Bi2O2) 2 layers
of the intergrowth BIT-SBTi were found to be significantly
different from those of BIT and SBTi. For normal BLSFs,
the Bi ions in (Bi2O2) 2 layers are all identical from the
viewpoint of crystallography,13 and the distance between two
adjacent Bi ions along the a axis is the half of parameter a.
On the other hand, there are two kinds of Bi ions in Bi2O2
layers for BIT-SBTi. One Bi ion was found to move toward
the other Bi ion along the polarization direction by about 2%
of parameter a, resulting in an enhancement of ferroelectric
polarization. Actually, BIT-SBTi had a larger P r than constituent BIT and SBTi, which would be partially attributed to
the displacement of the Bi ions in the Bi2O2 layers. It seems
that the lattice mismatch between the blocks of BIT and
SBTi in the intergrowth oxides causes significant structural
stress in the Bi2O2 layers. Furthermore, two kinds of Bi ions
in the Bi2O2 layers for BIT-SBTi are in different crystallographic environments; one bonds to the apex oxygen of TiO6
octahedra in BIT blocks, while the other is connected with
that in SBTi blocks. These crystallographic factors would
lead to the displacement of Bi ions in the Bi2O2 layers.
In summary, dielectric and DTA measurements showed

Noguchi, Miyayama, and Kudo

3641

that T C of intergrowth BIT-SBTi was 610 C and the ferroelectric phase transition was of the first-order type. It was
found that BIT-SBTi has a large 2 P r of 30 C/cm2, which is
twice as large as that of SrBi2T2O9. As a result of the Rietveld analysis for BIT-SBTi, one Bi ion in Bi2O2 layers was
displaced to the other Bi ion along the polarization direction
by about 2% of parameter a, which would contribute to the
large 2 P r .
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