Crystal structures and ferroelectric properties of SrBi2Ta2O9 and

Sr0.8Bi2.2Ta2O9
Y. Shimakawa, Y. Kubo, Y. Nakagawa, T. Kamiyama, H. Asano et al.
Citation: Appl. Phys. Lett. 74, 1904 (1999); doi: 10.1063/1.123708
View online: http://dx.doi.org/10.1063/1.123708
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APPLIED PHYSICS LETTERS

VOLUME 74, NUMBER 13

29 MARCH 1999

Crystal structures and ferroelectric properties of SrBi2Ta2O9

and Sr0.8Bi2.2Ta2O9
Y. Shimakawaa) and Y. Kubo
Fundamental Research Laboratories, NEC Corporation, 34 Miyukigaoka, Tsukuba 305-8501, Japan

Y. Nakagawa, T. Kamiyama, and H. Asano

Institute for Materials Science, University of Tsukuba, 1-1-1 Tennodai, Tsukuba 305-8577, Japan

F. Izumi
National Institute for Research in Inorganic Materials, 1-1 Namiki, Tsukuba 305-0044, Japan

~Received 21 September 1998; accepted for publication 1 February 1999!

Crystal structures of ferroelectric materials of stoichiometric SrBi2Ta2O9 (T C5300 C) and
Sr-deficient-and-Bi-excess Sr0.8Bi2.2Ta2O9 (T C5400 C) were refined by neutron powder
diffraction. Bi2O2 layer and TaO6 octahedra are considerably distorted and atomic displacements
along the a axis cause ferroelectric spontaneous polarization. In Sr0.8Bi2.2Ta2O9, both Bi substitution
and cation vacancies at the Sr site were revealed and a chemical composition of
~Sr0.82Bi0.12!Bi2Ta2O9.0 was obtained. The calculated polarization of Sr0.8Bi2.2Ta2O9 is larger than
that of the stoichiometric sample, which is consistent with observations of remanent polarization in
thin-film capacitors. The Bi substitution and the cation vacancies at the Sr site enhance structural
distortion in the TaO6 octahedra and lead to the larger ferroelectric spontaneous polarization and the
higher Curie temperature. 1999 American Institute of Physics. @S0003-6951~99!03413-0#

In recent years a lot of attention has been given to the

use of ferroelectric thin films in nonvolatile memory applications @ferroelectric random access memories ~FeRAMs!#.
Ferroelectric SrBi2Ta2O9 ~SBT! has attracted renewed interest as a potential material for such devices due to its fatiguefree nature,1,2 though its fundamental ferroelectric properties
were studied in the early 60s.3 To obtain thin-film capacitors
with high performance ~large remanent polarization, low coercive field, and so on!, phases in the vicinity of the stoichiometric composition have been extensively studied and recently SBT films synthesized with Sr-deficient-and-Biexcess compositions, such as Sr0.8Bi2.2Ta2O9, were found to
show significantly improved ferroelectric properties.4,5
SrBi2Ta2O9 is a so-called Bi-layered Aurivillius compound and the structure consists of Bi2O2 layers and double
perovskite-type TaO6 octahedral units ~Fig. 1!. The crystal
structure of SrBi2Ta2O9 was studied using electron and neutron diffraction techniques, and orthorhombic distortion with
space group A2 1 am was revealed.6,7 Structures of offstoichiometric phases, however, have never been studied. In
addition, cation substitutions expected from a Sr-deficientand-Bi-excess composition have not been confirmed. Because of the constraint of the electrical charge neutrality in
the compound, substitution of trivalent Bi ions for divalent
Sr ions should accompany either cation vacancies or interstitial excess oxygen atoms from ionic considerations. Such
nonstoichiometry for off-stoichiometric samples should be
clarified. Structure refinement using high-resolution neutron
diffraction yields information on the crystal structures and
chemical compositions of the samples. Thus, we are able to
discuss structural and compositional differences between stoichiometric and off-stoichiometric compounds.

This letter describes the results of structure refinements

of stoichiometric SrBi2Ta2O9 and Sr-deficient-and-Bi-excess
Sr0.8Bi2.2Ta2O9 by neutron powder diffraction. Since atomic
displacements from positions with higher symmetry cause
spontaneous polarization, we are able to estimate ferroelectric polarization from refined positional parameters of constituent atoms. The relationship between structural distortion
and ferroelectric properties is also discussed.
Powder samples of SBTs were prepared by solid-state
reaction. Mixtures of SrCO3, Bi2O3, and Ta2O5, with the
ratios of Sr:Bi:Ta51:2:2 and 0.8:2.2:2 were sintered at
1000 1100 C for 30 h in air with intermediate grindings.
The obtained samples were confirmed to be a single phase by

FIG. 1. ~a! a-c and ~b! b-c projections of the crystal structure of
SrBi2Ta2O9. The structure is drawn with the positional parameters refined
by neutron diffraction. Dashed lines perpendicular to the b and c axes represent glide and mirror planes, respectively. P s denotes the ferroelectric
spontaneous polarization.

a!

Electronic mail: shimak@frl.cl.nec.co.jp

0003-6951/99/74(13)/1904/3/$15.00

1904

1999 American Institute of Physics

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Shimakawa et al.

Appl. Phys. Lett., Vol. 74, No. 13, 29 March 1999

1905

TABLE I. Refined structural parameters for SrBi2Ta2O9. Numbers in parentheses are standard deviations of the last significant digit. B eq is the equivalent isotropic thermal parameter obtained from refined anisotropic thermal
parameters. No vacancies were detected for all sites, and thus, occupation
parameters were fixed at 1.0: Space group; A2 1 am. a55.52237(18) , b
55.52408(17) , and c525.02641(50) . Note that R wp54.90%, R p
53.73%, R I51.37%, R F 51.03%, and R e54.64%.
Atom

B eq ( 2 )

Sr
Bi
Ta
O~1!
O~2!
O~3!
O~4!
O~5!

0.0
0.4634~8!
0.5104~13!
0.5248~14!
0.5219~12!
0.7381~13!
0.7554~14!
0.7909~12!

0.2567~9!
0.7764~6!
0.7480~7!
0.2892~13!
0.6990~11!
0.9923~8!
0.9867~8!
0.9807~8!

0.0
0.19996~7!
0.41482~7!
0.0
0.34187~11!
0.25076~13!
0.06964~10!
0.58359~11!

0.69
1.54
0.39
1.04
1.55
0.85
0.62
0.91

both x-ray and neutron diffraction. Capacitance of the diskshaped samples was measured at temperatures from 0 to
600 C using a conventional LCR meter with a frequency of
100 kHz. Time-of-flight neutron powder diffraction data
were collected at room temperature using the Vega diffractometer at KENS.8 Structural parameters were refined by the
Rietveld technique using the program RIETAN.9
The result of the structure refinement of the SrBi2Ta2O9
sample is listed in Table I. For all sites no anomalous occupancies were observed, indicating stoichiometric composition as expected from the nominal one. The obtained structural parameters are essentially the same as those reported
before.7 In Fig. 1, the crystal structure of SBT is illustrated
as projections on a-c and b-c planes. Both Bi2O2 layer and
TaO6 octahedra are considerably distorted. Four kinds of BiO~3! bonds with lengths of 2.51, 2.31, 2.30, and 2.19 , are
included in the Bi2O2 layer ~though these bonds are equivalent in the tetragonal structure!. The TaO6 octahedra are
buckled along the b axis with a tilting angle of about 6.5
from the c axis @which is obtained from a Ta-O~1!-Ta bond
angle of 167.0#. With the A2 1 am orthorhombic symmetry,
the a axis is the polar axis. Atomic displacements along the a
axis from the corresponding positions in the parent tetragonal (I4/mmm) structure cause ferroelectric spontaneous polarization. Displacements along the b and c axes, in contrast,
are cancelled due to the presence of glide and mirror planes,
respectively, thus, they do not contribute the total polarization.
The contribution of each constituent ion to the total
spontaneous ferroelectric polarization is calculated as
P s5S i ~ m i 3Dx i 3Q i e ! /V,

~1!

where m i is the site multiplicity, Dx i is the atomic displacement along the a axis from the corresponding position in the
tetragonal structure, Q i e is the ionic charge for the ith constituent ion, and V is the volume of the unit cell. The calculated polarization is 18.2 mC/cm2. In Fig. 2, the contribution
of each ion to the total spontaneous polarization is illustrated
by setting the position of the Sr site at the origin. It should be
noted that large atomic displacements of Bi31 in the Bi2O2
layer and of O~5!22 in the TaO6 octahedron play an important role in the large ferroelectric spontaneous polarization in
SBT. Although the displacements of Ta51 and O22 ions in

FIG. 2. Schematic drawing of the contribution of each ion to the total

ferroelectric spontaneous polarization for SrBi2Ta2O9 ~closed arrows! and
Sr0.8Bi2.2Ta2O9 ~open arrows!. The position of the Sr site on the a axis is
fixed at the origin.

the TaO6 octahedron contribute to the total polarization oppositely, net polarization caused by the distortion of TaO6
enhances the total ferroelectric polarization.
The structure refinement of Sr0.8Bi2.2Ta2O9 revealed that
cation vacancies as well as Bi substitution exist at the Sr site.
In the initial refinement, the 20% Bi substitution at the Sr site
that was expected from the nominal composition of
~Sr0.8Bi0.2!Bi2Ta2O9 was assumed, and the result gave an unreasonably large thermal parameter for the Sr site (B eq
51.36 2 ). This value is twice of that for the stoichiometric
sample (0.69 2 ), while the refined thermal parameters for
the other sites are comparable between the two compounds.
Since such a large B eq parameter is often seen at a site with
vacancies, this result strongly suggests the existence of vacancies at the Sr site. Because no excess oxygen atoms were
detected in the refinement, a model with the cation vacancies
accompanied by the Bi31 substitution for Sr21 is quite reasonable from ionic considerations of the charge neutrality.
Then, the occupancy of (Srx Biy ) under the constraint of 2x
13y512 was refined. The result of the final refinement of
the Sr0.8Bi2.2Ta2O9 sample is given in Table II. The occupancy for the Sr site is (Sr0.82Bi0.12h 0.06), where h represents vacancies, and the thermal parameter for this site decreased to a reasonable value of 1.00 2 .
TABLE II. Same as for Table I, but for Sr0.8Bi2.2Ta2O9 : a
55.51415(8) , b55.51187(8) , and c525.0322(2) . Note that R wp
53.73%, R p52.75%, R I51.34%, R F 51.19%, and R e54.32%.

Atom

B eq ( 2 )

Sr/Bia
Bi
Ta
O~1!
O~2!
O~3!
O~4!
O~5!

0.0
0.4638~5!
0.5161~8!
0.5329~9!
0.5267~8!
0.7387~8!
0.7574~9!
0.8043~9!

0.2558~6!
0.7752~4!
0.7467~5!
0.2948~9!
0.6966~6!
0.9930~5!
0.9811~5!
0.9725~5!

0.0
0.20006~4!
0.41493~5!
0.0
0.34157~7!
0.25051~8!
0.06959~7!
0.58423~7!

1.00
1.38
0.52
1.17
1.41
0.80
0.75
0.89

The occupancy was refined to be Sr/Bi50.82(2)/0.12(2).

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1906

Shimakawa et al.

Appl. Phys. Lett., Vol. 74, No. 13, 29 March 1999

In Sr0.8Bi2.2Ta2O9, the lattice parameters a and b are

smaller ~by 0.15% and 0.22%, respectively! while c is
slightly larger ~by 0.02%! than those in the stoichiometric
sample, and thus, structural change mainly occurs in the a-b
plane. The distortion of the TaO6 octahedron is more pronounced than that in SrBi2Ta2O9. The tilting angle of the
octahedra increases to 7.5 @Ta-O~1!-Ta bond angle: 165.0#,
also indicating more pronounced buckling of the octahedra.
As shown in Fig. 2, the calculated ferroelectric spontaneous
polarization for the off-stoichiometric sample is
20.0 mC/cm2, which is larger than that for the stoichiometric
sample. Since the observed P s is 1/3 of the calculated P s of
20.0 mC/cm2 in randomly oriented polycrystalline sample,
this calculated P s corresponds to 6.7 mC/cm2 in polycrystalline form, which agrees well with the observed spontaneous
polarization of about 7 mC/cm2 in P-E hysteresis.10 The enhanced spontaneous polarization is mainly caused by the
larger distortion of the TaO6 octahedra. This finding is consistent with observations in thin-film capacitors, where Srdeficient-and-Bi-excess materials show remanent polarization, P r , larger than that of the film synthesized with the
stoichiometric composition.4,5 As shown in the crystal structure in Fig. 1, the TaO2 plane in TaO6 octahedra is the densest plane in the unit cell. Thus, the Bi2O2 layer is under
tensile stress while the perovskite-like unit is under compressive stress. The substitution of smaller Bi31 ions for Sr21
ions should cause such compressive stress in the perovskitelike unit to become pronounced, as a result, the mismatch
between the perovskite-like unit and the Bi2O2 layer will
increase in Sr0.8Bi2.2Ta2O9, leading to the larger distortion in
the TaO6 octahedra.
The structural distortion is also related to the ferroelectric Curie temperature. Figure 3 shows the temperature dependence of the dielectric constant e for the SrBi2Ta2O9 and
Sr0.8Bi2.2Ta2O9 samples. They show typical ferroelectric behavior with peaks at characteristic ~Curie! temperatures, T C ,
and the transitions are of second-order type. T C for the stoichiometric material is 300 C, while that for the Srdeficient-and-Bi-excess compound increases to 400 C. The
dielectric constant above T C obeys the Curie-Weiss low of

e 5C/ ~ T2T 0 ! 1 e 1 ,

~2!

where C is the Curie constant, T 0 is an extrapolated transition temperature, and e 1 is a temperature-independent term.
T 0 s obtained from the fit of Eq. ~2! are 278 and 391 C for
the stoichiometric and off-stoichiometric samples, respectively, and these temperatures are quite close to T Cs. As the
structural distortion increases, the ferroelectric Curie temperature increases.

FIG. 3. Temperature dependence of the dielectric constant e for SrBi2Ta2O9

and Sr0.8Bi2.2Ta2O9. The dielectric constants in the figure are normalized by
the values at room temperature. The inset figure shows the Curie-Weiss
behavior of the dielectric constants. e 8 and e 18 are normalized in the same
manner.

In conclusion, structural distortion in Sr-deficient-andBi-excess ferroelectric Sr0.8Bi2.2Ta2O9 is more pronounced

than that for stoichiometric SrBi2Ta2O9, leading to the larger
ferroelectric spontaneous polarization and the higher Curie
temperature.
The authors thank T. Tatsumi and Y. Miyasaka for giving us helpful information on SBT materials and FeRAM
devices. They also thank R. Lang and K. Kobayashi for their
support during this work.

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