Chemical Physics Letters 378 (2003) 395399

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Crystal structure and disorder of the fast oxide-ion

conductor cubic Bi2O3
Masatomo Yashima *, Daiju Ishimura
Department of Materials Science and Engineering, Interdisciplinary Graduate School of Science and Engineering,
Tokyo Institute of Technology, Nagatsuta-cho 4259, Midori-ku, Yokohama-shi 226-8502, Japan
Received 4 July 2003; in nal form 4 July 2003
Published online:

Abstract
Accurate nuclear density distribution of cubic bismuth oxide (d-Bi2 O3 ) has been obtained by the maximum entropy
method (MEM)-based pattern tting combined with the Rietveld method using neutron-powder-diraction data. The
result shows for the rst time that the oxide ions have a complicated disorder spreading over a wide area and shift to the
h1 1 1i directions from the ideal uorite site. These features are responsible for the high oxide-ion conductivity.
2003 Elsevier B.V. All rights reserved.

1. Introduction
Solid oxides with the uorite-type structure
such as zirconia-, ceria- and bismuth oxide-based
materials are fast oxide-ion conductors, which
enables the use as good electrolyte materials for
applications to solid oxide fuel cells and oxygen
sensors [17]. To develop better electrolyte materials requires a better understanding of the conduction mechanism, and crucial to this is the
knowledge of the disorder of mobile ions at high
temperatures where the materials work eciently.
The bismuth oxide d-Bi2 O3 with the uorite-type
structure has the highest oxide-ion conductivity in
the known compounds. The crystal structure of
the d-Bi2 O3 has been the subject of a number of
*

Corresponding author. Fax: +81-45-924-5630.

E-mail address: yashima@materia.titech.ac.jp (M. Yashima).

investigations for almost 100 years [4,5,812]. But

until now, the accurate disorder of oxide ions has
not been derived yet. Here we report the accurate
disorder in the d-Bi2 O3 . Determination of the
disorder was carried out by a combined technique
of Rietveld renement [13,14] and a maximum
entropy method [15,16]-based pattern tting [17]
of the neutron-powder-diraction data measured
at 778 C. The oxide ions have a complicated
disorder spreading over a wide area and shift to
the h1 1 1i directions from the ideal uorite site.
This feature would be responsible for the fast
oxide-ion conduction of d-Bi2 O3 .

2. Experimental procedure
Commercial bismuth-oxide powders were calcined at 400 C for 12 h to remove the carbonates

0009-2614/$ - see front matter 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.cplett.2003.07.014

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M. Yashima, D. Ishimura / Chemical Physics Letters 378 (2003) 395399

30000

111
25000

20000

Intensity

15000

10000

5000

20

30

40

50

60

70

80

90

100

110

120

130

140

150

2 /

Fig. 1. Rietveld tting result for neutron-diraction data of Bi2 O3 measured at 778 C. Red crosses (+ symbols) and green line denote
observed and calculated intensities, respectively. Up and down short verticals indicate the positions of possible Bragg reections of dBi2 O3 specimen and the alumina phase of the sample stage, respectively. The 1 1 1 is the index of the peak at the lowest 2h position.
(For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

and then pressed into pellets. Neutron powder

patterns of the d-Bi2 O3 with good counting
statistics were obtained at 778.3
1.4 and
759.4
0.4 C in air using a furnace with MoSi2
heaters [18,19] and a diractometer with a 150multi-detector system, HERMES [20], at the JRR3M reactor. The wavelength of incident neutron

. The powder patterns were measured
was 1.8207 A
in the range from 2h 20 to 148. The present
neutron-powder-diraction pattern of the d-Bi2 O3
(Fig. 1) was very similar with that in the literature
[10,11]. The maximum intensity was 29 610 counts
for the data at 778 C. All the peaks were indexed
by the uorite-type structure with Fm3m symmetry
and by a small amount of the second phase from
an alumina stage. The Sillen model (Space group
Pn3m) [8,10] did not yield indices for some observed peaks, indicating no possibility of this
model.
The experimental data were analyzed by a
combination of Rietveld analysis [13,14] and the
maximum entropy method [15,16] (MEM)-based
pattern tting [17]. It is well known that the MEM
can produce a nuclear density distribution map

from the neutron-diraction data [17,21]. In MEM

analysis, any kind of complicated nuclear density
distribution is allowed as long as it satises the
symmetry requirements.

3. Results and discussion

First, Rietveld analysis was done using three
structural models shown in Figs. 2ac. The isotropic harmonic model was used for the atomic
displacement parameters of Bi at 4a site and the
oxygen at 8c position, while the anisotropic displacement parameters were rened for the oxygen
at 32f site (Table 1). The Battle model (Fig. 2c)
gave the best t with the observed neutron-diffraction data, comparing with other models. The
present weighted reliability factors (R-factors)
based on the Rietveld analyses, Rwp were 4.75%,
3.81% and 3.77% for the Gattow and Schroder [9],
Harwig [10] and Battle et al. [11] models, respectively. The calculated prole with the Battle model
agreed well with the observed one (Fig. 1). The
rened crystal parameters based on the Battle

M. Yashima, D. Ishimura / Chemical Physics Letters 378 (2003) 395399

397

Fig. 2. Structural models for d-Bi2 O3 . (a) Gattow model based on an ideal uorite-type structure: average distribution of six oxygen
atoms at the site (8c) of Fm-3m (xxx, x 1=4); (b) Harwig model: average distribution of six oxygen atoms at the site (32f) of Fm-3m
(xxx, x 1=4 d); (c) Battle model: six oxygen atoms are distributed at the 8c and 32f sites; and (d) scattering amplitude distribution of

3 obtained by the combination technique of Rietveld renement and the
d-Bi2 O3 at 778 C with equicontour surface at 0.3 fm/A
maximum entropy method-based pattern tting. To simplify only the region of 0 6 y 6 1=2 is drawn. Red and yellow spheres denote the
bismuth and oxygen atom sites, respectively.

Table 1
Structure parameters of d-Bi2 O3 measured at 778 C
Atom

Site

2 )
U (A

Bi
O1
O2

4a
8c
32f

1
0.23(22)a
0.13(5)a

0
0.25
0.335(21)

0
0.25
x(O2)

0
0.25
x(O2)

0.078(2)
0.08(5)
0.121b

, Rwp 3:77%, Rp 2:69%, Re 1:62%, Goodness of t, Rwp =Re 2:33, RI 4:56%,

Space group: Fm3m; a 5:65499 A
RF 4:54%. g, occupancy; B, isotropic atomic displacement parameter; x, y and z, fractional coordinates.
a
The total oxygen content was xed to be 6 in a unit cell: 8gO1 32gO2 6.
b
Equivalent isotropic atomic displacement parameter calculated using the rened anisotropic atomic displacement parameters,

2 ; U12 O2 U23 O2 U31 O2 0:00730 A

2 .
U11 O2 U22 O2 U33 O2 0:122 A

model are shown in Table 1. The present unit-cell

and positional parameters agreed with those in the
literature [11].
Second, the MEM analysis was done using the
structural factors obtained by the Rietveld analysis

with the Battle model. Number of structure factors

derived in the analysis was 12. The present results
of the MEM analyses would be reliable, because
the 1 1 1 peak intensity at the lowest 2h position
that is the most important information for the

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M. Yashima, D. Ishimura / Chemical Physics Letters 378 (2003) 395399

MEM analysis was measured (Fig. 1). The MEM

calculations were done using a computer program
PR I M A [22], with 64  64  64 pixels. To reduce
the bias imposed by the simple structural model,
an iterative procedure named by REMEDY cycle
[17] was employed after the MEM analysis. In the
sixth REMEDY cycle, the R-factor based on the
Bragg intensities, RI was improved from 4.56% to
1.82%. In the MEM analysis, the R-factor based
on the structure factors, RF was also improved by
the REMEDY cycle from 1.54% to 0.89%. The
MEM map obtained after the sixth REMEDY
cycle provided much information on the complicated disorder of oxide ions (Fig. 2d), comparing
with the previous models (Figs. 2ac). The previous simple models consisted of atom spheres are
no longer appropriate to describe the positional
disorder of oxide ions.
To visualize the structural disorder at 778 C,
the MEM nuclear density distribution map on the
(1 1 0) plane is shown in Fig. 3. The present study

reveals for the rst time that the oxide ions in the
d-Bi2 O3 have a complicated disorder and spread
over a wide area, compared with Bi ions. Two
maxima of the nuclear density are clearly seen at
the 32f sites near an ideal 8c position of the oxide
ion on the (1 1 0) plane (arrows in Fig. 3). The
distance between the two maxima is estimated to

. Bulges in the h1 1 1i directions indicate a
be 1.36 A
possible diusion mechanism [23] where the oxide
ions move through a face of the surrounding Bi
tetrahedron to the octahedral cavity and then reentering a neighboring anion site. Bulges in the
[0 0 1] directions suggest another diusion path
where the oxide ions move along the c axis. This
feature was also conrmed in the MEM analysis of
the same sample measured at a dierent temperature 759 C. Previous neutron-powder-diraction
works [10,11] suggested some disorder of oxide
ions assuming four or ve split sites for an ideal 4c
position of the oxide ion as shown in Figs. 1b and
c, but failed to indicate the accurate positional

3
Fig. 3. Scattering amplitude distribution on (1 1 0) plane of d-Bi2 O3 at 778 C with white contours in the range from at 0.3 to 4.0 fm/A
3


(0.2 fm/A step). Oxide ions have a disorder along [1 1 1] directions. The possible conducting paths of the oxide ion are seen along
h0 0
1i and h1 1 1i directions.

M. Yashima, D. Ishimura / Chemical Physics Letters 378 (2003) 395399

disorder. In this work, we have successfully obtained the accurate disorder of oxide ions in dBi2 O3 by means of the MEM-based pattern tting
of neutron powder data. The above complicated
disorder of oxide ions would be responsible for the
fast oxide-ion conduction.

Acknowledgements
We acknowledge very much to Dr. K. Ohoyama and Mr. K. Nemoto for the use of the
HERMES diractometer, and to Mr. A. Sakai and
Mr. M. Mori for experimental assistance. Figs. 2
and 3 were drawn using the computer program
VE N U S developed by Dilanian and Izumi [22].
This work was partly supported by the Grant-inAid for Scientic Research (B) of The Ministry of
Education, Culture, Sports, Science and Technology of Japan.

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