Paper

Journal of the Ceramic Society of Japan 115 [11] 780–785 (2007)

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Shigeomi TAKAI, Takayuki SHINOHARA, Akinori HOSHIKAWA,ಓStefanus HARJO,ಓKenichi OIKAWA,ಓಓ
Toru ISHIGAKI,ಓTakashi KAMIYAMAಓಓಓand Takao ESAKAí
Department of Materials Science, Faculty of Engineering, Tottori University, 4–101, Koyamacho-Minami, Tottori 680–0945
Neutron Science Research Center, JAERI, Tokai-mura, Naka-gun, Ibaraki 319–1195
Center for Proton Accelerator Facility, JAERI, Tokai-mura, Naka-gun, Ibaraki 319–1195

Institute of Materials Structure Science, High Energy Accelerator Research Organization, 1–1, Oho, Tsukuba, Ibaraki 305–0801

Powder neutron diffraction experiments with Rietveld analyses were carried out on pure and Ta-substituted
Zn2TiO4 at room temperature to investigate the defect structure together with the oxide ion conduction mechan-
ism. The refined structure of pure-Zn2TiO4 agreed well with the previously reported inverse spinel-type structure
with cubic symmetry. For Zn2
x2Ti1
xTaxO4 solid solutions of cubic phase, the tantalum substitution as well as
the vacancy formation was made at the octahedral cation site, while the tetrahedral cation site was occupied by
zinc ions without any significant deficiency. Essentially the similar results were attained in the tetragonal phase
obtained by long-term annealing. By evaluating the occupation factors of tentatively introduced oxide ion inter-
stitials at various positions, oxide ion conduction was supposed to be made with the interstitialcy diffusion
mechanism, where displacement of a regular oxide ion toward the cation vacancy enabled the migration of other
oxide ions through the oxide ion vacancy at which the displaced oxide ion had been initially.

Received July 27,2007;Accepted Septmber 20,2007

Key-words : Neutron diffraction, Inverse spinel, Crystal structure, Defect, Oxide ion, Ionic conductivity, Inter-
stitialcy

1. Introduction phase; the tetragonal single phase can be obtained without

Zn2TiO4 with the inverse spinel-type structure is known as a
based material of oxide ion conductors Zn2
x2Ti1
xTaxO4 2
10
3 Scm
1 at 1000 C for x0.35.1,2 In that case, cation
vacancies, as expected in the nominal chemical formula, were
estimated to be formed due to the charge compensation from
the powder density measurements. Very few systems, e.g.
apatite-type structured compounds, have been reported as the
cation-vacancy-enhanced oxide ion conductions.3–6 Compar-
ing with most oxide ion conductors in which oxide ion vacan-
cies play an important roll for the ionic diffusion, the conduc-
tion mechanism was thought to be quite different from the
typical vacancy diffusion process, because this type of substi-
tution does not increase the number of oxide ion vacancies,
but the cation site vacancies. It is much more interesting that
oxide ions in the spinel-type structure compose the cubic
closest packed configuration in the present system.7 There-
fore, a simple oxide ion migration is unlikely to occur by inter-
stitial diffusion mechanism in a channel structure as the
apatite-type compounds. However, we have obtained very
little structural information about this solid solution to evalu-
ate the conduction; it has been still uncertain even where the
tantalum ions or cation vacancies are.
As to Ta-substituted oxide of Zn2
x2Ti1
xTaxO4, cubic
Fd 3̃m and tetragonal phases P 4122 or P 4322 have been
reported.8–13 The latter structure is derived from the former
with ordering of the two types of octahedral cations. The cell
relations between these phases are expressed as atac 2
and ctac, where the subscripts are the abbreviations of
tetragonal and cubic phases. While the tetragonal phase is
obtained even for Zn2TiO4 x0 by annealing the cubic-
phased sample at intermediate temperatures c.a. 450 C,
tantalum substitution facilitates formation of the tetragonal
í
Corresponding author; E-mail address: esaka
chem.tottori-u.ac.jp
T. Esaka
780
heat-treatment for x0.6.14 This tetragonal phase also
represents the oxide ion conduction with a slight higher
electric conductivity.
In the present study, neutron diffraction experiments were
carried out to determine the precise structure including the
defect structure, and to clarify the conduction mechanisms of
the Ta-substituted Zn2TiO4 solid solutions.
2. Experimental
Zn2TiO4 and Zn2
x2Ti1
xTaxO4 x0.10, 0.12, 0.14, 0.15,
0.16 and 0.60 samples were prepared by conventional solid
state reaction method. Stoichiomietric mixtures of ZnO,
TiO2 anatase type and Ta2O5 were fired at 1000 C, finely
crushed using mortar and paste, palletized under a hydrostatic
pressure of 200 MPa, and thereafter sintered again at 1200 C
for 10 h. To obtain the tetragonal phase in x0.15, the
sample powder with a cubic phase was annealed at 600 C
for 1000 h. Crystalline phases were confirmed by X-ray
diffraction Shimadzu XRD–6000, monochromatic CuKa
radiation.
Powder neutron diffraction data were collected by the TOF
neutron diffractometer Vega at the pulsed spallation neutron
facility KENS.15 The powder samples were charged in a
vanadium cylindrical cell of 8 mm in diameter and 30 mm in
height, which was set in the diffractometer. Diffracted neu-
trons were detected by PSDs installed in a backward bank with
2u ranging from 145 to 175 . The obtained diffraction data
were analyzed by means of the Rietveld refinement program
RIETAN-TN.16 The neutron scattering lengths used for the
refinements are 5.6, –3.37, 6.91 and 5.803 fm for zinc, titani-
um, tantalum and oxygen, respectively.17 X-ray diffraction
coupled with RIETAN–200018 was also employed only for
evaluation of tantalum distribution among the two octahedral
sites in the tetragonal phase. Interatomic distances and bond
angles were calculated by means of ORFFE.19
 Shigeomi TAKAI et al. Journal of the Ceramic Society of Japan
3. Results and discussion
3.1 Structures of cubic Zn2
x2Ti1
xTaxO4
Prior to the analysis of the Ta-substituted oxides, the struc-
ture of Zn2TiO4 with cubic symmetry was at first confirmed.
Figure 1 shows the measured and Rietveld-refinement patterns
of the neutron diffraction data for pure Zn2TiO4. Rietveld
analysis was carried out based on the inverse sinel-type
structure
Fd 3̃m, Z8 where tetrahedral cation sites
8a
are occupied by only zinc ions and octahedral ones
16d by
both zinc and titanium ions, as the conventional expression Zn
ZnTiO4. The finally converged structure parameters with
fairly good Rwp were listed on the topside in Table 1. The
equivalent temperature factor Beq of octahedral cation site
Fig. 1. Measured and refined neutron diffraction patterns of pure-
Zn2TiO 4.
: observed; solid line: calculated.
Table 1. Refined Structure Parameters of Pure and Tantalum Substituted Zn2TiO 4 of Cubic Phase
115 [11] 2007 781

16d seemed larger in comparison with that of tetrahedral
one
8a, which presumably indicates differences in ther-
mal vibration or the displacement from the average position
between zinc and titanium ions. Any better fit was not
attained assuming lower symmetry, which denied even the
short range ordering of octahedral cations.
Structure refinements were then carried out on the Ta-sub-
stituted system, Zn2
x2Ti1
xTaxO4 with cubic symmetry,
emphasizing the tantalum-substitution as well as the cation
vacancy formation positions. The measured and refined
diffraction patterns of the sample x0.15
Zn1.925Ti0.85
Ta0.15O4 were shown in Fig. 2
a. The occupation factors
of the tantalum ions initially introduced at the tetrahedral site
decreased down to negative during the Rietveld operation
whereas it remained positive for the octahedral site regardless
of the cation vacancy sites. This suggested that the tantalum
ion would occupy only the octahedral sites. Reliable factors
Rwp were compared among the next three typical vacancy
models considering the cation vacancy formation sites; Zn0.925
0.075Zn1.0Ti0.85Ta0.15O4, Zn0.96250.0375Zn0.9625Ti0.85Ta0.15
0.0375O4 and Zn1.0Zn0.925Ti0.85Ta0.150.075O4, where 
denotes a vacancy. The obtained Rwp values of 5.72, 4.95
and 4.52 for each configuration, respectively indicated that
the cation deficiency preferably occurs at the octahedral sites.
Moreover, when the distribution of zinc ions were refined with
fixing the titanium and tantalum ions to occupy the octahedral
sites, the converged occupation factors of tetrahedral and
octahedral sites were g4
Zn1.008 and g8
Zn, Ti, Ta
0.958, respectively, suggesting that cation vacancies were also
 782 Neutron Diffraction Study on the Defect Structure of Ta-Substituted Zn2TiO4 Oxide Ion Conductors
Fig. 2. Rietveld refinement neutron diffraction patterns of
a cubic
and
b tetragonal phases of Zn2
x2Ti1
xTa xO 4
x0.15. The
tetragonal phased sample was obtained by annealing the cubic one.
formed at the octahedral position.
For other compositions of cubic Zn2
x2Ti1
xTaxO4
x
0.10, 0.12, 0.14 and 0.16, the procedure above resulted in
essentially the similar defect structures. Namely both tan-
talum-substitution and the cation vacancy formation were
made at the octahedral site. Based on this defect structure
model, the finally refined structure parameters are summa-
rized in Table 1. Compositional dependences of the lattice
parameters and the interatomic distances between the central
cations and the neighboring oxide ions rM-O in oxygen tetrahe-
dron and octahedron are plotted in Fig. 3. The lattice
parameter and rM-O of the oxygen octahedron appeared to
grow with the tantalum substitution, while rM-O of the oxygen
tetrahedron does not vary or slightly decreases. Taking into
account the similarity of ionic radius between Ti4
74.5 pm
and Ta5
78 pm in the 6 fold coordination,20 the expansion
of oxygen octahedra was supposed to be due to the vacancy
formation with effective charge –2, or oxide ion displacement
discussed later.
3.2 Structure of tetragonal Zn2
x2Ti1
xTaxO4
Neutron diffraction pattern of annealed Zn2
x2Ti1
xTaxO4

x0.15 with tetragonal symmetry is represented in Fig. 2

b. Rietveld refinements were carried out based on the space
group P4322
Z4, in which the octahedral position sprits
into 4a and 4b sites and oxide ion into two general sites
8d,
while the tetrahedral site corresponds to 4c. From the prelimi-
nary refinements, the tetrahedral site
4c was estimated to be
exclusively occupied by zinc ions without deficiency. For the
octahedral cation site, 4a and 4b positions were converged to
be mainly occupied by zinc and titanium ions, respectively,
which was consistent with the previous report on the undoped
tetragonal-Zn2TiO4.13 Such ordering is also consistent with
the metal to oxygen bond lengths rM-Os in oxygen octahedra,
taking into account that the ionic radii of Zn2, Ti4 and Ta5
are 88.0, 74.5 and 78 pm, respectively; the interatomic dis-
tances from 4a cation site primarily occupied by Zn to the
oxide ion site
rM4a-O are larger than those from 4b site
mainly occupied by Ti or Ta
rM4b–O as listed in Table 2.
Since the variation of tantalum distribution between the two
octahedral sites
4a and 4b did not apparently improve the
reliable factors in the present neutron diffraction, a labo-
ratory-scale X-ray diffraction coupled with angle-dispersion
Fig. 3. Compositional dependence of
a lattice parameters,
b
bond lengths between tetrahedral cation to oxide ion and
c those
from octahedral cation to neighbouring oxide ions in cubic Zn2
x2
Ti1
xTa xO 4.
Rietveld program
RIETAN–2000 was used to estimate the
tantalum substitution site. As a result, tantalum ions were
found to occupy 4a site predominantly. The finally obtained
structure parameters are tabulated in Table 3, where tempera-
ture factors were applied as only isotropic ones. Since the total
occupancy of the octahedral sites are 0.978 and 0.947 for 4a
and 4b sites, respectively, cation vacancy was created at both
of the octahedral sites, and hence the defect structure govern-
ing the oxide ion conduction was supposed to resemble with
that of cubic phased sample.
The structure parameters with poorer fitting for the heavily
substituted composition x0.60 were comparatively listed in
Table 3. In this composition, octahedral 4a sites in addition to
4b were partly occupied by tantalum ions, while tetrahedral
sites were occupied by only zinc ions as same as the results of
x0.15. On the other hand, ordering of zinc and titanium
between 4a and 4b sites became moderate in comparison with
x0.15. Since the converged occupancy of the tetrahedral
position is larger than unity, slight amount of oxide ion vacan-
cy might be formed in addition to the cation vacancy at the
octahedral sites 4a and 4b. Nevertheless, the conduction
mechanism was estimated to be preserved up to this composi-
tion, assuming that the number of cation vacancy is much
larger than the oxide ion vacancy.
3.3 Oxide ion conduction mechanism
In the above section, the structures of Ta-substituted
Zn2TiO4 oxide ion conductors have been determined
emphasizing the position of the tantalum and the created
cation vacancy. If the behavior of the oxide ion neighboring
the cation vacancy is a key of the oxide ion diffusion, it would
be expedient that cation vacancies are preferably created at
 Shigeomi TAKAI et al. Journal of the Ceramic Society of Japan 115 [11] 2007 783

Table 2. Bond Lenghs
pm between Cation and Oxide Ion in Oxygen Polyhedra of Zn2
x2Ti1
xTaxO 4

Table 3. Refined Structure Parameters of Tetragonal Zn2
x2Ti1
xTaxO 4

octahedral sites rather than tetrahedral ones, because the

oxygen octahedra share the edges with each other while the
tetrahedra were isolated. Hitherto, the relationship between
cation deficiency and oxide ion conduction were still in
vague. Considering the oxide ion diffusion in the closely
packed sublattice without apparent vacancy, one might guess
the interstitialcy diffusion mechanism as observed in AgBr
system.21
,22
Namely, oxide ion is supposed to be pushed by
other mobile oxide ions into a relatively stable interstitial posi-
tion created by tantalum substitution. The created oxide ion
interstitial would in turn push other oxide ions or migrate
toward the newly formed oxide ion vacancy. This assumption
explains well the obvious activation energy decrease and the
ionic conduction increase with the tantalum substitution. In Fig. 4.
a Crystal structure of cubic Zn2
x2Ti1
xTaxO 4
x0.15.
Black, gray and white spheres denoted the tetragonal and octahedral
the present section, oxide ion displacement for the interstitial-
cations and oxide ions, respectively.
b Coordination view centered
cy diffusion is discussed in terms of the structure refinements. around the oxide ion with the fractional coordinates
0.87, 0.13,
A regular oxide ion coordinates with one tetrahedral and 0.13. Atomic displacements for all ions were represented by the ellip-
three octahedral cations in the spinel-type structure. Thermal soids with SCAL2 factor to be 1.54.
ellipsoid of an oxide ion derived from the anisotropic tempera-
ture factors in cubic Zn2x2Ti1xTaxO4
x0.15 seemed to
extend perpendicular to the tetrahedral cation site, or rather
toward the octahedral positions as illustrated in Fig. 4
b. introduced at various position and their calculated occupation
This corroborates the above assumption that the oxide ion factors obtained by Rietveld refinement were compared. In
would shift toward the cation vacancies at the octahedral site this process, the introduced oxide ion interstitial is to have a
for other oxide ions to migrate. In order to ensure the oxide fixed isotropic temperature factor Biso of 1.0104 pm2
1.0
ion displacement, oxide ion interstitials were tentatively Å2 under the constraint that the total number of oxide ions in
 784 Neutron Diffraction Study on the Defect Structure of Ta-Substituted Zn2TiO4 Oxide Ion Conductors
Fig. 5.
a  Occupation factors of the oxide ion interstitials located
on the line from an oxide ion to the tetrahedral site
triangles and to
the octahedral one
circles for cubic Zn2
x2Ti1
xTaxO4
x0.15.
Taking into account of the number of equivalent site, the plotted g

O i to the tetrahedral site was tripled for the comparison.
b g
O is
for pure Zn2TiO 4. The plotted symbols were compatible with those in

a.
c Schematic illustration of oxygen tetrahedron and octahedron
to indicate the introduced interstitial position.
a unit cell is preserved. In addition, isotropic temperature
factors were employed for all ions during this procedure, since
the slight variations of anisotropy for the regular ions would
critically contribute to the very small occupancy of intersti-
tials. Figure 5
a shows the converged occupation factors of
the oxide ion interstitials located on the line ranging from the
regular oxide ion position to the tetrahedral
 or octa-
hedral centers
 for cubic Zn2
x2Ti1
xTaxO4
x0.15.
On x-axis labeled as rOi-OrM-O, zero and unity correspond to
the regular oxide ion and the central cation positions in oxygen
polyhedra, respectively, which can be seen in the schematic
illustration of Fig. 5
c. Since the oxide ion interstitials con-
cerned are of Wyckoff notation 32e and 96g in the oxygen
tetrahedron
 and octahedron
, respectively, the plot-
ted occupancy in the oxygen octahedron
 was tripled
taking into account the number of equivalent site in a unit cell
in Fig. 5
a. In that case, the interstitial occupancy in octahe-
dron
 become positive in the region rOi-OrM-O0.5, while
that in the tetrahedron
 barely reached up to zero around
the cation site. This suggests that oxide ion would shift toward
the octahedral center rather than the tetrahedral one and oxide
ion diffusion should make use of the cation vacancy created
by the tantalum substitution. One might suspect that oxide ion
migration toward the cation vacancy surrounded by negatively
charged oxide ions would be difficult due to the repulsive
force, but in the closely packed configuration of oxide ions,
other direction for oxide ion displacement seems not to greatly
reduce the repulsive force.
On the other hand, Fig. 5
b shows the occupation factors
of oxide ion interstitials in pure Zn2TiO4
x0 obtained by
means of the similar procedure. In this composition, the calcu-
lated occupation factors of the assumed interstitials remained
negative entirely. Although it might be difficult to compare
exactly the absolute values of such small occupation factors of
the interstitials between the different samples, relative tenden-
cies of the positional dependence of the interstitial occupancy
can be still discussed. At higher rOi-OrM-O region, the intersti-
tial occupancy in the oxygen octahedron become larger in
comparison with that on tetrahedron for x0.15, whereas
that in octahedron does not exceed the tetrahedron for x0.
Therefore, enhancement of the occupation factor was essen-
tial in the oxygen octahedron observed for x0.15, which
ensured the assumption that cation vacancy is necessarily for
the oxide ion shift to make the interstitialcy diffusion.
In the tetragonal phase, the similar discussion seemed much
difficult due to the poorer refined data based on very small
occupancy of the introduced oxide ion interstitials. However,
since the cation vacancies were formed at the both octahedral
position of 4a and 4b, oxide ion displacements were also
expected to take place toward these octahedral sites. Further
precise structural study should be required to clarify the ionic
conduction properties of the tetragonal phase, e.g. the origin
of the sprit of dielectric relaxation phenomena or enhance-
ment of electric conductivity.14
The present study has estimated the tendency of the oxide
ion shift for the oxide ion diffusion in terms of the occupation
factors of the tentatively introduced oxide ion interstitials.
Although no significant discussion has been made for tetrago-
nal phase, regular oxide ion at least in the cubic phase is likely
to shift toward the oxygen octahedral center rather than tetra-
hedral one, suggesting that cation vacancy causes the inter-
stitalcy diffusion of oxide ions. Further precise conduction
mechanism might be provided from the ab initio calculation to
find the relatively stable position on which oxide ion would
migrate. In addition, nuclear density map synthesis via MEM
analyses or conventional Fourier methods based on the high
temperature neutron diffraction data would directly predict
the oxide ion conduction path. On the other hand, a different
approach to design the compound with controlled defect
structure might be valid to clarify the relationship between the
cation vacancy and oxide ion conduction. The present study
would be the first step of such a series of investigations.
4. Conclusion
The crystal structures of cubic and tetragonal Zn2
x2Ti1
x
TaxO4 were investigated by means of TOF neutron diffraction.
The cation vacancy formation accompanied by the tantalum-
substitution occurs at the octahedral site of the inverse spinel-
type structure for all the solid solutions. The calculated
occupancies of the tentatively introduced oxide ion interstitials
showed the positive values around the octahedral center posi-
tion, while they remained negative in the oxygen tetrahedron
for cubic phase of Ta-substituted compounds. This indicated
that the regular oxide ion would shift toward the center of the
oxygen octahedron, which would cause other oxide ions to
migrate.
Acknowledgements This work has been carried out in part
under the Visiting Researcher's Program of the KEK, and partial-
ly supported by a grant-in-aid from the Ministry of Education,
Science, Sports and Culture. Rietveld program for TOF neutron
 Shigeomi TAKAI et al. Journal of the Ceramic Society of Japan 115 [11] 2007 785

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