J O U R N A L O F M AT E R I A L S S C I E N C E : M AT E R I A L S I N E L E C T RO N I C S 1 4 ( 2 0 0 3 ) 1 4 9 1 5 6

Comparison of electronic structures of doped ZnS

and ZnO calculated by a rst-principle
pseudopotential method
YOJI IMAI, AKIO WATANABE
National Institute of Advanced Industrial Science and Technology (AIST), AIST Tsukuba
Central 5, Higashi 1-1, Tsukuba, Ibaraki 305-8565, Japan
ISAO SHIMONO
Hokkaido Industrial Technology Center, 397, Kikyo-cho, Hakodate, 041-0801, Japan
Email: imai_y@aist.go.jp

Electronic band calculations of doped and undoped ZnO and ZnS have been done using
density functional theory under the local density approximation so as to clarify the reason of
the difference in behaviors of doped ZnO and ZnS. The reason why the electrical conductivity
of ZnS is difcult to be increased by doping was discussed. In the case of doped ZnS, an
impurity level was generated at deep position below the bottom of the conduction band of
the host ZnS lattice and Fermi level was located at this impurity level. On the contrary, the
shape of the density of states curve and the band structures of doped and undoped ZnO are
alike with each other and the donor band is hybridized with the conduction band of the ZnO
host material. This seems to result in contribution of doped electrons to electrical current in
the case of doped ZnO.
# 2003 Kluwer Academic Publishers

1. Introduction 3610 2 O cm has been reported in Al-doped ZnS under

There has been increasing attention to the wide and direct
band gap semiconductor materials for blue and ultra-
violet optical devices. Among them, ZnO and ZnS are
promising because they are comprised of very abundant
elements and can be readily deposited as a thin lm by
several methods.
The crystal structures of both are related with each
other in that ZnO, wurtzite structure, can be considered
as two interpenetrating hexagonal close-packed lattices
of Zn and oxygen, while ZnS, zincblend structure, can be
considered as two interpenetrating face-centered cubic
(fcc) lattices. Both have a tetragonal arrangement of four
equidistant nearest neighbors. However, the behaviors of
those to the control of conduction type and conductivity
are different with each other.
ZnO has a direct bandgap of 3.4 eV at room
temperature [1] but is known to show n-type conduction
owing to its native donor defects such as oxygen
vacancy. Addition of a small amount of IIIa elements
impurities such as aluminum (Al) cause a marked
decrease in resistivity to about 3610 4 O cm [25]
and has been used as transparent conductive lms,
varistor, and solar cell window. On the other hand, ZnS, a
semiconductor with a direct bandgap of 3.7 eV [1], has
been investigated as a light emitting diode (LED) and
there has been a difculty in growing low resistivity ZnS
by conventionally used growth methods. Typically, lm
resistivities of ZnS doped by IIIa elements are in the
range 1100 O cm [68], though resistivity as low as
09574522 # 2003 Kluwer Academic Publishers
the very limited deposition conditions [9].
Since Al-doped ZnO shows negative temperature
dependence of the conductivity [10] and Al-doped ZnS
shows positive dependence [7], one may consider that the
marked difference in resistivity is related with the so-
called Mott transition, metalinsulator transition accom-
panying an abrupt rise in conductivity as a particular
parameter is varied such as impurity concentration.
However, the screening constant in the electron-hole pair
(exciton) in ZnO and ZnS lattice must not be so different
since it is determined by m* =es, where es is the dielectric
constant of the lattice (ZnO or ZnS) and m* is the
effective electron mass in the lattice in case the electron
concentration, n, is xed. Their numerical values are as
follows; m* =m0 is 0.28 for ZnO and 0.34 for ZnS, where
m0 and m* is the free electron mass and the effective
electron mass in the lattice [1]. es =e0 is 8.75 for ZnO and
8.5 for ZnS, where e0 and es is the dielectric constant of
free space and the lattice [1].
Therefore, simple models do not seem to be able to
account fully for the big difference in conductivity of
doped ZnO and ZnS. This state of affairs has provided
the motivation for the present work, the purpose of which
is to calculate the electronic structures of doped ZnO and
ZnS so as to understand the difference. The results of the
rst-principle calculation of the doped ZnO and ZnS will
be shown in the present paper.
The paper is organized as follows: in the next section,
the calculation method is described. The results of the
149
calculation are presented and discussed in Section 3.
Finally, the summary of the results are presented in the
last section.
2. Methods
The calculation has been done using Cambridge serial
total energy package (CASTEP) developed by Payne et
al. [11], which is a rst-principle pseudopotential method
based on the density-functional theory (DFT) describing
the electronelectron interaction, a pseudopotential
description of the electroncore interaction, and a
plane-wave expansion of the wavefunctions. This code
has been successfully applied for the calculations of the
electronic structures of non-stoichiometric or doped iron-
disilicides [12, 13]. The pseudopotential used is the
ultrasoft pseudopotential generated by the scheme of
Vanderbilt [14] which is bundled in the Cerius2 graphical
user interface1. The Zn3d (and Ga3d) states were
explicitly treated as a part of the valence. Local density
approximation (LDA) with generalized gradient
correction (generalized-gradient-corrected local density
approximation; GGA) [15] was used for the method of
approximation to the exchange-correlation term of the
DFT.
As for the crystal structures for calculation, the lattice
parameters and atomic arrangements of undoped ZnO
and ZnS have been collected from the literatures [16, 17].
Since the zincblend structure (cubic ZnS) results from
the diamond structure when Zn atoms are placed on one
fcc lattice and S atoms on the other fcc lattice, primitive
cell of ZnS contains one Zn atom and one S atom
(Zn1 S1 ). On the contrary, wurtzite structure (ZnO)
derives from the hexagonal closed packed structure
consisting of two interpenetrating simple hexagonal
lattice. Therefore, the primitive cell of wurtzite structure
consists of two Zn atoms and two O atoms (Zn2 O2 ).
As a doping element for calculations, we adopted
gallium (Ga) because it is widely used as a doping
element of ZnS for LED use. Preliminary calculations
using a different doping element, namely Al, did not
bring about big difference on the results. We constructed
a supercell by doubling, triplicating, quadruplicating, . . .
each primitive translation vector of the primitive cells of
undoped Zn2 O2 or Zn1 S1 to make cells of Zn16 O16 ,
Zn8 S8 , Zn54 O54 , Zn27 S27 , Zn64 S64 , and so on. Then,
replacing one of the zinc atoms by an impurity atom (Ga)
produced the model of doped ZnO or ZnS. That is, the
calculations of the doped ZnO or ZnS were done for
Zn53 Ga1 O54 or Zn26 Ga1 S27 , and so on. No relaxation for
substitution of the atom has been considered.
Calculations on ZnO or ZnS for more dilutely doped
states could not be done because of the limited
computational resources.
Expansion of the valence electronic wavefunctions in
a plane-wave basis set up to an energy cutoff of 250 eV. It
has been conrmed preliminarily that the pseudopoten-
tial used here is soft enough to obtain well-converged
shape of the DOS curves and the relative position of the
Fermi level in the DOS curves if the above value of an
energy cutoff is used.
The DOS curves were obtained by broadening discrete
energy levels using the Gaussian smearing function of
150
0.07 eV full-width at half-maximum (FWHM) on a grid
of k-points generated by Monkhorst-Packe scheme [18].
In the case of Zn27 S27 or Zn26 Ga1 S27 , the spacing of the
sampled k-points in the reciprocal space was 0:4 nm 1 ,
which makes fourteen k-points sampled from the
irreducible part of the Brillouin zone. However, we are
obliged to use the spacing of 0:5 nm 1 , which makes
four k-points sampled in case of Zn54 O54 or Zn53 Ga1 O54 .
Only one k-point could be sampled in case of
Zn63 Ga1 S64 .
All the angular momentum projection (s, p, d, . . .) on
all the atoms are also performed to give a partial density
of states (PDOS). Calculations of the band structure (BS)
along several high-symmetry lines in the Brillouin zone
have also been conducted.
3. Results and discussion
At rst, we conducted the calculations for undoped ZnO
and ZnS using their primitive cells (Zn2 O2 and Zn1 S1 ,
respectively) so as to compare the present calculations
with the previous ones. The results are given in Fig. 1(a)
and (b). Those results are in good agreement with the
previous calculations for ZnO, using empirical pseudo-
potential method [19], and for ZnS using modied
orthogonalized plane wave method [20].
Both have similar features. The valence bands extend
down to about 10 eV below the Fermi level, shown by the
broken lines in the total DOS curves (located at 4.0 eV
for ZnO and at 4.5 eV for ZnS), and can be divided into
two main parts. The conduction bands are rather gently-
sloping.
Partial DOS of Zn4s, Zn4p, Zn3d, S4s, S3p, O3s, and
O2p components have also been calculated. The results
are roughly shown in Fig. 1(a) and (b) by arrows which
present the range of the main contribution of each PDOS
to the total DOS. The deepest valence band is mainly
composed of O3s or S4s orbital. The upper valence band
is divided still more into two parts; a peak with high DOS
values which is located at about 2.5 eV and a rather
gently-sloping part with relatively low DOS value. The
former is composed of Zn3d orbital and the latter is of
Zn4s, 4p and O2p or S3p orbitals. The conduction band is
composed of Zn4s, Zn4p and O2p or S3p.
It should be noted that O2p orbital in ZnO is rather
sharp and not broadened by overlapping of wavefunc-
tions with other orbitals, compared to the case of S3p
orbital in ZnS. This implies that electrons from O2p
orbital are bounded at the oxygen atom and not
contribute so much to the bottom of the conduction
band. This can be expressed numerically by the Mulliken
population analysis [21], presented by Table I. The net
charge of Zn in ZnO is 0.82 whereas that in ZnS is 0.5.
This suggests that bond in ZnO is more ionic than that in
ZnS. Bond overlap population between Zn and O is much
smaller than that between Zn and S.
The detailed representation for the partial DOS near
their Fermi level are presented in Fig. 2(a) and (b). As is
clearly seen, the uppermost valence bands are mainly
composed of S3p or O2p whereas the lowermost
conduction bands are of Zn4s and Zn4p in ZnO and
Zn4s, Zn4p, S3p, and S4s in ZnS. Contribution from O2p
 T A B L E I Mulliken population analysis of undoped ZnO and ZnS

(a) ZnO Partial population Atomic Net charge

population in e units

3s 2p
O 1.85 4.97 6.82 0.82
4s 3p 3d
Zn 0.62 0.59 9.97 11.18 0.82

Bond overlap population Length (nm)

O-Zn 1.09 1.975

O-Zn 0.31 1.988

(b) ZnS Partial population Atomic Net charge

population in e units

4s 3p
S 1.82 4.68 6.50 0.50
4s 3p 3d
Zn 0.84 0.68 9.98 11.50 0.50

Bond overlap population Length (nm)

S-Zn 1.86 2.331

2.2 eV for ZnS. This calculated value for ZnS is about

Figure 1 Total densities of states, left, and band structures, right, of
Zn2 O2 in wurtzite structure, (a), and of Zn1 S1 in zincblend structure,
(b). Broken lines in these and succeeding gures show the positions of
Fermi level. Units in the DOS curves are electrons/(cell eV).
and O3s to the lowermost part of the conduction band of
ZnO is scarcely observed.
The calculated direct band gap is 1.0 eV for ZnO and
60% of the measured value (3.7 eV) as is often
experienced in the LDA calculation, while that for ZnO
is as small as 30% of the measured value (3.4 eV) though
the reason of the discrepancy is not claried.
When one of the eight atoms of Zn in Zn8 S8 is
replaced by an impurity atom (Ga), that is, when a
composition of the unit cell is Zn7 Ga1 S8 , the Fermi level
shifts upward into the conduction band as shown in Fig.
3. It should be noted that donor band is not resolved and
is hybridized with the conduction band of the ZnS host
materials. This might be due to the fact that the present
cell with a GaGa distance of 0.76 nm is smaller than the
exciton wavefunctions of the shallow state which can be
roughly estimated to extend up to a* es =e0
m0 =m* aB 1:33 nm where aB is the Bohr radius.
However, this is not the case when concentration of
doped element is smaller. The BS and the DOS of
Zn26 Ga1 S27 are shown in Fig. 4, where one of the twenty-
seven atoms of Zn in Zn27 S27 is replaced by an impurity
atom (Ga). Here, BS along high-symmetry lines in the
Brillouin zone is shown by the right gure and the total
DOS is shown by the middle gure. Partial DOS of Ga is
shown by the left gure. As shown by the middle gure
representing the total DOS, the Fermi level exists isolated
from the bottom of the conduction band, which is
different from the previous case of Zn7 Ga1 S8 . For
comparison, the total DOS and the BS of the undoped
Zn27 S27 are shown in Fig. 5. The isolated energy level of
Zn26 Ga1 S27 derives from the 244th band of Zn27 S27 .
Fermi level is located just on this band. This new 245th
band of Zn26 Ga1 S27 is composed mainly of Ga 4s orbital
and the atomic orbitals from neighboring S atoms, as
well as neighboring Zn atoms. The left gure in Fig. 4.
which shows the partial DOS of Ga atom, indicates that
the energy of Ga4s is located at this level. Among the
whole amount of contribution to the Fermi level, the
contribution of each atomic orbital, calculated from the
local DOS values of atomic orbitals of all atoms, is as
151
Figure 2 (a) Total density of states (DOS) and Zn 4s, 4p, 3d and O 3s, 2p partial DOS of Zn2 O2 in wurtzite structure. (b) Total DOS and Zn 4s, 4p, 3d
and S 4s, 3p partial DOS of ZnS in zincblend structure. Units in this and succeeding DOS gures are electrons/(cell eV) for total DOS and electrons/
(atom eV) for partial DOS.
follows; 27% from Ga4s, 1% from Ga4p, 21% from the
S3p orbital of the four nearest-neighboring S atoms (Ga
S distance; 0.233 nm), 3% from the S4s orbital of them,
10% from the Zn4s of the twelve nearest-neighboring Zn
atoms (GaZn distance; 0.381 nm), and 10% from the
Zn4p of them. Contribution from orbitals of other 37
atoms (23 of S and 14 of Zn) is less than 30% when
totaled. Thus, orbitals of doped Ga in ZnS lattice interact
mainly with those of the nearest four S atoms in the host
lattice as well as those of the nearest twelve Zn atoms and
make a new energy band.
As the atomic sites of the doped Ga are randomly
distributed in the host ZnS lattice, so-called Anderson
localization [22] of the wavefunction may proceed and
the electronic energy might not be presented by the
continuous curves, such as shown by the middle of Fig. 4.
However, the present calculation could clearly show the
generation of the impurity levels below the bottom of the
conduction band of the host ZnS lattice. The energy
difference of the Fermi energy and the bottom of the
conduction band (the 246th band) is about 0.6 eV at G,
17% of the calculated gap between the 243th and the
246th band. Thus, the Fermi level is located rather deep
152
and can act as electron trap. Contribution of the electrons
at this level to the electric current would be small.
Therefore, doped ZnS is considered to be not metallic.
The same could be concluded using the model of more
dilutely doped Zn63 Ga1 S64 , though not shown here, and
the congergence with respect to dilution of dopants could
be conrmed.
The results of the doped ZnO are quite different. The
results for Zn53 Ga1 O54 are presented in Fig. 6. For
comparison, results for undoped Zn54 O54 are given in
Fig. 7. Though splitting of the degenerate states by Ga
doping (for example, the 487th band and the 488th band
at A0 0 0.5 and M0 0.5 0 and the 488th band and the
489th band at G0 0 0) could be observed, the shape of
the DOS and BS are not varied so much from those of
undoped ZnO. The donor band is not resolved and it
hybridizes with the conduction band of the ZnO host
lattice. Though the convergence with respect to dilution
of dopants could not be conrmed because of limitation
of the computational resources used, it is unlikely to
affect the present results signicantly, judging from the
following considerations: (1) The spatial overlap (SO) of
the exciton wavefunction would not be different so much

Figure 3 Total density of states and Ga 4s, 4p partial densities of states
of Zn7 Ga1 S8 .
for ZnO and ZnS since SO can be estimated to extend up
to a* eS =e0 m0 =m* aB and a* for ZnS and ZnO do
not differ so much if calculated using the values stated
above; (2) Convergence with respect to dilution is
conrmed for doped Zn27 S27 as described above; (3)
The average separation distance between doped Ga
atoms in Zn53 Ga1 O54 is 1.09 nm, which is larger than that
of Zn26 Ga1 S27 of 1.02 nm. Therefore, it would be
unreasonable to attribute the reason of the unresolved
Figure 4 Total density of states, middle, Ga 4s, 4p partial densities of states, left, and band structures (BS), right, of Zn26 Ga1 S27 . Plotted in the BS
gures in this and succeeding gures are the numbers which express the order countered from the bottom of the valence band. It should be noted that
Zn3d and Ga3d states are explicitly treated as a part of the valence.
donor level of Zn53 Ga1 O54 to too short distance between
doped atoms in Zn53 Ga1 O54 .
The Ga partial DOS curve, shown left, indicates that
the energy of Ga 4s orbitals are broadened, which is
different from the case of Zn26 Ga1 S27 . This suggests that
electrons from the doped Ga atoms occupy the conduction
band of the host ZnO lattice and contribute to the electric
current, resulting in metallic behaviors of the doped ZnO.
This is contrary to the case of doped ZnS where orbitals
due to excess electrons from Ga in ZnS lattice interact
with S4s or S3p orbitals in the host lattice and make a new
energy band which can act as an electron trap, resulting in
little contribution of electrons to the electric current.
Thus, the present calculations could clearly show the
difference of the electronic structures of doped ZnO and
doped ZnS which would cause the difference in the
conductivity of doped ZnO and ZnS. One may consider
that this difference is caused by the difference in the
crystal structure. As stated in the Introduction, ZnO and
ZnS have different symmetry. This structural difference
may cause the different character of doped element.
Therefore, additional calculations for hexagonal ZnS and
hypothetical cubic ZnO have been done.
As for the hexagonal ZnS, crystal data of high
temperature phase (a 0.3823 nm, c 0.6261 nm) [23]
have been used. For the hypothetical cubic ZnO, lattice
constant of 0.4567 nm was assumed so that the volumes
per ZnO are the same as that of real hexagonal
ZnO( 0:0238 nm3 ).
The results for the hypothetical cubic ZnO (Ga-dope,
Zn26 Ga1 O27 ) are presented in Fig. 8. The DOS curve is
alike that of Zn53 Ga1 O54 and Ga4s partial DOS extend
well above the Fermi energy, indicating metallic
behavior. On the contrary, the DOS curve of
Zn53 Ga1 S54 in hexagonal modication, shown in Fig.
9, is like that of Zn26 Ga1 S27 in cubic zincblend structure.
153

Figure 5 Total density of states, left, and band structures, right, of
Zn27 S27 in zincblend structure.
Ga4s partial DOS is energetically localized. Thus, the
different behaviors between ZnO and ZnS are not due to
the crystal structure but must be due to the anion of the
host material.
As described above, O2p and O3s orbital do not
contribute so much to the bottom of the conduction band
of ZnO. Orbitals introduced by doping of Ga atom into
the ZnO host lattice do not interact with orbitals from
oxygen atoms since the energy levels of Ga 4s and O3s or
O2p are so much different. They can hybridize only with
orbitals derived from atomic orbitals of Zn and make
Figure 6 Total density of states, middle, Ga 4s, 4p partial densities of states, left, and band structure, right, of Zn53 Ga1 O54 .
154
conduction bands. Thus, excess electrons introduced by
doping enter into these conduction bands and are able to
move almost freely, resulting in contribution to electric
conduction. On the other hand, orbitals introduced by
doping into ZnS do hybridize with S3p and S4s orbital
and make a new energy band well below the conduction
band. Excess electrons introduced by doping are trapped
at this level.
It should be stated here that the present speculation is
based on the electronic structure of doped materials with
an assumed concentration of dopants. Numerous
attempts to understand the maximum doping limits in
semiconductors from a different point of view have been
explored such as self-compensation theory [24].
According to this, the donor impurities doped in ZnS
introduce Zn vacancies which act as acceptors and hence
they are easily compensated. This theory states that the
formation of charged native defects becomes more
pronounced as the band-gap increase. One may consider
that this is the reason for the ineffectiveness of doping of
ZnS to improve conductivity. However, this theory
seems not to be sufcient to explain the different
behavior of doped ZnO and ZnS since both have nearly
the same band gap and the formation of charged native
defects would not differ in both cases.
Recent theory for doping limit in semiconductors in
terms of the amphoteric defect model [25] is attractive
since this explains experimentally observed trends in
carrier saturation in semiconductors. This adopts the idea
of the position of the Fermi level stabilization energy
deduced from the empirically determined Fermi energy
position in a heavily damaged semiconductor and
Schottky barrier height. The relation of this model and
the quantum dynamical calculations of doped system
such as discussed here are left to future study.
Figure 7 Total density of states, left, and band structure, right, of
Zn54 O54 .
Figure 8 Total density of states and Ga4s,4p partial densities of states
of Zn26 Ga1 O27 with a hypothetical zincblend type structure.
4. Conclusions
The reason why the electric conductivity of ZnS is
difcult to be increased by doping compared to the case
of ZnO was discussed from the electronic band
calculations. In the case of doped ZnS, an impurity
level was generated at deep position below the bottom of
the conduction band of the host ZnS lattice and the Fermi
Figure 9 Total density of states and Ga4s,4p partial densities of states
of Zn53 Ga1 S54 with a wurtzite type structure.
level was located at this impurity level. The contribution
of the electrons at this level to the electric current was
considered to be small. On the contrary, the shape of the
curve of the density of states and the band structure of
doped and undoped ZnO are alike with each other and the
donor band is hybridized with the conduction band of the
ZnO host lattice. This seems to result in a contribution of
doped electrons to increased electric current in doped
ZnO.
Acknowledgments
The authors would like to express their sincere gratitude to
Dr. Masaaki Sugie of the National Institute of Advanced
Industrial Science and Technology, Japan (AIST) for his
kind technical assistance during the calculations. They are
also grateful to TACC (Tsukuba Advanced Computing
Center), AIST, for the nancial support.
Notes
1. Cerius2 is a trademark of Accelrys Inc.
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