.

_^ ^ „ OCT 14 1975

175118 '- c
y NSRDS-NBS 49

Transition Metal Oxides

U.S. DEPARTMENT OF COMMERCE/National Bureau of Standards

NSRDS
Ice dat*

Crystal Chemistry, Phase

Transition and Related Aspects

 NATIONAL BUREAU OF STANDARDS

The National Bureau of Standards was established by an act of Congress March 3, 1901.
1

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Mil Bureau of Standards
)V 1 1974
p
&
5aSo transition Metal Oxides
U573
1
Crystal Chemistry, Phase Transition
Iq-i
and Related Aspects

C. N. R. Rao and G. V. Subba Rao

Department of Chemistry
Indian Institute of Technology
Kanpur-16, India

t>
N$RD6-KB5 »o. ^

NSRDS

U.S. DEPARTMENT OF COMMERCE, Frederick B. Dent, Secretary .OVAJTIO/u

W.*5. NATIONAL BUREAU OF STANDARDS, Richard W. Roberts, Director

» * %

Issued June 1974

 Library of Congress Catalog Number: 73-600267

NSRDS-NBS 49
Nat. Stand. Ref. Data Ser., Nat. Bur. Stand. (U.S.), 49, 138 pages (June 1974)
CODEN: NSRDAP
© 1974 by the Secretary of Commerce on Behalf of the United States Government

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1974

For sale by the Superintendent of Documents, U.S. Government Printing Office

Washington, D.C. 20402 (Order by SD Catalog No. C13. 48:49) Price SI. 70
Stock Number 0303-01190
 Foreword

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Richard W. Roberts, Director

iii
 Preface

As part of our program in presenting critical reviews of phase transitions of inorganic solids,*
we have surveyed the phase equilibria, crystal chemistry, and phase transitions of transition metal
oxides in detail. Transition metal oxides form an interesting series of materials for the study of a
variety of solid state phenomena, many of which arise from the presence of different d-electron
configurations. Crystal structure transformations in several of the transition metal oxides are ac-
companied by significant changes in electrical, magnetic, and other properties and we have, there-
fore, briefly presented the recent data on the various properties of these oxides. We trust that this
monograph will not only serve as a source of valuable information, but also provide a fascinating
case history of an important class of solid state materials.
In this paper, we have covered the binary oxides of 3d-, 4 d-, and 5d-transition metals with
important references to the literature up to 1973.
The authors acknowledge the support by the National Bureau of Standards through their
Special International Programs. The authors’ thanks are due to G. Rama Rao for his assistance in
the preparation of the manuscript.

* The first monograph of this series is on binary halides by C. N. R. Rao and M. Natarajan, NSRDS-NBS-41, 1972. (Supported by NBS Project G-77).

IV
 Contents
Page
Foreword iii

Preface iv
Symbols and abbreviations 1
Introduction 1

I. Oxides of 3 d transition elements

1. Scandium oxide 7
2. Titanium oxides 9
3. Vanadium oxides 31
10. Chromium oxides
4. 50
5. Manganese oxides 54
6. Iron oxides 60
7. Cobalt oxides 69
8. Nickel oxides 75
9. Copper oxides 79
Zinc oxides 81
II. Oxides of 4 d transition elements
10.
1. Yttrium oxides 83
2. Zirconium oxides 85
3. Niobium oxides 92
4. Molybdenum oxides 99
5. Technitium oxides 102
6. Ruthenium oxides 103
7. Rhodium oxides 104
8. Palladium oxide 105
9.
10. Silver oxides 106
Cadmium oxides 107
III. Oxides of 5 d transition elements
1. Lanthanum oxides 109
2. Hafnium oxides Ill
3. Tantalum oxides 113
4. Tungsten oxides 117
5. Rhenium oxides 123
6. Osmium oxides 125
7. Iridium oxides 127
8. Platinum oxides 127
9. Gold oxides 128
Mercury oxides 129
IV. Some recent studies 130

v
... .
 Transition Metal Oxides

Crystal Chemistry, Phase Transitions and Related Aspects

C. N. R. Rao and G. V. Subba Rao

A survey is made of the data describing the thermodynamics of phase equilibria, crystal
chemistry and phase transformations of binary oxides of 3 d, id, and 5 d transition metals. Changes
in electrical, magnetic, and other properties which accompany phase transitions are discussed-
Nearly complete coverage of the literature is provided up to 1973.

Key words: Crystal structure transformations; critical data, transition metal oxides; electronic
properties; phase equilibria; phase transitions; magnetic properties.

Symbols and Abbreviations T — Superconducting transition temperature

sc

T m — ransition temperature (Morin

AFMR —Anti -Ferromagnetic Resonance T
transition)
—Transition temperature
APW —Augmented Plane Wave t

—Temperature °C (degree Celsius)

B — Crystal Racah parameter t in
TEC —Thermal Expansion Coefficient
field
bp —boiling point TGA— Thermo Gravimetric Analysis
C — Heat capacity at constant pressure
p
—Thermoehemical = 4.1840 Joules A V—Volume change
eal
C — Heat capacity at constant volume
calorie
— ongitudinal sound-wave velocity
cl
v

CS — Crystallographic shear — Shear sound-wave velocity

vs

DTA—Differential Thermal Analvsis UHF —Ultra High Frequency

d—Density
W—Watt
a — Seebeck
E — Energy of activation angle
coefficient;
of* — rohlich polaron coupling constant
Ef — ermi
ft

a — Thermal diffusivitv (x/C

level
E — Band gap td pd)
g
— electronic charge —Angle
/3

7 — Angle
e
EMF —Electro Motive Force
ESCA — Electron Spectroscopy Chemical for
7g Griineisen constant
Analysis —Dielectric constant
e

ESR — Electron Spin Resonance do — Debye temperature

AG — Gibbs energy change
free
— Thermal conductivity
k

H—Enthalpy Mb — ohr magneton

AH—Enthalpy change Md — mobility
rift

h —hours Mh — mobility
all

k — Knight shift
— Resistivity
p

k — Boltzmann constant Ap — Jump in resistivity

a — Conductivity
LCAO —Linear Combination of Atomic Orbitals
M — Spontaneous magnetization X — Magnetic susceptibility
Xm — Molar magnetic susceptibility
0
M — Saturation magnetization
s
Z — Number of molecules per unit
min — minutes cell

m— electron mass
free
m* — Effective electron mass Introduction
mp —melting point
m —Effective polaron mass
p
*
Transition metal oxides probably form one of the
NMR — Nuclear Magnetic Resonance
n — Refractive index most interesting class of solids, exhibiting a variety

n — number of charge
c carriers of novel properties These properties un-
[1-5]. 1
P— Pressure: atm = 101325 Nm~ =
1 2
doubtedly arise from the outer d electrons of the
-2
1013250 dyn cm transition metal ions. These d electrons can neither
P — Partial pressure of oxygen
02
Rh— Hall constant
be described by a collective electron model (as in

AS— Entropy change the case of s and p electrons) nor by a localized

T— Temperature degrees Kelvin
in electron model (as in the case of / electrons which
Tc — Curie temperature
Tn — Neel temperature Figures in brackets indicate the literature references on page that appear
1

at the end of each section.

1
are tightly bound to the nuclei). Outer d electrons erally, when compounds deviate from stoichiometry,
are not screened from the neighboring atoms by the an increase in density indicates interstitials and a
outer core electrons, and the intermediate character decrease denotes vacancies. Electrical conductivity
of these electrons shows itself in terms of localized of oxides is markedly affected by deviations from
electron behavior in some oxides and collective elec- stoichiometry. Similarly, foreign metal ions, present
tron behavior in some others; in a few instances, as impurities or doped intentionally, would also
both kinds of d electrons can exist simultaneously. cause marked changes in the properties of metal
In recent years, the field of transition metal oxides oxides. There are many instances where foreign im-
has been a subject of intensive study by chemists purities stabilize a particular phase. Thus, sulfate
and others interested in solid state materials. A ion stabilizes the anatase phase of Ti 0 2 while Fe +3
study of the properties of these oxides not only stabilizes the high temperature pseudobrookite phase

serves as one of the best introductions to solid state of Ti 3 0 6 .

chemistry and materials science, but also provides a Transition metal oxides exhibit a wide range of
wealthy source of fascinating research problems for magnetic properties: TiCh, ZrC>2, V2O6, and M0O3
experimental and theoretical investigations. are diamagnetic; metallic TiO and Re03 are Pauli-
Transition metal oxides of the general formulae paramagnetic; VO2, Nb02, and Ti 2 03 are paramag-
MO, M2O3, M0 2, M2O5, MO3, M„0 2 n-1, MrAn+i are netic; MnO, CoO, NiO, V2O3 and O2O3 are anti-

known to exist. The nature of bonding in these ferromagnetic with well-defined Neel temperatures;
oxides varies from purely ionic (e.g., NiO, CoO) to Mns0 4 and Fes0 4 are ferrimagnetic; OO2 is

purely covalent (e.g., 0 s 0 Ru 04, 4 ); metallic bonding ferromagnetic. The magnetic properties of binary
is seen in oxides like TiO, NbO, and Re03. The oxides have been reviewed by Goodenough and
crystal structure of transition metal oxides varies others [
1, 3 , 4, 8].

from cubic to triclinic symmetry. Simple binary Transition metal oxides show a spectacular range
oxides of the composition, MO, generally possess of values of electrical conductivity. At one extreme
the rock-salt structure, while the dioxides, M0 2, we have the insulator behavior as typified by MnO
possess fluorite, rutile, distorted rutile or even more (<r« 10
-15 _1
£2 cm -1 ), and at the other extreme we have
complex structures; many sesquioxides, M2O3, pos- oxides like Re03, Cr 0 2 Ru02, TiO, and NbO with
,

sess the corundum structure. Transition metals form metallic conductivities (fig. 1 ). In between these
important ternary oxides like perovskites, spinels, extremes we have a large number of oxide semicon-
bronzes, and garnets. Many
of these oxides show ductors. The mechanism of conduction in such semi-
interesting phase transitions from one crystal struc- conducting oxidesmay involve the hopping of charge
ture to another accompanied by changes in magnetic, carriers Nb205) or the excitation from the
(as in
electrical, and other properties. valence band to the conduction band (as in SrTiOs
Many transition metal oxides show a wide range and Sn02). Of special interest are the transition
of non-stoichiometry as in the case of oxides of metal oxides which exhibit insulator (or semicon-
titanium, vanadium, iron, and niobium. Deviations
from stoichiometry can be due to cation deficiency
(as in Fes 0 4) or anion deficiency (as in ZnO). Large
deviations from stoichiometry cause marked changes
in unit cell dimensions or in crystal structure. In
many oxides, the defects are so highly ordered
that we cannot really consider them as ordinary
defect solids TiO, NbO). Similarly, many
(e.g.,

oxide phases which may appear as nonstoichiometric

could truly be stoichiometric compositions (with
narrow ranges of homogeneity) resulting from dif-
ferent modes of sharing of the metal-oxygen poly-
hedra (e.g., Ti n 0 2 „-i and similar Magneli phases)
[
6 7 ]. In oxides where there are wide ranges of
,

homogeneity lattice constants vary with composi-

tion; a typical case is that of TiO* ( 0.8 ^ x^ 1 . 2 ).

In such oxides a comparison of the pyknometric

density with the x-ray density will be useful; gen- Figure 1. Resistivities of highly conducting (
metallic ) oxides.

2
Parameters

Latt.

emu/g.)

H.(x10

cm

it,a

K
<*,/uV/

AT

Endo—

mole

deg.

Cp.cal/

3
IQ
x

Counts,

Figure 2. Phase transitions in metal oxides investigated by various techniques.

3
ductor)-to-metal transitions; typical of these oxides RHENIUM
TRIOXIDE
are V0
2 3, V0 2, and Ti 2 0 3 (fig. 2). Conduction in
ROCKSALT
MO
CORUNDUM
M2 03
RUTILE
M0 2
(PEROVSKITE)
M0 3
oxides can be electronic or ionic; for example, lith-
ium-doped NiO is a pure electronic conductor while
Ca-doped Zr0 2 is a pure ionic conductor. d'°

A number of authors have recently reviewed elec-

tron transport and related properties of transition
metal oxides [3-5, 9-15]. Of the various attempts to
explain these properties, the qualitative approach
of Goodenough [5, 16-18] based on principles of
chemical bonding has been eminently successful.
With empirically derived criteria for the overlap of
cation-cationand cation-anion-cation orbitals as de-
termined by the crystal structures, Goodenough has
attempted to provide a unified understanding of
the magnetic and electrical properties of variety of
inorganic materials including simple transition metal
oxides, perovskites, spinels, bronzes, sulfides etc.
Goodenough two classes of oxides, those
distinguishes
Figure 3. Schematic one-electron energy level diagrams for
having large interactions between d electrons on different cation electronic configurations in various crystal struc-
neighboring atoms or ions because of large cation- tures ( after Vest and Honig ).

cation interactions via a small cation-cation separa- Dotted lines show predicted Fermi levels.

tion (Class I)and those having large interactions

between d electrons of neighboring atoms because
of large cation-anion-cation interactions via a large electrical transitions of three transition metal oxides
covalent mixing of anionic p orbitals into the cationic (V 2 0 3 , V0 2, and Ti 2 0 2 ) in order to illustrate the
d orbitals (Class II); there are also oxides belonging wealth of information available in the literature.
to Class I-II where the two mechanisms coexist. There is considerable doubt concerning the mech-
Our knowledge of the band structures of transition anism responsible for the observed changes in V 2 0 3
metal oxides is far from satisfactory. A detailed dis- and V0 2 Both these transitions are related to the
.

cussion of the theoretical models would be outside changes in crystal structure that occur simultane-
the scope of this work and the reader is referred to ously. The situation is not straight-forward since
the various reviews [1-5] and other articles listed the structural changes could themselves be deter-
at the end of this section. The intuitive approach mined by the electronic properties of the oxides.
based on molecular orbital theory provides crude Thus, it is possible that distortions occur at the
but reasonable approximations. In figure 3 is shown criticaltemperature in such a way as to create a
a summary of the over-simplified one-electron energy gap at the Fermi level. This may lower the energy
diagrams for a few crystal structures with the pre- of the occupied electron states or raise the energy
dicted Fermi levels for the various d electron con- of the unoccupied states. If initially the band is
figurations. This figure predicts either metallic or half-filled and then split into two (accompanying
semiconducting behavior for any crystal structure the crystalline distortion) there will be a transition
depending on the number of d electrons in the cation. from metallic behavior of the symmetric phase
Such models will undoubtedly provide a basis for (rhombohedral in V 2 0 3 and rutile in V0 2 ) to semi-
further studies which may eventually turn out to be conducting properties for the less symmetric phase
technologically important. We may note here that (monoclinic in V 2 0 3 and V0 2 ).
the properties of highly conducting oxides such as Several other mechanisms have been proposed to
TiO can be satisfactorily explained on the basis of account for the transition in V0 2 3. (i) One of the
such elementary band structure models. The status mechanisms invokes the onset of antiferromagnetism
of our understanding of the electrical properties of (whose existence has been verified by polarized
the metal oxides which exhibit electrical transitions neutron scattering). Here, the potential of the elec-
is,however, in a constant state of flux; there are trons differs for the spin-up and spin-down align-
many theories, none of which is entirely satisfactory ments of vanadium ions of the antiferromagnetic
and the field is rapidly developing [4, 10-15]. In phase and there is a doubling of the unit cell in the
figure 2 we have summarized the recent data on the magnetic superlattice. This is accompanied by a

4
splitting of the band, (ii) A combination of the two a gap of ~0.06 eV from the next higher one. The
preceding mechanisms has also been invoked. The pure material is, therefore, an intrinsic semiconduc-
band gap opening up under the combined action tor at liquid helium temperatures. With increase in
of both these effects would be sufficiently large to temperature, the distension of the unit cell is in such
cause a decrease in the carrier density and account a direction as to widen the bands and eliminate the
for the increase in resistivity. This would mean that gap. The material thus gradually is converted into
the mobility remains nonactivated and essentially an overlap material. All these theories of the semi-
unchanged. On the other hand, if either of the two conductor-metal transitions have been discussed in
mechanisms (distortion or antiferromagnetism) were the various references listed at this introduction and
alone to operate, there would be a decrease in carrier they are again referred to in the respective sections
density of only two orders of magnitude. In such a in the text.

case a change in mobility of five orders of magnitude It was our purpose initially to review phase transi-
would be necessary to account for the observations. tions of transition metal oxides in this monograph.
The mobility low-temperature monoclinic
in the We soon came to the conclusion that such a review
phase would then be low enough to correspond to an would be incomplete unless the relevant information
activated process, (iii) The possibility that band on the crystal chemistry, phase equilibria as well as
overlap may occur in VO 2 3 has been proposed, based electrical, magnetic and other important properties

on transport measurements. In this event, the transi- are also included. This is because, phase transitions
tion could be thought of as being driven by the in many of these oxides are associated with inter-
coulomb interaction between the holes and electrons esting changes in various properties (as in fig. 2).

(simultaneously present in the overlapping bands). In the phase transitions of some of the oxides like

This would result in a distortion which lifts the Ti0 2 and Zr0 2 electronic factors may not be very
band overlap. The insulating phase, according to this important, but the transitions themselves are of
mechanism, would be an 'excitonic insulator.’ academic and technological interest. The phase
Accordingly, the transition can be entirely sup- equilibria and crystal chemistry of many of the
pressed by application of hydrostatic pressure. Re- transition metal-oxygen systems are not fully in-
sistivity studies of the metallic phase under com- vestigated. As new phases of these oxides get estab-
pression down to liquid helium temperatures indicate lished, there will undoubtedly be further scope for
the presence of overlapping bands, (iv) It has been the study of phase transitions and other properties.
suggested that V2O3 may be an example of a ’Mott The Magneli phases of titanium and vanadium serve
insulator.’ This implies that small changes in inter- to illustrate this point. We have tried to keep the
atomic distances in the lattice causes sufficient altera- future possibilities in mind in presenting the avail-
tions in the band overlap to change the system from able information on transition metal oxides.
itinerant to localized behavior, (v) The effect of We have presented the information on the binary
electron correlations has also been considered im- oxides of the 3d, 4 d, and 5 d transition metals by
portant, since the bands in V 2 0 3 are relatively nar- firstsummarizing the general features of the phase
row. According to this theory, if the bandwidth is equilibria, phase transitions and physical properties
within a certain narrow range and is further reduced in each metal-oxygen system followed by a detailed
(by temperature changes or so) then a splitting into tabulation of the data. This tabular presentation of
two sub -bands takes place. It should be possible to the data is expected to give a brief summary of the
devise a single, comprehensive theory, in which the present status of knowledge on each oxide system.
possibilities discussed above become special cases. The material on each oxide system forms a self-

To decide among the various alternatives it is neces- contained section by and includes the relevant
itself

sary to obtain more detailed experimental data. The information on all the important properties. Such
case of the VO2 transition is similar to that of V2O3, a review of transition metal oxides is not presently
with the exception that VO 2 does not exhibit mag- available in the literature and we hope that this
netic order. present effort will be well-received by chemists, solid
Ti 2 03 differs from the cases discussed earlier in state scientists and others.
that, this oxide undergoes a transition over a rather The various binary oxides discussed in the paper
wide temperature range. It does not exhibit either areshown in table 1. We have listed most of the
magnetic order or undergo a crystallographic transi- important references to the literature (up to 1973)
tion. A band broadening model has been suggested on each oxide system and we apologize for any
to account for the transition of Ti 2 03 At low tem- . omissions due to oversight or errors in judgement.
peratures, the completely filled band is separated by Crystallographic data only from the recent literature

5
 i »

s.c.,

O o: o otc ow>
•a: -3 paramagnetic;

s u; u S3
S3

Pauli

O! Oi Oj Oi
to:*
o o pp,
3 hoi 3 3
<
1

Ui <\ <3

paramagnetic;

i! o O o o Ol p,
Zi ns «» M
z CU Ph A Hi

ferrimagnetic;

metals'

°! ql
0 ol O'
Ui Ui fe,

transition

of oi oi o! o3
«l
UhI £j
«l
fel PP oCD
antiferromagnetic;

e
o
semiconductor.

ft,
oxides
« 0 a

af,
stable
CP
o-.
O' q| q| oi degenerate

of
> Cl Cl c i
C;
o o
s| SI Si Si u v V
0 0 0 H H Ph pp ferromagnetic;

properties

/,

o oo>
O'
O O Oi
o O transition;

electrical

S S S! $ $ ?! diamagnetic;

CP
i—

and
>
o-. d,
o. O.
O' o0 d o o
Oi
s
U
CN |

o o o; 0-
q Oo semiconductor-metal

£ ol symbols:
Magnetic
0 0 0
y
I

h u
U: a
u u 73
1
a S s s £
1.1.
o
o following

<N oi o
K*'
>1
O!
>! >1
o o exhibits
existence.

V B. I
> > <F‘ the

TABLE
CP
H ,

V
> <N
o
with
doubtful

O, CD to

31
o <N| q vi o
o>

d
o
H
oj o /d!
O qi Ol d -Q O' i e o'
o qj shown
or

> <5j >•

s0 > >1 >il >1 > za .a!
Z! ^ VI ja -Q
-a;
Z:
CO «i
0.
0, 0 0 1 C3 a 0 a a z Z z 73 H d 1

are
semiconductor;

known

not

o. CV.
properties ,

(??),

oj o
L?
N
to* o oCO
d oj
Si
CP a S s S s fr! detail;

>
HH
u V electrical
metal;

CD H in
_*iV r-l ,
O o oj O; o: q:
r~
SA © q Si Sj
.^Ti

HI S
oa ol
<-M
>—
1
and

A r< e. i
a f a ;
a
i

i
N Sh
1 1

l investigated

Magnetic

superconductor;

qo o not

s
X 73 i &
a (?),

6
have been quoted and well-established data on stand- istry, Ed. C. N. R. Rao (Plenum Press, New York,
1970).
ard substances found in the papers have not been [7] Chemistry of Extended Defects in Nan-Metallic Solids,
repeated. Studies on solid solutions of oxides, liquid Eds. L. Eyring and M. O’Keeffe (North Holland Publ.
Co., Amsterdam, 1970).
oxides, oxide hydrates and thin films have not been [8] Menyuk, N., in Modern Aspects of Solid State Chem-
included and the review pertains only to the bulk istry, Ed. C. N. R. Rao (Plenum Press, New York,
1970).
properties of oxides in solid state. Effects of impuri- [9] Bosman, A. J., and van Daal, H. J., Adv. Phys. 19, 1
ties have been discussed wherever results are rele- (1970).
[10] Adler, D., Rev. Mod. Phys. 40, 714 (1968).
vant. We must add that the information on the [11] (a) Mott, N. F., Phil. Mag. 20, 1 (1969); Rev. Mod.
phase transitions of ternary oxides and other systems Phys. 40, 677 (1968).
(b) Zinamon, Z., and Mott, N. F., Phil. Mag. 21, 881
is very vast, but does not fall within the scope of (1970).
this monograph. We have not included any general [12] (a) Honig, J. M., IBM J. Res. Dev. 14, 232 (1970).
(b) Honig, J. M., in Modern Aspects of Solid State Chem-
discussion of the theory of phase transitions of in- istry, Ed. C. N. R. Rao (Plenum Press, New York,

organic materials as this subject has been adequately 1970).

[13] Rice, T. M., and McWhan, D. B., IBM J. Res. Dev.
reviewed elsewhere [19-21]. 14, 251 (1970).
[14] Doniach, S., Adv. Phys. 18, 819 (1969).
[15] Hyland, G. J., J. Solid State Chem. 2, 318 (1970).
[16] Goodenough, J. B., Bull. Soc. Chim. France 4, 1200
References (1965).
[17] Goodenough, J. B., Czech. J. Phys. 17B, 304 (1967).
[18] Goodenough, J. B., J. Appl. Phys. 37, 1415 (1966); 39
[1] Goodenough, J. B., Magnetism and the Chemical Bond 403 (1968).
(John Wiley-Interscience, New York, 1963). [19] Rao, C. N. R., and Rao, K. J., in Progress in Solid State
[2] Howe, A. T., and Fensham, P. J., Quart. Rev. (Chem. Chemistry, Yol. 4, Ed. H. Reiss (Pergamon Press,
Soc. London), 21, 507 (1967). Oxford, 1967).
[3] Adler, D., Solid State Phys., Eds. F. Seitz, D. Turnbull, [20] Rao, C. N. R., in Modern Aspects of Solid State Chem-
and H. Ehrenreich 21, 1 (1968). istry, Ed. C. N. R. Rao (Plenum Press, New York,
[4] Rao, C. N. R., and Subba Rao, G. V., phys. stat. solidi 1970).
(a) 1, 597 (1970). [21] Rao, C. N. R., and Natarajan, M., Crystal Structure
[5] Goodenough, J. B., in Progress in Solid State Chemistry, Transformations in Binary Halides, IN at. Stand. Ref.
Vol. 5, Ed. H. Reiss (Pergamon Press, Oxford, 1971). Data Ser., Nat. Bur. Stand. (U.S.), 41, 53 pages
[6] Anderson, J. S., in Modern Aspects of Solid State Chem- (July 1972).

I. Oxides of 3 d Transition Elements

1.1. Scandium Oxide by accompanied by an increase in co-

8.3 percent)
ordination number from six- to seven-fold for two
Scandium apparently forms only one oxide, SC2O3. thirds of the metal atoms. No change in the crystal
Petru and Dufek [1] reported a grey-black oxide, structure is noticed at 30 or 80 kbar pressure at
which they believed to be a monoxide, ScO, obtained 1273 K (or at 89 kbar at 1573 K) and at 110 kbar
by the hydrogen reduction of SC2O3 at 2170 K; this at 1273 K, poorly crystallized high pressure phase
monoxide has, however, not been characterized. SC2O3 of SC2O3 is obtained [8, 9].

is cubic [2-5] and has the C-type rare-earth oxide SC2O3 is a semiconductor at all temperatures [10
structure in which the metal atoms are distributed 13] and considerable ionic contribution to the total
in the ratio 1 3 into two crystallographically distinct
: conductivity is noticed at and below 1100 K [11,
sites each with six-fold coordination. The structure 12] .

is open and can be described as a defect

relatively SC2O3 forms a complete series of solid solutions
fluorite form in which one fourth of the anions are with ln 2 0 3 [9, 14], Y2O3 [15, 16], Yb 2 0 3 [15], and
absent. No magnetic ordering is known in SC2O3 Cr 2 C>3 [17] and binary systems of the type M0 2 -
and heat capacity data [6, 7] do not indicate any Sc 2 0 3 where M = Ti [18], Zr [18-21], Hf [22, 23], Th
phase transformations in the range 53 to 1800 K. [24], and U [24] and CaO-Sc2C>3 [25] have been in-
Reid and Ringwood [8] found that SC2O3 transforms vestigated in detail in the literature. Generally, solid
to the monoclinic B-type rare-earth oxide structure solution formation occurs up to certain composition
at 130 kbar pressure and 1273 K. The unit cell and the binary systems exhibit considerable ionic
volume decreases by 7.8 percent (density increases conductivity.

7
 .

Scandium oxide

Oxide and description Data Remarks and inferences References

of the study

SC2O3

Crystal structure and melting point. Ordinary form: This relatively open C-type [4, 8, 26].
Cubic; space group, Ia3; Z = 16; structure adopted by many
is

a =9.844 ±0.002 A. High-pres- rare-earth oxides and is closely

sure form: Monoclinic; space related to the fluorite structure.
group, C2/m; Z = 6; a = 13.173 The high pressure form is denser
±0.01 A; 6=3.194±0.005 A; and is akin to the B-type struc-
c = 7.976±0.01 A; 0 = 1OO.4O°± ture adopted by the rare-earth
0.05°. Melting point =2740 K. oxides. The transformation does
not involve the intermediate
corundum structure.

Electrical properties. Semiconductor behavior in the [10-13].

range 370-1870 K; reliable data
on pure and single crystal ma-
terial are not available.

Optical properties. Optical energy gap = 5.4 eV; in- [27, 28]
frared stretching frequency =
635 cm -1 .

References [14] Schneider, S. J., Roth, R. S., and Waring, J. L., J. Res.
Nat. Bur. Stand. (U.S.), 65A (Phys. and Chem.), No. 4,
345-374 (July-Aug. 1961).
[1] Petru, F., and Dufek, V., Z. Chem. 6, 345 (1966). [15] Hazek, B., Petru, F., Kalalova, E., and Dolezalova, J.,
[2] Milligan, W. O., Vernon, L. W., Levy, H. A., and Z. Chem. 6, 268 (1966).
Peterson, S. W., J. Phys. Chem. 57, 535 (1953). [16] Trzebiatowskii, W., and Horyn, R., Bull. Acad. Polon.
[3] Reid, A. F., and Sienko, M. J., Inorg. Chem. 6, 521 Sci., Ser. Sci. Chim. 13, 311 (1965).
(1967). [17] Tresvyatskii, S. G., Pavlikov, V. N., and Lopato, L. M.,
[4] Geller, S., Romo, P., and Remeika, J. P., Z. Crystallogr. Izv. Akad. Nauk SSSR Neorg. Mater. 2, 269 (1966).
124, 136 (1967); 126, 461 (1968). [18] Collongues, M. R., Queyroux, F., Perez, M., Jorba, Y.,
[5] Norrestam, R., Arkiv for Kemi 29, 343 (1968). and Gilles, J.-C., Bull. Soc. Chim. France 4, 1141
[6] Weller, W. W., and King, E. G., US Bur. Mines Rept. (1965).
Invest. No. 6245 (1963). [19] Lefevre, J., Rev. Hautes Temp. Refract. 1, 229 (1964).
[7] Pankratz, L. B., and Kelley, K. K., US Bur. Mines [20] Thornber, M. R., Bevan, D. J. M., and Graham, J.,
Rept. Invest. No. 6198 (1963). Acta Cryst. 24B, 1183 (1968)
[8] Reid, A. F., and Ringwood, A. E., J. Geophys. Res. 74, [21] Spiridonov, F. M., Popova, L. N., and Popils’kii, R. Ya.,
3238 (1969). J. Solid State Chem. 2, 430 (1970).
[9] Prewitt, C. T., Shannon, R. D., Rogers, D. B., and [22] Komissarova, L. N., and Spiridonov, F. M., Dokl. Akad.
Sleight, A. W., Inorg. Chem. 8, 1985 (1969). Nauk SSSR 182, 834 (1968).
[10] Noddack, W., and Walch, H., Z. Elektrochem. 63, 269 [23] Kalinovskaya, C. A., Spiridonov, F. M., and Komissa-
(1959). rova, L. N., J. Le8s-Comm. Metals 17, 151 (1969).
[11] Schmalzried, H., Z. Physik. Chem. 38, 87 (1963). [24] Trezebiatowskii, W., and Horyn, R., Bull. Acad. Polon.
[12] Tripp, W. C., and Tallan, N. M., Bull. Am. Ceram. Soc. Sci., Ser. Sci. Chim. 13, 303 (1965).
47, 355 (1968). [25] Trezebiatowskii, W., and Horyn, R., Bull. Acad. Polon.
[13] Zyrin, A. V., Dubok, V. A., and Tresvyatskii, S. G., Sci., Ser. Sci. Chim. 13, 315 (1965).
Khim. Vysokotemp. Mater., Tr. Vses. Soveshch. 2nd [26] Noguchi, T., and Mizuno, M., Solar Energy 11, 90 (1967).
Leningrad 59 (1965, Publ. 1967); Chem. Abstr. 69, [27] Companion, A. L., J. Phys. Chem. Solids 25, 357 (1964).
62562t (1968). [28] Petru, F., and Muck, A., Z. Chem. 6, 386 (1966).

8
 1.2. Titanium Oxides vacancies [3-6, 12-16], a low temperature ordered
monoxide recently characterized by Watanabe et al.
The Ti-0 system has been studied exhaustively by [17], an ordered TiOi. 2 B [18-20], a sesquioxide Ti 2 Os

various workers over the past several years. DeVries with a narrow homogeneity range, Ti 3 06, Magneli
and Roy [1] reviewed the available literature up to phases of the general formula Ti n 0 2n _i (4^71^10)
1954 and gave a tentative phase diagram. Since then, and Ti0 2 The phase diagram of Porter and Roy [5]
.

different groups of investigators [2-6] have con- is reproduced in figure 1.1. Recent studies have re-
tributed much to the understanding of the various vealed the complicated nature of the Ti-0 phase
phases in the Ti-0 system. The important phases diagram; according to Hirabayashi and co-workers
of the systems are the following: TieO (reported by [21], below 670 K, there is an almost infinite number

Kornilov and Glazova and characterized by

[7, 8] of ordered phases in the composition range 0.09 <
Yamaguchi et al. [9]), Ti 3 0 (reported by Kornilov O/Ti<0.40 and also a number of higher Magneli
and Glazova [7, 8] and characterized by Jostsons phases (n^ll-53; range, 1.90 <0/Ti< 2.00) (22, 23].
and Malin [10]), rhombohedral Ti 2 0 [3-6, 8, 11], a Titanium oxides show a wide variety of interesting
cubic monoxide, TiO*, having a wide homogeneity electrical, magnetic and optical properties and inter-

range (0.75 ^ 1.30) with disordered rock salt esting phase transitions. We shall now critically dis-
structure at high temperatures containing many cuss some important aspects in this section.

Figure 1.1. Ti-TiO* phase phase diagram showing various

oxide phases ( after Porter and Roy [5]).
TiO z <0.70): Metallic titanium exists in two allo-
(a: orthorhombic structure and is observed in specimens
tropic modifications, a (low temperature, hexagonal) which were rapidly cooled from the melt (of TiO*;
and (3 The a—>j3 transition
(high temperature, bcc). cubic high temperature modification) and not well
occurs at 1155 K
Oxygen addition to Ti stabi-
[2, 6]. annealed at low temperatures as well as in thin foils
lizes the a phase and oxygen can be dissolved (of TiO x ) annealed at temperatures greater than
interstitially up to ~30 atom percent [6]. From 870 K or heated by an intense electron beam [17,
measurements of resistivity [7, 24], Seebeck co- 31].Thus, the high temperature cubic TiO 0 7 -TiO 1.26 .

efficient [7] and rate of oxidation [25], it was sug- phase transforms, on cooling, to various ordered
gested that a stable phase, TieO, may exist. Recently, phases having different crystal symmetries by means
Yamaguchi [9] have fully characterized this
et al. of vacancy (both cation and anion) disorder-order
phase. Ti 6 0 is hexagonal with ordered superlattice mechanism. It is important to note, however, that
structure. Electron/neutron diffraction and DTA it is possible to retain the cubic phase at room
studies show an order-disorder transition at ~710 K; temperature by quenching from above 1270 and K
the phase is stable up to ~1100 K. ' a great deal of work has been done on these quenched
Ti 3 0 and Ti 2 0 have a hexagonal ordered structure cubic phases.
and they differ from the solid solutions of Ti and Detailed investigations on well-characterized sam-
oxygen by the ordered arrangement of the oxygens ples by Banus and Reed [28] and Taylor and Doyle
in the suboxide lattice and by the greater stability [29] have shown that the cubic lattice parameter
of the chemical bond [3, 4, 7, 8, 10]. Andersson [26] and the density increase with increasing * in TiO*
found that the so-called 5-phase of TiO x (* = 0.65) (in the range 0.86-1.24); p and dp/DT (negative)

has a hexagonal structure and the isotropy in TEC are small and increase slightly, a (n-type) increases
values are probably connected with the occurrence and xm is extremely small and unchanging, indi-
of the close metal-metal contacts, which are present cating that TiO is a typical metallic oxide [14, 28-
both parallel and perpendicular to the c axis. 30, 33]. TiO becomes superconducting at liquid
helium temperatures [15-34]; Hulm found
et al. [15]
TiOx (0.70 ^ ^ 1.30): The rock salt type TiO that Tsc varies from 0. 1-1.0 K as * increasesfrom
phase exists over a wide composition range depend- 0.92 to 1.10; for other values of *, at atmospheric
ing on the temperature, e.g., from TiOo .70 to TiOi .25 pressure, the materials are normal conductors down
at 1673 K and TiOo.9 to TiOi.26 at temperatures to T <0.08 K.
below 1260 K [3-6]. An important feature of this Annealing TiO* at 50-60 kbar pressure and at
phase, as shown from density and lattice parameter 1573 K decreases the total number of vacancies con-
measurements, is that its crystal structure has vary- siderably (by ~17 percent) [28, 35]; according to
ing proportions of both titanium and oxygen vacan- Taylor and Doyle [29], complete removal of vacan-
cies [3, 12-14, 16, 27-30]. At the composition
4, cies in TiO* is possible by proper selection of tem-
TiOo.70, the titanium lattice is almost perfect (-~4 perature and pressure (e.g., 77 kbar and ~1850 K).
percent vacancies, extrapolating to zero at ~TiOo.B) The removal of vacancies is accompanied by a rise
and about 30 percent of the oxygen sites are vacant. (for a given *) in lattice parameter, density and Tsc
In TiOi. 30 the oxygen lattice is perfect and about
, (from 0.7 to 2.3 K for TiOi. 00 )* slight increase in p
25 percent of the Ti sites are vacant. Even in the and a and decrease in compressibility and TEC.
stoichiometric oxide, TiOi.oo* about 15 percent of These changes in properties are completely reversi-
both Ti and O sites are vacant. These vacancies are ble and are unambiguously due to the pressure
arranged randomly at temperatures above the equi- effect because reheating the samples in the absence
librium temperature, 1260 K; at lower temperatures, of applied pressure (say at ^1570 K) causes them
however, ordering of the vacancies occurs and the to revert to the original vacancy concentration and
cubic rock salt structure of TiOi .00 transforms to lattice parameter [28, 29]. Recently, Iwasaki et al.
monoclinic phase [3, 4, 12, 17, 20, 31]. This mono- [36] have studied the effect of pressure on the lattice
clinic phase was first noticed by Naylor [32] from parameters of TiOo .82 and TiOi. 2 B and essentially
enthalpy studies. The oxygen-rich TiOi .26 becomes obtained the same results as those of Banus and
ordered after long annealing treatments at 1070 K Reed [28] and Taylor and Doyle [29]. The change
and the crystal symmetry changes from cubic to in a parameter is small for both the samples; for
tetragonal [18]. There is another ordered structure, TiOo .82 the decrease is considerable for smaller pres-
the so-called 'transition structure’ [17] observed over sures while TiOi .26 shows a decrease at relatively
a wide composition range TiO 0 7 -TiO
. 1 . 2 B; this has an higher pressures (10-60 kbar).

10
5
TiO* forms solid solutions with VO* and NbO* have noted that in the range 100 to 300 K, the ma-
but the solubility is low (^10 percent) [30, 37]. terial behaves as an intrinsic semiconductor with a

On the other hand, Gel’d et al. [37] noticed that the band gap of 0.03-0.05 eV (depending on the sample)
oxygen -rich phases TiOi .20 and VO 1.25 have an appre- and the drop in p beginning at ^400 K and extend-
mutual solubility (~20-25%). BeO, MgO,
ciable ing up to 470 K. The drop in p in the 400 to 470 K
andCaO also appear to form solid solutions (up to range was about hundred-fold. The resistivity of
^50%) [37], Loehman, Rao, and Honig [30] found Ti 2 0 3 goes through a shallow minimum at ^800 K
that the vacancy concentration is decreased in TiO x and rises again with further increase in temperature.
after solid solution formation; both TiO and (Tio .96 Hall data [52] below 273 K indicated the charge
Vo.os)0 show metallic behavior. carriers to be positively charged and with high mobil-
Since the low temperature ordered TiO z phases ities. Seebeck coefficient of pure Ti 2 0 3 is positive at

have been characterized only recently, reliable data ordinary temperatures [51, 53] (Loehman [53] re-
on the physical properties are lacking at present on ports smaller values compared to Yahia and Fred-
these materials. erikse [51] for pure Ti 2 0 3 ) and drops to smaller
values in going through the transition region (400 to
Ti20 3 Ti 2 0 3 has a narrow range of homogeneity
: 470 K).
(*=1.49-1.51 in TiO x ) [3, 4] and has the rhombo- The nature of the semiconductor-to-metal transi-
hedral crystal structure at room temperature tion in Ti 2 0 3 has been discussed by various workers
[12, 38, 39] and shows an unusual behavior in in the literature [54-64]. The gradual decrease in p
the thermal expansion of the lattice parameters and a in the region of the transition, the broad
in the range 450 to 650 K [12]. A more recent nature of the anomalies in x, heat capacity and
study on pure material shows that the abrupt
[40] DTA measurements indicate that Ti 2 0 3 is a relatively
change in lattice parameters sets in at a lower wide band material and that the semiconductor-to-
temperature (~400 K); the c/a ratio increases metal transition is of higher order [52, 54, 58-64].
and there is a 7 percent decrease in the volume Since the absence of antiferromagnetism is definitely
of the unit cell in the range 390 to 470 K. There established in this material [47], a plausible mechan-
is no change in the crystal symmetry in this ism appears to be that of band broadening or shift-
temperature range. Magnetic susceptibility does not ing [58, 61, 62, 64-66]. The presence of c axis pairs in
show any significant anomaly in the range 400 to the corundum structure to produce a cation sub-
550 K even though a two fold increase in the magni- lattice band [54] together with a strong trigonal
tude has been noted [12, 41-43]. The existence of crystal field will produce a filled band with one 3d
long range magnetic order in Ti 2 0 3 has been much electron per Ti 3+ ion (figure 1.2). The rapidly in-
debated on the basis of various experimental in-
vestigations [38, 44-46], but recent neutron diffrac-
tion study by Moon et al. [47] have clearly confirmed
the absence of antiferromagnetism in Ti 2 0 3 below
400 K. A specific heat anomaly has been reported
in Ti 2 0 3 in the range 450 to 600 K [32, 48]. Rao et al.

[49] have found a broad endothermic peak (centered

around 410 K) in the DTA curve (see figure 2 in
introduction section).
Electrical properties have been examined by many
workers in the literature [12, 33, 38, 50, 51]. Morin
[33]found that below 450 K Ti 2 0 3 is a semiconductor
with a small energy gap (E ~
0.05 eV); above this
ff

temperature it behaves like a metal with a ten-fold

drop in resistivity at T Yahia and Frederikse [51]
t.

observed the semiconductor-to-metal transition at

450 K, the drop in resistivity being of a factor of 40.
Abrahams [38] noticed the transition, but found that
T was ~660 K. Honig and Reed [52] have carried
t

out a detailed investigation on highly pure and

nearly stoichiometric single crystals of Ti 20 3 they ; Figure 1.2. Schematic band strurture of T^Oa ( after [65]).

11
creasing c a ratio in the vicinity of 400 to 470 K and Keys have suggested that the transition
[73]
[40] brings the anions and cations much closer and in Ti 3 0 5
may correspond to a semiconductor -to-
thus provides for a progressively greater overlap metal transition. X-ray studies of Asbrink and
among the corresponding wave functions (Note that Magneli [70] showed the presence of metal-metal
c a ratio at room temperature is anomalously small; bonding in the low temperature form of Ti 3 0 5 and
see figure 1.5). This, in turn, leads to narrowing above T these bonds get broken. Based on con-
t ,

and then to a disappearance of the valence band- siderations of the localized versus collective electron
conduction band separation (figure 1.2). The p-type behavior of the d electrons in Ti n 0 2n _i Magneli
nature of the charge carriers can be explained by phases, Goodenough [74] has suggested that a
assuming that either the carriers in the valence semiconductor-to-metal transition may exist in
band dominate the conduction or with a model in- Ti 3 0 5 .

volving joint participation of electrons and of holes Bartholomew and Frankl [75] made resistivity
with comparable effectiveness. measurements on flux grown Ti 3 0 5 single crystals
Honig and co-workers [52, 67] have shown that a and confirmed the semiconductor-to-metal transition
slight amount of impurity remarkably affects the in this material. Recently, Rao and co-workers
electrical properties of this material. A variety of [49] have examined the transition in Ti 3 0 5 in detail
values of T t as well as the magnitude of the change employing high temperature x-ray diffraction, DTA,
in p (at Treported in the literature [33, 38, 51]
t) electrical resistivity, ESR and Mossbauer techniques.
may as well be due to the small amounts of impurities These workers established the first order nature of
in the samples of Ti 2 03 employed in the investiga- the transition in Ti 3 0 5 with appreciable latent
tions. heat and hysteresis; no magnetic ordering was
Ti 2 03 forms solid solutions with V2O3 throughout noted in the low temperature phase. At T (448 K), t

the composition, but the solid solutions so formed p drops by two orders of magnitude and below
are not ideal and do not obey Vegard’s law [30, 68]. T Ti 3 05 is semiconducting with Ea of ~0.3 eV.
t ,

The interesting observation is that at rc — O.l in Slight amounts of Fe and reduce the transition W
(Tii-j Fz) 20 3 the values of o, c, and a are the same temperature and the magnitude of resistivity
as the corresponding values for pure Ti 2 03 after it discontinuity and at about 5 percent Fe dopant
undergoes the electrical transition [30, 40]; the c concentration completely suppress the transition.
^3 percent by
parameter of Ti 2 03 is increased by Since metal-metal bonding in Ti 3 0 5 has been
the incorporation of ~20 percent V C>3 while the 2 definitely established [70], it appears that Good-
corresponding a parameter contracts by —T.5 per- enough’s model [54, 55, 61, 74] would be applicable
cent. This strongly lends support to the idea [39] in explaining the transition in this material. Ac-
that strong metal-metal bonding across the octa- cording to Goodenough, in the titanium and
hedral edges takes place in Ti 2 C>3. Recent resistivity vanadium oxides, in the high temperature high
data on (Tii-zV^Os show that for 0^x^0.04,
[69] symmetry phases, the cation -cation distance is

p undergoes a change in almost the same temperature greater than the critical cation-cation separation
range as undoped Ti 2 0 3 samples with high x are
; (see [61] for details) and the charge carriers move
metallic at room temperature and exhibit no transi- in partially filled cation sublattice d bands and
tion. This observation is consistent with the crystal metallic behavior is exhibited only in the materials
data of Loehman, Rao, and Honig [30]. with well-defined Fermi surface. As the temperature
is lowered through T however, the band breaks t ,

Ti 3 0 5 Ti 3 0 5 the precursor of the Ti„0 2n _i Magneli

: , up into pairs of atoms that are bonded by homopolar
shear structures, is monoclinic at room temperature. bonds in which the conduction electrons are trapped
Asbrink and Magneli [70] reported that Ti 3 0 5 and a change to lower crystal symmetry (and
transforms to a distorted-orthohombic (more exactly, semiconducting phase) occurs to produce a filled

monoclinic) structure reversibly at ~390 K, where band separated from an empty band by a finite

as Naylor from his enthalpy data, indicated a

[32] energy gap. The atomic rearrangements at T t are
transition at ~450 K. Keys and Mulay [43], Mulay subtle in Ti 3 05 [49, 70] and it appears that these are
and Danley [71], and Vasilev and Ariya [72] showed sufficient to bring about an electrical transition in
that xm of Ti 3 0 5 shows a sharp discontinuity at this material. According to Goodenough’s model,
~460 K, with a 30 K hysteresis on cooling; both we expect electrons to be the charge carriers in
above and below the T xm is temperature in- t , Ti 3 05 and the available Seebeck coefficient data
dependent. Keys, Mulay, and Danley [43, 71] [76] seem to confirm this prediction.

12
 Iwasaki et have reported the existence of a
al. [77] croscopy and diffraction by Hyde and co-workers
metastable form of Ti 3 0 5 (designated as D) which [22, 23] showed the existence of a new family of
is identical with the high temperature form of T 13 O 5 ordered phases, Ti„ 02 n-i (15^n^36) derived by
1
[49, 70] (D' form), hut the two differ in their proper- CS planes parallel to (132). Possibility of the exis-
ties with respect to oxidation. D and D' forms can tence of another Ti n 0 2 „_i (n> 35) family (Oil) shear
be prepared by the hydrogen reduction of anatase planes was suggested by these workers since con-
and rutile respectively at ~1520 K and give almost tinuous streaking along (Oil )
directions was observed
identical x-ray diffraction patterns, but on oxidation occasionally in the electron diffraction patterns of
at ~920 K, D gives rutile while D' gives a mixture reduced rutile and detailed studies are yet to be
of anatase and rutile modifications of Ti02. The low made. Studies are also necessary in the composition
temperature form (M form of Iwasaki et al. [77]) range 9<n<15, (i.e., TiOi. 8 89-TiOx. 933 ).
can be prepared by the vacuum sintering of TiCh The rutile based Ti n 0 2 „_i series with 4 ^ n ^ 9 have
(anatase form) and Ti metal at ''-'1520 to 1570 K periodic stacking faults introducing extra planes of
and and anatase on oxidation. For the
yields rutile metal ions for every n planes in one crystallographic
phase transition D'—»M, Iwasaki and his co-workers direction (121) and Magneli [79, 82] has pointed
report a T slightly greater than 373 K. The D form
t
out that the condensation of the defects into com-
could easily be changed to the M
form by cooling mon planes can minimize the elastic energy of the
from 1620 K under vacuum. These observations sug- crystal. Goodenough [74, 85] has recognized that
gest that differences in the oxygen coordination such systems exhibiting shear structures may con-
around Ti may give rise to stable and metastable tain collective d orbitalsand that the regularity of
modifications of ThOs and the T as well as electrical
t the spacings between these shear planes is due to

and related properties may also differ accordingly. the existence of a Fermi surface and to the energy
From this point of view, careful reinvestigation of stabilization achieved by either creating or increas-
the transition in Ti 3 0 5 is worthwhile on well char- ing the energy discontinuity across a Brillouin zone
acterized samples of this material. surface at the Fermi surface. This stabilization is

greater, the narrower the bands are, and hence

Ti n C> 2 n-i: The existence of Magneli phases in the spontaneous crystallographic distortions could result
Ti-0 system was first reported by Andersson et al. at lower temperatures. Also, since the existence of a
[3,4] in 1957. These are a homologous series of tri- Fermi surface is a collective electron property [61],
clinic phases of composition Ti„02 n -i with 4 ^ n ^ 9. it can be argued that crystallographic distortions in

They are bounded by monoclinic Ti 3 Os on one side the Magneli phases may also be associated with the
and by reduced rutile (TiCh-x) on the other. The metal-to-semiconductor transitions (on cooling) As a .

structures with 4 ^ n ^ 9 can be described [3, 4, 22, matter of fact, the available data indicate that elec-
23, 78-84] as being built-up of slabs of rutile-type tronic transitionsdo occur in these materials associ-
structure which have infinite extension parallel to ated with crystal distortions; however, the crystal
the (121) plane and have a characteristic finite width distortions appear to be minor (at least in Ti 4 C> 7 ,

corresponding to n TiOe octahedra (where n is the for which detailed high temperature x-ray data are
integer in the chemical formula, Ti n 02 n -i) in the third available [75, 86]) and do not involve structural
direction. The adjacent by
slabs are mutually related changes but only minor discontinuities in the lattice
crystallographic shear (CS), the shear plane and parameters at the transition temperature.
shear vector being (121) and [Oil] respectively in Detailed x-ray [75, 86], xm-T [43, 71, 72], DTA
the idealized Ti n 02 n -i structure. This CS causes the [75] and P-T [75, 87] studies show that there are
titanium atom positions in one slab to correspond two phase transitions in Ti 4 07 at —'125 and at
,
'

to unoccupied or interstitial positions in the next 150 K. There is 8 to 10 K hysteresis associated with
slab and decreases the crystal symmetry from tetra- the first transition and some structural changes;
gonal to triclinic while decreasing the size of the the 150 K transition is associated with a change
unit cell. However, the structure of TiioOi 9 ( = 10) from semiconductor to metal behaviour as well as
cannot be explained in this way and the structure magnetic susceptibility and DTA anomalies, but no
is not yet known. apparent structural change. TuOg exhibits transi-
Anderson and Hyde [81] suggested that rutile- tions at 130 and 136 K and resistivity measurements
based shear structures other than the (121) family indicate discontinuities at these temperatures, but
probably exist, in particular, a (132) family in re- the sample remains semiconducting above T [43, t

duced rutile. Detailed studies using electron mi- 71, 75]. DTA and xm-T measurements indicate a

13
 '

transition in TigOn at 122 K [43, 71, 75], but the stood. There is considerable evidence for the forma-
resistivity data indicate a T; of ~130 K and semi- tion of both titanium interstitials and oxygen va-
conductor behavior above and below this tempera- cancies [61, 104-108]; the atmosphere in which the
ture [75]. According to Bartholomew and Frankl defects are formed seems to be an important factor.
[75], Ti 8 0i5 exhibits semiconductor behavior in the Since the anatase-rutile transformation involves an
range 78 to 295 K and no transitions exist in this overall contraction or shrinkage of the oxygen struc-
material, xm -T data are not available at present. ture as indicated by a volume shrinkage of ^8 per-
The detailed physical properties of Ti 7 0i3 and TigOn cent and a cooperative movement of ions (displacive
are not known at present. and reconstructive transformation [94, 109, 110]),
the removal of the oxygen ions would be expected
Ti0 2 Titanium
: dioxide, Ti0 2 has, a narrow homge- to accelerate the transformation; formation of tita-

(x —
neity range 1.983-2.000 in TiO x ) [3-6, 88], and
-
nium interstitials would inhibit the transformation.
exists in three polymorphic forms, namely, anatase This implies that a reducing atmosphere or doping
(tetragonal), brookite (orthohombic) and rutile , with an ion of lesser valence state (Cu 2+ or Co 2+ ) ;

(tetragonal) at atmospheric pressure. In each of would accelerate the transition as indeed found ex-
these, Ti 4+ ion surrounded by an irregular octa-
is perimentally. Vacuum or doping with anions will
hedra of oxide ions, but the number of edges shared similarly give rise to Ti 3+ interstitials and hence the
by the octahedra of oxide ions, but the number of inhibition of the transformation process and would
edges shared by the octahedra increases from two increase the temperature of the anatase-rutile transi-
(out of twelve) in rutile to three in brookiteand to tion.

four in anatase. form of Ti0 2 is the most

The rutile Yoganarasimhan and Rao [94] noticed that the
stable form and both anatase and brookite transform and crystallite size of anatase increase
particle size
to rutile on heating. High pressure modifications of markedly in the region of the crystal structure trans-
Ti0 2 have been reported by Dachille and Roy [89], formation; smaller particle size and larger surface
Bendeliani et al. [90], and McQueen et al. [91]. area of anatase samples favor the transition. De-
Phase transformations involving various modifica- tailed x-ray studies indicated that the unit cell ex-
tions of Ti0 2 have been extensively studied in the pands prior to the transformation to rutile.
literature. Recently, Vahldiek [111] examined the effect of
Anatase transforms irreversibly and exothermally pressure on the anatase-rutile transformation. Elec-
to rutile in the range 880 to 1200 K depending on trical resistance and quenching experiments indi-

the method of preparation of the sample and at cated that T and AH for the transition decrease
t

atmospheric pressure, the transformation is time with the applied pressure; at a pressure of 1 bar, j

and temperature dependent and is also a function AjFT-—— 2.8 kcal/mol and his observations corrobo- }

of the impurity concentration. Rao and co-workers rated the data of earlier workers. Discontinuous l

[92-96], Sullivanand Cole [97], Iida and Ozaki [98], change was observed at T at various applied
in p t

Suzuki and Kotera [99], and Shannon and Pask pressures and the irreversibility of the anatase-rutile j

[100] have carried out systematic investigations of transition at high pressures (up to 24 kbar) was
the anatase-rutile transformation. The rate of trans- confirmed.
formation of spectroscopically pure Ti0 2 in the anat- Kubo et al. [112] and Tekiz and Legrand [113] ob- j

ase modification was found to be immeasurably slow served the transition of anatase to rutile by grind-
below 885 K and extremely rapid above 1000 K ing; anatase-type Ti0 2 obtained from TiCR method
[92, 101]. The transition is a nucleation-growth pro- is changed to rutile after grinding for 96 h, while
cess, and follows the first order rate law with an Ti0 2 (anatase form) obtained from the H S 04 method
2

activation energy of ~90 kcal/mol (fig. 1. 3a). Im- changed to an amorphous state.
CuO, CoO, Li 2 0, and Na 2 0 and re-
purities like Brookite, the orthorhombic modification of Ti0 2
ducing atmospheres accelerate the transformation occurs in nature; it has not been possible to prepare
while sulphate, phosphate, and fluoride anions, P 5+ this polymorph in pure form in the laboratory.
and S 6+ ions
and vacuum stabilize the anatase modi- Brookite-rutile transformation was first reported by
ficationand inhibit the transition process [94-96, 98, Schossberger [114] and examined in detail by Rao
100, 102-104]. Values of T and activation energy t
and co-workers [115]. Below 990 K, the rate of
are generally higher in impure samples than in the transition is extremely slow and sluggish and above
pure sample. this temperature, it follows a first order rate law
The defect structure of Ti0 2 is not yet fully under- with little or no induction time (fig. 1. 3b). The

14
Figure 1.3. Transformation of anatase (a) and brookite (6) as a function of temperature at different times ( after Rao and co-workers

/A And /b are the fractions of anatase and brookite forms in the mixture. Kinetics of transformation of anatase and brookite to rutile are shown in (c) and (d)
respectively (/r = fraction of rutile).

15
transition is irreversible with an energy of activa- resistivity, Seebeck coefficient and Hall mobility
tion ~60 kcal/mol and — (100=fc75) cal/mol. studies over a range of temperatures have not been
DTA studies give 7\« 1020 K. able to provide a clear understanding of the mecha-
As regards the comparison of the anatase-rutile nism of conduction in pure and doped Ti0 2 [1 lb-
and brookite-rutile transformations, it may be men- 120; 122b— 122d] multiple band conduction seems
;

tioned that the kinetics and mechanism are exactly to be conclusively proved, but the existence of band
similar (fig. 1. 3c and 1. 3d), but the energy of activa- or hopping (large or small polaron) type of conduc-
tion is larger in the anatase-rutile transition; the tion is still in dispute.
entropy of activation and negative for the
is large As mentioned earlier, the defect structure of Ti02
brookite-rutile transition while it is small and has a isnot yet completely understood and evidence is in
positive value for the anatase-rutile transition. This favor of both anion vacancies and Ti interstitials
discrepancy may be understood in terms of the [61, 104-108, 123, 123a]. Hauffe [123a] and Rudolph
change of symmetry (lower to higher) in the former [123b] noted that in the range 882 to 1273 K,
case and the absence of such a change in the latter p a Po 2-1/n where n from 5.7 to 4.4 whereas
varies
case. Greener et al. n = 4 above 1470 K
[123] obtained
A new high pressure modification of TiOa was and no dependence of p on p 02 below 1170 K (ideally,
synthesized by Dachille and Roy [89] at pressure 15- n should be 6, 5, and 4 for anion vacancy, Ti 4+ and
100 kbar and temperatures 298 to 773 K. It forms Ti 3+ interstitial mechanisms respectively). High tem-
easily from anatase, but appears to be metastable perature Ea values (1.8 eV) of both workers agree
with respect to rutile.The structure of this modifica- very well. Internal friction measurements [123c] on
tion is not known. The new form converts slowly to vacuum-reduced rutile (for 1-3 h at 1530 K), on
rutile on heating between 770 to 973 K via a short- the other hand, indicate that the predominant point-
range order phase. defects are neither anion vacancies nor cation inter-
According to McQueen et al. [91], rutile at ordinary stitials and the observed data in the range 50 to 300
temperatures transforms to an orthorhombic modi- K are best explained by assuming that Ti interstitials
fication at 330 kbar pressure with considerable de- are associated in pairs in TiC> 2 . Resistivity studies
crease in volume (^21%). Bendeliani et al. [90] on rutile under various pressures [124] indicate a
have synthesized the orthorhombic modification at large decrease in p up to ^6 kbar; at higher pres-
~70 kbar pressure and 970 K (pressures 40-120 sures (up to ^100 kbar), the resistance change was
kbar and 670 to 1770 K, under hydrothermal condi- small suggesting that Ti 02 retains semiconductor
tions). This phase reverts to rutile on heating to behavior over a large pressure range with the possibil-
720 to 870 K. The detailed physical properties of ity of exhibiting metallic conduction at very high
this phase are not known at present. pressures [124, 125]. Preliminary results of Kawai
Even though the anatase and brookite modifica- and Mochizuki [125a] actually indicate a highly
tions have not been investigated in detail, extensive conductive state in Ti0 2 at pressures greater than 2
literature is available on various physical properties Mbar.
of the rutile modification of TiC>2 [43, 116-120] and TiC>2 in the rutile modification forms solid solu-
have been treated in detail in many review articles tions with other transition metal oxides with rutile
[57, 61, 63, 116, 121, 122]. Stoichiometric TiC>2 shows related structures; thus, solid solutions with VO 2
a temperature independent susceptibility consisting [126-131], Zr0 2 [132, 133], Nb0 2 [134-136], Mo0 2

of a diamagnetic and a Van Vleck contribution [43, [134], Ta0 2 [135], W0 2 [137, 138], Ir0 2 [139] are
121, 122a]. Ti0 2 has a high room temperature re- known and the physical properties are well investi-
sistivity and exhibits semiconducting behavior; in- gated. Inmost of the cases, undistorted rutile struc-
trinsic conduction seems to set in only at very high tures formed and the properties of ZO 2
are
temperatures (>1500 K) with a large energy gap =
(Z transition metal) are modified by the presence
(~3 eV). Doped or reduced Ti0 2 has a lower re- of Ti(> 2 .

sistivity and exhibits impurity conduction. Detailed

16
 Titanium oxides

Oxide and description Data Remarks and inferences References

of the study

TiO* (*<0.70)
TieO

Crystal structure and Hexagonal; space group, P31C; a = 5.14 A, The transition appears to be an [9]

phase transformation. c = 9.48 A. DTA shows a transition at order -disorder type with respect
~710 K; AH = 360 cal/mol; AS = 0.51 to the interstitial positions of the
e.u. oxygens; no superlattice reflec-
tions are noted in electron dif-
fraction patterns of a sample
quenched from 970 K.
TiaO

Crystal structure. Hexagonal; space group, P312; a =5.1418 The structure consists essentially of [10].
A, c = 14.308 A. a close-packed hexagonal arrange-
ment of Ti atoms with every sec-
ond layer of octahedral interstices
normal to the c axis vacant; one
third of the oxygen sites in the
occupied layers are empty and
these vacancies have an ordered
arrangement in the direction of
the c axis. Physical properties of
Ti 3 0 are not known in detail at
present; it appears to be stable
up to ~1670 K.
TijO

Crystal structure. Rhombohedral; space group, P3ml; a = The ordered structure, described as [4, 11, 26]
2.959 ±0.003 A; c =4.845 ±0.004 A. TEC TioOi-y exhibits a homogeneity
(293-773 K): ||“: 10.3 X 10-«/ o C; C :9.2X
||
range which increases as the tem-
10“«/ o C. perature is lowered.

TiOo.es (5-oxide) Hexagonal; space group, P6/mmm; Z — 3; This is a deficient interstitial solu- [26].
a=4.9915 A; c = 2.8794 A. TEC: (293- tion of oxygen in a metal atom
773 K): ||° = 10.0Xl0 -6 /°C; || e =9.0X lattice.
0
io-«/ c.

TiO* (0.70^ *0.25)

Crystal structure and [28]

physical properties.

17
 Titanium oxide — Continued

Oxide and description Data Remarks and inferences References

of the study

High temperature quenched (cubic, Fm3m) phases:

Decrease in
Composition Density Lattice % Vacancies vacancies Tsc* P (300 K)
X (g/cm 3 ) parameter, (Total) (after pres- (K) (10 4 fi cm) (mV/°C)
.(A) sure treat-
ment), %

0.86 5.057 4.189 31.5 14 <1.3 2.8 4

0.91 5.025 4.186 29.9 12 <1.25 ~3.0 5
1.00 5.000 4.184 28.0 17 1.35 2.8 8
1.18 4.907 4.173 24.7 11 1.7 3.4 11
1.24 4.870 4.170 23.3 22 2.0 3.6 12

• Pressure treated samples (at 50—60 kbar and 1370 to 2070 K).
No magnetic susceptibility was observed for any TiO z samples down to the limit of the senstiivity of the magnetometer (Xji~ 150 X 10" 6 emu); Hall I

voltage observed was very small and no meaningful results could be obtained.

Vacancy filling in TiOi.oo

and physical properties. [29].

TEC
Conditions of Density Lattice para- % Vacancies Compressi- (X10 6 7a Tsc
study (g/cm 3 ) meter, a (A) (total) bility (X10 13 deg -1 ) (K)
cm 2 /dyne) at 298 K

1773 K, 1 bar; 2 days, 4. 97 ±0.003 4.1796 28.8 5. 5 ±0.08 6.73 1.18 0.7
quenched.

1923 K, 77.4 kbar; 5. 69 ±0.009 4.2062 0.0 4. 2 ±0.008 6.30 — 2.3

sudden quench.

The gradual increase in density and lattice parameter with decrease in vacancy concentration under various pressure and
temperature treatments are studied in detail. An empirical equation correlating the lattice parameter, pressure and tempera-
ture i6 deduced from experimental data.

18
 Titanium oxide — Continued

Oxide and description Data Remarks and inferences References

of the study

Compressibilities of Experimental values are 1.6(4) and 2.8(7) X These values compare well with [34].
TiOz. 10 -13 cm 2 /dyne for x=0.82 and 1.25 re- those of other transition metal
spectively. monoxides.

Seebeck coefficients of Small and negative (

—5 to —10 juY/°C) for These results are in agreement with [140, 141].
TiOz (0.8 1.2). all x in TiOz a increases with x and tem-
• those of Banus and Reed [28].
perature. Qualitative description of the
band structure is given; Ef
changed appreciably with the
composition x.

Plasma resonance in Reflectance data show the plasma edges in The studies indicate the metallic [14, 142].
TiOz. TiOz in the range eV and
3. 6-4.0 the ac- nature of TiOz. A band of 2.5 eV
tual value depends on x to some extent. in the reflectance spectrum is as-
The color of TiOz is correlated with these signed to an interband transition.
plasma edges.

Band structure of TiO. Tight binding and AP^

methods of theo- Calculations on TiOz taking into ac- [143-145].
retical calculation of the band structure count the vacancy concentration
of TiO indicate that the 3 d bands are and composition do not seem to
wide (~6 eV) and the electrical conduc- be satisfactory in explaining the
tion can be assumed to take place in the observed data. As pointed out by
wide band. Most of the transport proper- Honig et al. (ref. [4], p. 130) cation-
ties are predicted in good agreement with anion-cation overlaps also should
experiment. be taken into account in comput-
ing the band structure in addi-
tion to the direct cation-cation
overlap in order to get a reason-
able picture of the band model in
oxide materials. Results of
Kawano [141] indicate that the
Fermi level and density of states
shift with the stoichiometry in
TiOz.

Low temperature
ordered structures

Phase, stability range

and conditions of
observation:

TiOo.r-TiOo.g: thin Orthorhombic; space group, 1222; Z=6; This structure results from the or- [17, 19, 31].
foils (of TiO z ) heated a' = a V2; b —3a \/2; c' —a ( is the lat- dering of the oxygen vacancies
above 870 K in the tice parameter of the original, high tem- only since there are more oxy-
electron microscope or perature, cubic cell of TiOz). gen vacancies than titanium
heating by an intense vacancies in the oxygen deficient
electron beam. alloys; all oxygen vacancies are
distributed on every third (110)
plane in the original rock salt
type lattice while the Ti va-
cancies are distributed randomly.

19
 Titanium oxide — Continued

Oxide and description Data Remarks and inferences References

of the study

TiOi.oo (composition Monoclinic; space group, A2/m; Z = 12; a = The transition temperature is [14, 17, 19,
range TiO 0 90 -TiO
. 1 . 10 ); 5.855 A; 6=9.340 A; c = 4.142 A; 0 = around 1190-1220 K; but the 20, 28, 31].
quenched from 1773 K 107.53°. Vacancy concentration, 16.7%. process is slow (and requires long
and annealed for two p (300 K) = 2X10 ~ 4 V cm; p (77 K)=7X periods of annealing) since this is
-5
days (1170-1220 K). 10 ficm. Positive temperature coeffi- a disorder -order transformation.
cient; Absolute value of p is much lower This structure can be described
than that of the cubic phase. in terms of vacancy ordering:
i.e., in every third (110) plane of
the original cubic cell, half of the
%
titanium and half of the oxygen
atoms are missing alternately.
The spacing of this (110) plane
is slightly larger than that of the
other {110} planes, and as a re-
sult, the symmetry of the original
cubic structure is lowered to
monoclinic. Essentially the same
structure has been observed in
the composition range TiOo. 90-
TiOj.io which implies that a
small excess or deficiency of
titanium and oxygen vacancies
can be tolerated in TiOi.oo
structure.
TiOi .19

Samples annealed for Both types of ordered structures, TiO and Electron diffraction patterns indi- [18, 31].
long periods below TiOi. 25 , are noticed. cate that the ordered phases co-
973 K. exist as alternate thin layers of
TiOi.oo and TiOi .25 parallel to
(210 } c planes.
TiOi .25

Alloy annealed for 7 Tetragonal; space group I4/m; Z = 10; a = The type of ordered structure in [18, 31,
days at 973 K and then ao-\/lO/2 =6.594 A; c = ao = 4.171 A. (ao is TiOi .25 is different from that in 146, 147].
at 673 K. the original cube cell edge). [Vacancy TiOi.oo; the oxygen sublattice is

concentration, ~22%]. fee and fully occupied while the

titanium sites get ordered similar
to Ni 4 Mo and Au 4 Mn type super
structures.

Transition structure Both ordered TiO and TiO 1.25 structures The appearance of the transition [31].

(range TiO0 -TiO

. 7 1 .
Samples rapidly cooled
from the melt and not
well annealed at lower
temperatures.
25 ). coexist, the amount of the latter increas- structure is of importance for
ing with the oxygen content of the speci- understanding the process of
men. The transition structure observed transformation from the dis-
occasionally in the TiOi .25 specimen seem ordered to the ordered form.
to be due to insufficient ordering treat- When the disordered specimen of
ment and it is considered that the transi- any composition is cooled to the
tion structure would ultimately transform equilibrium temperature, the
to the ordered TiOi .25 structure. vacancies concentrate firstly on
every third atomic plane parallel
to the (110) plane of the original

20
 Titanium oxide — Continued

Oxide and description Data Remarks and inferences References

of the study

rock salt structure, but are

randomly distributed on these
planes giving a diffraction pat-
tern of the transition structure.
On further annealing, the vacan-
cies are distributed into the
proper positions to make the
ordered structure of TiOi .26
type. Watanabe et al. [31] point
out that the high temperature
cubic and orthorhombic TiO*
observed by Hilti [19] are the
same as the 'transition
structures.’

TisOj

Crystal structure and T = 300 K: Hexagonal (corundum); space There is no change in the crystal [30, 39, 40].
high temperature group, R3C;
6; a ^5.1572 ±0.0002 A; symmetry 300=500
in the range
x-ray studies. c* 13.600 ±0.001 A. K but the thermal expansion
T*540 K: parameters behave in an
Hexagonal; space group, R§C; Z = 6; anomalous way; the a parameter
5.122 A; c- 13.90 A. AV (on heating from decreases while c parameter in-
300 to 500 K) = -7%. creases. The unit cell volume
decreases.

Magnetic properties. Xm K)~1.0X10 -4 cgs units and shows

(300 Xm -T data and polarized neutron [12, 41-43,
a two fold increase in the range 400 550— diffraction datado not indicate 47].
K. Xm below 400 K is almost temperature magnetic order in T^Oa below
independent. 400 K.
Magnetic moment <0.03 /ub-

Thermal properties. Cp(400 K)~0.2 cal/mol, deg. and shows a These data show the second (or [32, 48, 49].
broad X-type anomaly in the range 450- higher) order nature of the
600 K. AH (calc.)~36 cal/mol [48]; 215 transition
cal/mol [32], DTA shows a broad endo-
thermic peak (centered at ~410 K).

21
 8

Titanium oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

Electrical properties This is a careful study on well [52, 53].

of TiOi.501. characterized pure single crystals.
Temp- Rc a Various ranges of p and R c values
era- P (cm 3 / Ap/ Wl are encountered because of vari-
ture (ft cm) C) P
a
K) able sample purity; common
(K) impurities like C, N affect the
properties. The study by Honig
and Reed [52] emphasizes the
4.2 K (1.3-1. 8) — (b) 3-4 — need for painstaking efforts in
X104 (^200 the preparation and characteri-
kG) zation of oxide materials. Slight
77 K 0.2-0. 0.4- <10“ 3 anisotropy in p has been noted.
1.5 Impurity conduction seems to be
273 K ~10~ 2 0.08- <10- 3 56 predominant below 20 K; in the
0.11 range 100-300 K, intrinsic be-
600 K ~3 X 10~ 4 — — 45° havior is noted. Hall mobilities
are the highest encountered
hitherto in pure oxide materials;
(a) Magnetoresistance; Ap/po^H 2 . (b) at higher temperatures, ph seems
Not measurable, (c) At 400 K. to decrease. Magnetoresistance
Ea ( <20 K)~0.001-0.003 eV; data indicate that a multiband
Ea (100-300 K)~0 .027-0.050 eV. conduction exists in Ti 2 03 The .

T = 4.2 K: mh (calc.)~720-840 cm 2 / band model proposed (fig. 1.2)

Vs; n ~10 e
10
, cm -3 . can explain the observed data
without invoking a magnetic
ordering in Ti 2 03 at low
temperatures.

UHF Dielectric UHF (~10 GHz): * (T = 77 K)=30; The imaginary part of the dielec- [148].
constant studies. p (UHF) >p (DC). tric constant shows a maximum
at 225 K, but this is not con-
nected with any transition in
Ti 2 0 3 .

Raman spectroscopy Raman spectrum of Ti 2 C>3 exhibits seven The Raman results can be inter- [149].
modes as predicted for the corundum preted in terms of the electronic
structure. All the modes persist above the and structural changes during the
semiconductor-metal transition tempera- transition.
ture indicating absence of space group
-1
change. The Ai g mode at 269 cm (300
K) shows a 16% change in frequency and
increase in intensity at the transition.

TisOs

Crystal structure T = 300 K: Monoclinic; space group, C2/m; There is not much change in crystal [49].
and x-ray studies. Z = 4; a =9.80 A; 6=3.79 A; c = 9.45 A; symmetry at T but the unit cell
t

(3=91.75°. T>460 K: Monoclinic; a = volume increases. The transition

9.90 A; 6 = 3.78 A; c = 10.02 A; 0=90.75°. is of first order.
The c parameter and the unit cell volume
show jump at T< (448 K) on heating.

Magnetic properties. Xm (300 K)~10 8

cgs units; xm (600 K)~ Mulay and Danley [71] proposed a [43, 49, 71].
-4
2 X 10 cgs units, xm is temperature inde- new model to explain the mag-

22
 Titanium oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

pendent both above and below T large t; and the

netic behavior of Ti 3 Os
jump at T is noted with hysteresis; T
t t Magneli phases. According to
(heating) « 462 K; Tt (cooling) as 432 K. this, below T groups of cations
t,

Xii-T data and Mossbauer studies do not are distributed periodically

indicate long range magnetic ordering in throughout the lattice; within
the low temperature phase. these groups, the d electrons are
Rao et al. [49] have pointed out that the localized. However, 'constrained
Mossbauer data on Fe-doped Ti 3 Os type’ antiferromagnetism sets in
should be interpreted with caution since between specific neighboring d
Fe is known to stabilize the high temper- electrons through homopolar
ature phase of Ti 3 Os. Neutron diffraction bonding of cations. Neighboring
studies are urgently needed on Ti 3 Os to groups interact via thermal ex-
establish the presence or absence of mag- citation of electrons. Above the
netic order in this material. transition, this type of ordering
is modified by crystal structure
changes and 3d orbital overlap is
large enough to bring about a
nearly complete delocalization of
electrons over the entire lattice
and the behavior is described by
the 'free electron gas’ model.
This approach is a slightly modi-
fied form of the one proposed by
Goodenough [74].

Thermal properties. Heat content data on Ti 3 Os exhibit an The first order nature of the transi- [32, 49, 75].
anomaly at ~450 K. DTA shows a sharp tion is established. Fe doping
endothermic peak at 450 K; the peak is reduces T and at higher concen-
t

shown in the cooling curve at ~415 K; trations (5%) suppresses the

AH = 1.6 rt0.4 kcal/mol. transition; the transition at
lower concentrations does not
seem to be strictly first order.

Electrical properties. p (340 K)«20 ft cm; p (500 K)«0.6 ft cm.
Semiconductor behavior below 450 K;
Ea = 0.29 eV. Large drop in p at T (Bar- (
tholomew and Frankl [75] report a con-
tinuous change in p through Tt). Metallic
behavior above T m* (calc., high tem-
t;
perature form) «20 m; a (340 K)~ —60
mV/°C [76].
The first order semiconductor-to- [49, 71, 75,
metal transition is confirmed in 76].
Ti 3 Os; Rao et al. [49] stress the
the importance of the purity of
the material in determining the
resistivity discontinuity at Tt.

ESR Studies. Multiplet structure is noted in the ESR The multiplet structure appears to [49, 73].
spectra at 77 K. Well defined spectra are be due to inequivalent cation
not obtained at higher temperatures and sites in the structure of Ti 3 C> 5 .

in doped samples (at 77 K).

23
 Titanium oxides — Continued
Magneli phases, Ti n O„_i

n: phase Crystal structure, x-T and DTA Electrical properties References

studies

(T = 298 K: All phases are triclinic; space

group. Pi; Z = 2)
4; Th0 7 a = 5.600A; 6 = 7.134 A; c = 12. 468 A; a = Ti 4 0 7 is metallic at 300 K and p [43, 71, 72,
95.05°; 0 =95.20°; 7 = 108.70°; (calc. increases by a factor of 10 3 at 75, 79, 84,
density, 4.32 g/cm 3 ). 149 K on cooling and semicon- 86, 87].
T = 125
( and 149 ±2 K. Discontinuities ductor behavior in the range 130-
in the lattice parameters are noted at 149 K
(Ea ~0.04 eV). At ~125
the 149 K transition; the volume change K,
p shows an increase by about
is <0.001 and the extra reflections three orders of magnitude.
observed below 149 K
suggest a doubling No Seebeck coefficient data
of the unit cell. The 125 transition K available.
is associated with ~8-10 hysteresis K At 300 K, m* «*13m and Hall data
and some structural changes seem to give a mobility of ~1 cm /V 2
s,

take place at this temperature. increasing to 4 at -~160 K; below

DTA (heating curve) indicates both the 149 K, no Hall voltage could be
transitions but the cooling curve indi- measured and hence ph<0.01
cates only the 149 K transition. AH val- cm 2 /V s.

ues not known. Least square refinement of the

X-T data do not indicate the low tempera- structure has shown that the
ture transition. Probably long range mag- sharing of octahedral faces, edges
netic order is absent. and corners between rutile layers
is similar to that in corundum
structures. Average Ti-0 and
0-0 distances are 2.012 and
2.826 A respectively. Average
Ti-Ti distances in a rutile layer
are 2.972 and 3.576 A across a
shared octahedral edge and
comer respectively.
5; Ti 50 9 a = 5.569 A; 6=7.120 A; c = 8.865 A; <* = Discontinuities in p are noted at T t; [43, 71, 72,
97.55°; 0 = 112.34°; y = 108.50°. however, the sample appears to 75, 78, 79,
T< = 130 and 136 K. be semiconducting above 136 K. 84].
DTA and x-T studies show anomalies at Ea (<130 K)~0.04 eV;
these phase transitions; no AH values are m* (>136 K) ~ 11m.
known. Probably long range magnetic
order is absent.
6; TifiOn a = 5.56 A; 6 = 7.14 A; c = 24.04 A; a =98.5°; p dropsby a factor of 10 at 130 K [43, 71, 72,
0 = 120.8°; 7 = 108.5°. T = 122 K. t and the sample is semiconducting 75, 79, 84].
DTA and x-T studies show this transition; both below and above T t.

no AH is known. Probably long range Ea (<130 K)~0.08 eV; m*

magnetic order is absent, ( > 130 K) ~ 16 m. The T noted t

here is less than that obtained

(122 K) from DTA and x-T data.
7; ThOn o = 5.54 A; 6 = 7.13 A; c = 15.36 A; a = 98.9°; No data are available [79, 84].
0 = 125.5°; 7 = 108.5°.
No x-T, DTA data are available.
8; TigOis a = 5.57 A; 6=7.10 A;c = 37.46 A; a=97.2°; Semiconductor behavior in the [75, 79, 84].
0 = 128.8°; 7 = 109.6°. temperature range 78-295 K; no
DTA studies do not indicate a transition in indication of transformation.
the temperature range 78-295 K. x-T Ea ~0.09 eV.
data not available.
9; Ti 9 0i 7 o= 5.57 A; 6 = 7.10 A; c = 22.15 A; a =97.1°; No data are available [79, 84].

0 = 131.0°; 7 = 109.8°.
No x-T, DTA data are available.

24

n
 Titanium oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

Ti 02 ( anatase )

Crystal structure and T =298 K: Careful work up to the transition [150].

x-ray studies. Tetragonal; space group, I4/amd; Z = 4; point; the variation in the relative
a =3.7845 ±0.0001 A; c = 9.5143 ±0.0004 magnitudes of the values of TEC
A. TEC (300-985 K) ( /°C): ||
c
: 7.380 X are explained in terms of the inter-
10-6 +6.620 X10" 9 f + 1.771 X 10 -u ± t
2
;
c
: ionic distances. Earlier literature
3.533 X lO-6 + 5.610 X 10" + 4.315 X
9
t survey presented.
10 -12 1
2
, where t is the temperature in °C.

Kinetics of trans- The rate of transformation of pure anatase The irreversible transformation of [92-98, 100,
formation of anatase is exponential (fig. 1.3); energy of activa- anatase to rutile is reconstructive 102-104].
—» rutile and thermal tion is ~90 kcal/mol. The transition is and involves changes in the
properties. immeasurably slow below 880 K and ex- secondary coordination. The par-
tremely rapid above 1000 K and is accom- ticle size, the crystallite size and
panied by ~8% decrease in the unit cell the volume of the unit cell seem to
volume. A is H ~
—2.8 kcal/mol (exo- increase prior to the trans-
thermic). Impurities usually stabilize the formation. The impurities seem to
the anatase modification; T t as well as act by way of creating anion
the energy of activation are greater in vacancies or cation interstitials
these doped materials compared to pure in stabilizing the anatase phase.
rutile.
Smaller particle size and larger surface
area seem to favor the transition.

Effect of pressure on Discontinuous changes in the resistance of
the transition and
resistivity studies.
the anatase samples noted at T In the
range 3.8-24 kbar pressure, T decreases
with the application of pressure; ( dTt /
dP ) = —0.02° bar -1 p (300 K, pre-
pressed specimens, anatase) ~10 12 Q cm;
p (300 K, pressed at 3.8-24) kbar ~10
7
Q cm.
Detailed work on the effect of [111].
t. pressure on the transition. Aff
t for the transition also decreases
with pressure; the oxygen defi-
, ciency seems to be responsible for
the acceleration of the rate of
transition at higher tempera-
tures. The results are in accord
with the volume change associ-
ated with the anatase-rutile
transition.

Magnetic properties X=0.02X10 -6 emu/g (essentially inde- Not a very accurate value [122a]
of anatase. pendent of temperature) because of the presence of im-
purities; the observed variation
of x with T is expalined on the
basis of the presence of Ti +3 ions
in the anatase samples.
Ti 02 ( brookite )

Crystal structure T = 298 K Data on the naturally occurring [151].

Orthorhombic; space group, Pcab? Z = 8; pure brookite sample; contains
a =9.25±0.03 A; = 5.46±0.02 A; c = fi references to the earlier data.
5.16±0.01 A.

Kinetics of brookite The transition is irreversible and time and The enthalpy of transition is small [115].
rutile transition and temperature dependent (fig. 1.3); below compared to the anatase-rutile
thermal properties. 990 K, the transition is extremely slow. transition. This indicates that
Above 990 K, first order rate law is the polymorphic transformation
obeyed. Energy and entropy of activation may not be of the reconstructive

25
 |

Titanium oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

are ~60 kcal/mol and ~ —18 cal/mol type but only a modified order-
(at 1070 K) respectively. DTA shows an disorder type as applied to
exothermic peak at 1020 K; A —(100 diffusionless transitions in solids.
±75) cal/mol.

Ti 02 (high pressure)

Crystal structure and Orthorhombic; space group, Pban; Z — 4; The high pressure phase reported [90, 91].
transformation to a =4.529 A; 6 = 5.464 A; c = 4.905 A. This by two groups of workers pre-
rutile. phase is formed from rutile at ~330 kbar pared under different experi-
pressure at ordinary temperatures; it re- mental conditions appears to be
verts to rutile on heating at 720-870 K. identical. As expected, the high
A lower bound of 60 kbar is necessary to pressure phase is denser than
stabilize the higher pressure form with rutile and can be retained with-
respect to rutile at room temperature. out changes under normal condi-
tions of temperature and
pressure after quenching for in-
definite periods of time. Anatase
is metastable with respect to the
rutile and the high pressure
forms. Reaction boundaries for
these phases have been reported.
Ti 02 (rutile)

Crystal structure and T — 298 K; Tetragonal, space group, P42/ Careful work up to the high tem- [150, 152].
x-ray studies. mnm; Z = 2; a =4.5941 ±0.0001 A; c = peratures. Slight anisotropy in
2.9589 ±0.0001 A. TEC (303°-923 K) the TEC parameters is obvious
-9
( /°C): ||
c
: 8.816 XlO-«+3.653X IO t + and is explained in terms of the
6.329 X10" 12 t
2
; ± c
: 7.249 X10~ 6 +2.198 interatomic distances in the unit
-9
X10 t + 1.298X 10 -12 t
2
, where t is the cell of rutile.
temperature in °C. High pressure x-ray
studies indicate volume change, (V/Vo)
of 0.91 at 102 kbar [152] and 0.94 at 158
kbar pressure [91].

Magnetic, optical and X = (0.067 ±0.0015) XlO -6 emu/g for high The temperature independent x is [43, HO-
dielectric properties. purity single crystal rutile and tempera- due to diamagnetic and Van 121, 122b,
ture independent in the range 55-372 K; Vleck contributions. The free car- 123a, 153].
negligible anisotropy. rier absorption due to the elec-
is

Stoichiometric rutile shows continuous trons released by the oxygen upon

absorption in the
reduced samples exhibit free career ab-
sorption and characteristic bands (at 0.75
or 1.18 eV) depending on the sample re-
sistivity or degree of reduction. Optical
energy gap = 3.05 eV.
and exhibits anisotropy; at 300 K, eo
(||<0 =170; eodl*) =86; n(|K> 2.903; n(||*)
IR region [122b] but reduction; the bands in the re-
duced samples are believed to be
due to polaron absorption. The
environment of Ti sites in rutile,
the anisotropy and high numerical
eo has a high value values of eo make an interesting
comparison with BaTiC>3.

= 2.616.
At low temperatures, eo approaches limit-
ing values; at T—>0 K, «o(| c ) = 257 ; e 0 (||°)

= 111.Parker’s data [153] in the range

1.6-1060 K
indicate that rutile is not a
ferroelectric or antiferroelectric; how-
ever, the ionic polarizability of Ti is close

26
 Titanium oxides —Continued
Oxide and description Data Remarks and inferences References
of the study

to the critical value for a ferroelectric

polarization catastrophe at all tempera-
tures.

Electrical properties p (300 K) ~10 8 ficm for stoichiometric ru- Multiple band conduction is indi- [116-125a,
and high pressure tile; £
~3.1-3.4 eV; impurity conduction
ff
cated by the p, Rh and a data 154].
studies. is always predominant at low tempera- but many workers feel that
tures; donor levels of 0.03-0.15 eV are en- polaron type conduction is pre-
countered. dominant at low temperatures.
Reduced specimens have low resistivity The defect structure of Ti0 2 is

(~10 -2 to 10 4 Slcm), are n-type and ex- not yet completely understood.
hibit anisotropy in Rh, he and p. Aniso- Kawai and Mochizuki [125a]
tropy ratios, (po/pe) and ( Ra /Rc)H vary experiments at high pressures on
from 2.0 to 3.5 and 0.2 to 2.5 respectively the p behavior of Ti0 2 are signifi-
and exhibit interesting temperature de- cant; x-ray data at these high
pendence. pressures are highly desirable
p.H~ 0.1cm /V s. at 500 K; a (100 K) =
2
and will indicate whether the
— 1.0 mV/K. m* =20 mo. a shows large resistivity behavior actually
phonon drag effect at T below 20 K. corresponds to the insulator-
~lln
In the range 882-1273 K, p po 2 , metal (Mott) transition or not.
n 4.4 to 5.7; n =4 above 1470 K according
to Greener et al. [123]; both anion vacan-
cies and cation appear to play
interstitials
significant role. Ea (T>1000 K) =1.8 eV.
High pressure studies indicate a large
decrease in p up to 6 kbar ( dp/dP = —0.2
-1
XlO 4 flbar ); in the range 6-100 kbar,
change in p is small {dp/dP = 0.08 fihar -1 ).
Data of Kawai and Mochizuki [125a]
indicate that at pressures >2Mbar p of
Ti0 2 drops by a factor of 10® and ex-
hibits metallic behavior at room tem-
perature.

Thermal and Cp — 1 millijoule/K, mol at 4.2 K; CP ^T 3

It is evident that the degree and [118, 123c,
mechanical below 4 K with 0 d = 758 K. type of reduction brings about 155].
properties. Reduced Ti0 2 has large additional con- marked changes in these proper
tribution and independent of T below 13 ties in rutile.

K and is attributed to electrons which do

not become degenerate above 1 K.
k (200 K)=0.1 W/cm, K and exhibits
anisotropy above 25 K; goes through a
maximum at ~15 K indicating phonon-
phonon scattering in Ti0 2 .

Internal friction ( Q -1 ) goes through a

maximum at 323° in pure rutile with Q~ l
(| ;°) = 1 X 10 -4 at 1842 Hz and activation
energy of Reduced
14 ±0.4 kcal/mol.
rutile pronounced maximum
exhibits a
(()-i(||«)=12xl0— 4 at 394 K and 1838
Hz with activation energy = 23.5±1.0
kcal/mol) only along [100] direction and
not along [110] and [001] direction. The
results are discussed in terms of simple
and associated defects in pure and re-
duced rutile.

27
 Titanium oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

Band structure of Calculations using tight binding method in- Since there are no magnetic order [156].
rutile dicate relatively wide valence and con- complications in Ti 02 it is worth
duction bands (^-4 eV). The available while to compute the detailed
transport data can be interpreted assum- band structure of Ti 02 using
ing multiband conduction in Ti 02 even at various methods including spin-
low temperatures (~100 K). orbit coupling effects.

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[77] Iwasaki, H., Bright, N. F. H., and Rowland, J. F.,
J. Less-Comm. Metals 17, 99 (1969).
[78] Andersson, S., Acta Chem. Scand. 14, 1161 (1960).
[79] Magneli, A., in Transition Metal Compounds, Ed. E. R.
Schatz, (Gordon and Breach, Science Publishers, New
York, 1964), pp 109-122.
[80] Andersson, S., and Jahnberg, L., Arkiv for Kemi 21,
413 (1963).
[81] Anderson, J. S., and Hyde, B. G., Bull. Soc. Chim.
France 4, 1215 (1965); J. Phys. Chem. Solids 28,
1393 (1967).
[82] Magneli, A., in The Chemistry of Extended Defects in
non-Metallic Solids, Eds. L. Eyring and M. O’Keeffe
(North-Holland Publ. Co., Amsterdam, 1970), pp
148-163 and references therein.
[83] Anderson, J. S., and Khan, A. S., J. Less-Comm. Metals
22, 219 (1970).
Terasaki, O., and Watanabe, D., Japan Appl. Phys.
[84] J.
10, 292 (1971).
[85] Goodenough, J. B., Czech. J. Phys. 17B, 304 (1967).
[86] Marezio, M., Dernier, P. D., McWhan, D. B., and
Remeika, J. P., Mat. Res. Bull. 5, 1015 (1970);
See also, Marezio, M., and Dernier, P. D., J. Solid
State Chem. 3, 340 (1971).
[87] Nagasawa, K., Kato, Y., Bando, Y., and Takada, T.,
J. Phys. Soc. Japan 29, 241 (1970).
[88] Straumanis, M. E., Eijma, T., and James, W. J., Acta
Cryst. 14, 493 (1961).
[89] Dachille, F., and Roy, R., Bull. Amer. Ceram. Soc. 41,
225 (1962).
[90] Bendeliani, N. A., Popova, S. P., and Vereschagin,
L. F., Geokhimiya 5, 499 (1966); Chem. Abstr. 65,
3296f (1966).
[91] McQueen, R. G., Jamieson, J. C., and Marsh,
[112] Kubo, T., Kato, M., Mitarai, Y., Takahashi, j., and
Ohkura, K., Kogvo Kagaku Zasshi 66, 318 (1963);
Chem. Abstr. 59, 10824f (1963).
[113] Tekiz, Y., and Legrand, C., Compt. Rend. (Paris) 261,
3619 (1965).
[114] Schossberger, F., Z. Krist. 104, 358 (1942).
[115] Rao, C. N. R., Yoganarasimhan, S. R., and Faeth,
P. A., Trans. Faraday Soc. 57, 504 (1961).
[116] Frederikse, H. P. R., J. Appl. Phys. 32 2211 (1961).
[117] Becker, J. H., and Hosier, W. R., Phvs. Rev. 137A,
1872 (1965).
[118] Thurber, W. R., and Mante, A. J. H., Phys. Rev.
139A, 1655 (1965).
[119] Bogomolov, V. N., and Zhuze, V. P., Sov. Phys. Solid —
State (Enghsh Transl.) 8, 1904 (1967).
[120] Bogomolov, V. N., Kudinov, E. K., and Firsov, Yu. A.,
—
Sov. Phys. Sohd State (Enghsh Transl.) 9, 2502
(1968).
[121] Grant, F. A., Rev. Mod. Phvs. 31, 646 (1959).
[122] Austin, I. G., and Mott, N. F., Adv. Phys. 18, 41 (1969).
[122a] Senftle, F. E., Pankey, T., and Grant, F. A., Phys.
Rev. 120, 820 (1960).
[122b] Breckenridge, R. G., and Hosier, W. R., Phys. Rev.
91, 793 (1953).
[122c] Acket, G. A., and Volger, J., Physica 29, 225 (1963);
Phys. Letters 8, 244 (1964).
[122d] Bogomolov, V. N., and Shavkunov, P. M., Sov. Phys.
Sohd State (Enghsh Transl.) 5, 1481 (1963).
[123] Greener, E. H., Barone, F. J., and Hirthe, W. M.,
J. Am. Ceram. Soc. 48, 623 (1965).
[123a] Hauffe, K., Reaktionen in und an festen stoffen,
(Springer Verlag, Berhn, 1955), pp 135-140.
[123b] Rudolph, J., Z. ISaturforsch. 14a, 727 (1959).
[123c] Wachtman, J. B., Jr. and Doyle, L. R., Phvs. Rev.
135, A276 (1964).
[124] Vahldiek, F. H., J. Less-Comm. Metals 14, 133 (1968).
[125] Minomura, S., and Drickamer, H. G., J. Appl. Phys.
34, 3043 (1963).
[126] Marinder, B.-O., and Magneli, A., Acta Chem. Scand.
11, 1635 (1957).
[127] Riidorff, W., Walter, G., and Stadler, J., Z. anorg.
S. P., allgem. Chem. 297, 1 (1958).

29
 —

[128] Ariya, S. M., and Grossman, G., Sov. Phys. —

Solid et al. [15], Abei [16], and Kosuge [17]; in the range
State (English Transl.) 2, 1166 (1960).
[129] Sakata, K., and Sakata, T., Japan J. Appl. Phys. 6, 112 V0-V 0 by Andersson [18] and Andersson
2 6, [19] and
(1967). in the range VO -V O by MacChesney et
2 2 5, al. [20],
[130] Kristensen, I. K., J. Appl. Phys. 39, 5341 (1968).
[131] Rao, C. N. R., Natarajan, M., Subba Rao, G. V., and Theobald et al. [21], Sata et al. [22, 23], and Tilley
Loehman, R. E., J. Phys. Chem. Solids 32, 1147 and Hyde [24]. The available data have been sum-
(1971).
[132] Ksendzov, "Va. M., and Prokhvatilov, V. G., Zhur. Fiz. marized by a few workers [25, 26]. Stringer [26]
Khim. 31, 321 (1957). constructed a schematic phase diagram and sug-
[133] Keler, E. K., and Andreeva, A. B., Ogneupory 25, 320
(1960); Chem. Abstr. 54, 25663i (1960). gested a systematic nomenclature of the phases. A
[134] Marinder, B.-O., Dorm, E., and Seleborg, A., Acta modified phase diagram of Stringer [26] and
Chem. Scand. 16, 293 (1962).
[135] Riidorff, W., and Luginsland, H. H., Z. anorg. allgem. MacChesney et al. [20] (in the region VO 2 -V 2 O 5 )
Chem. 334, 125 (1964). are shown in figure 1.4.
[136] Sakata, K., Nishida, I., Matsushima, M., and Sakata,
T., J. Phys. Soc. Japan 27, 506 (1969). The V -0 system is quite a complex one. In addi-
[137] Chang, L. L. Y., Scroger, M. G., and Phillips, B., tion to the stable compounds like V2O3, VO2, and
J. Less-Comm. Metals 12, 51 (1967).
[138] Chang, L. L. Y., J. Am. Ceram. Soc. 51, 295 (1968). V 2 0 5 having narrow homogeneity ranges, compounds
[139] McDaniel, C. L., and Schneider, S. J., J. Res. Nat. Bur. with wide homogeneity range like VO, Magneli pha-
Stand. (U.S.), 71A (Phys. and Chem.), No. 2, 119-123
(Mar. Apr. 1967). ses of the general formula V n 02 n -i (4^n^8) and
[140] Samakhvalov, A. A., and Rustamov, A. G., Sov. Phys. V n 02n+i (n = 3, 4, and 6 ) exist. Several new unidenti-
Solid State (English Transl.) 5, 877 (1963).
[141] Kawano, S., Japan J. Appl. Phys. 8, 1264 (1969). fied phases also exist in the region VO2-V2O5 [21-24].
[142] Rao, C. N. R., Wahnsiealer, W. E., and Honig, J. M., Oxygen forms a solid solution with metallic vanad-
J. Solid State Chem. 2, 315 (1970).
[143] Yamashita, J., J. Phys. Soc. Japan 18, 1010 (1963). ium up to about 11 mol percent (VO0.4) distorting
[144] Ern, V., and Switendick, A. C., Phys. Rev. 137A, the cubic lattice of V Range VO0.6-VO0.8
[1, 2, 5 ].
1927 (1965).
[145] Schoen, J. M., and Denker, S. P., Phys. Rev. 184, 864 has not been accurately studied.
(1969). Vanadium monoxide has a wide homogeneity
[146] Harker, D„ J. Chem. Phys. 12, 315 (1944).
[147] Watanabe, D., Acta Cryst. 10, 483 (1957); J. Phys. range (VO 0 85 -VO 27 ) and all
. 1 .
the compositions have
Soc. Japan 15, 1251 (1960). been investigated experimentally. VO 1.5 (V 2 C> 3 )ap-
[148] —
Samokhvalov, A. A., Sov. Phys. Solid State (English
pears to have a very narrow range of homogeneity
Transl.) 3, 2613 (1962).
[149] Mooradian, A., and Raccah, P. M., Phys. Rev. B3,
[27]; different phases have been detected in alloys
4253 (1971).
[150] Krishna Rao, K. V., Nagender Naidu, S. V., and having compositions VO 1.44 and VOi.es. The existence
Iyengar, L., J. Am. Ceram. Soc. 53, 124 (1970). and stability of the Magneli phases, VnChn-i* with re-
[151] Yoganarasimhan, S. R., and Rao, C. N. R., Anal.
Chem. 33, 155 (1961). spect to the oxygen partial pressure and tempera-
[152] Clendenen, R. L., and Drickamer, H. G., J. Chem. ture have been examined by various workers [9, 11,
Phys. 44, 4223 (1966).
[153] Parker, R. A., Phys. Rev. 124, 1719 (1961). 12 , 17, 18]. VO 2 (V n 0 2 „_i, ) has a narrow n= 00

[154] Hernandez, W. C., and Kahn, A. H., J. Res. Nat. Bur. homogeneity range [10, 28]. Besides V 2 O 5 in the ,
Stand. (U.S.), 67A (Phys. and Chem.), No. 4, 293-299
(July-Aug. 1963). series V„0 2 „ + i, V 3 O 7 [29], V 4 0 9 [30] and V 6 0i 3 [18]
[155] Keesom, P. H., and Pearlman, N., Phys. Rev. 112, 800 have been prepared and characterized.
(1958).
[156] Kahn, A. H., Frederikse, H. P. R., and Becker, J. H.,
in Transition Metal Compounds, Ed. E. R. Schatz
VO: VO is unique in having an extremely wide
(Gordon and Breach, Science Publishers, New York,
1964). composition range essentially symmetric about the
stoichiometric composition together with an extra-
1.3. Vanadium Oxides ordinarily high vacancy content (^20%). It has a
cubic rock salt structure and the lattice parameter a
The vanadium-oxygen system has been extensively increases with increasing oxygen content but the
studied by several workers in the different homo- density decreases; however, the increase in a is not
geneity ranges by employing a variety techniques. linear with x in \O x whereas the density versus x
In the range V-VO, by Seybolt and Sumsion [1], plot is linear. According to the recent study on well-
Schonberg [2], Rostoker and Yamamoto [3], Ozerov characterized and annealed VO x samples, the lower
[4], and Cambini et al. 5 ]; in the range V-V2O3, by
[
limit for the single phase cubic region appears to
Klemm and Grimm 6 ], and Westmann and Nord-
[ be between 0.75 and 0.79 and the upper limit, 1.30
mark [ by Morozova et al.
7 ]; in the range V2O3-V2O4, [31]. Mathewson et al. [32] first noticed that the
[
8 ], Katsura and Hasegawa [9], and recently by x-ray density of VO 1.00 (6.50 g/cm 3 ) is approxi-
Kimizuka et al. [10], Okinaka et al. [11], and Ander- mately 15 percent higher than the pycknometric
son and Khan 12 ]; in the range V2O3-V2O5, by
[
value (5.6 g/cm 3 ) suggesting that the lattice is highly
Hoschek and Klemm [13], Burdese [14], Grossman defective at the stoichiometric composition. The

30
 Figure 1.4. (a) V-0 phase diagram ( after [26]). The various
phases and stability ranges have been discussed in detail by
Stringer, (b) VO2-V2O5 phase diagram showing the VnChn+i
phases ( after [20]).

variation of the defect concentration of the cationic Because of the wide homogeneity range and large
and anionic lattices across the phase field has been number of vacancies, VO* shows interesting physical
examined by many workers [7, 27, 31, 33-36]. At and chemical properties. With increase in * in VO x ,

the oxygen rich phase limit the anion lattice is p, dp dT, and xm increase linearly with abrupt in-
nearly perfect with almost zero anion vacancies while creases in slopes at x = 1.00, while a changes smoothly
at the vanadium rich phase limit, however, the cation from n-type to p-type at *=1.02. The metal rich
lattice still contains ~13 percent vacancies. Banus VO is a semimetal with weak temperature-inde-
and Reed [31] and Taylor and Doyle [36] have found pendent paramagnetism and higher * changes to a
that annealing the VO x at high temperatures (~1570 semiconductor with a small energy gap and a strong-
K) and high pressures (^50-60 kbar) decreases the er temperature-dependent paramagnetism. Con-
total number of vacancies (by about 6-13%) re- trary to the earlier reports [37-40], recent studies on
sulting in an increase in the density by ~1 percent well characterized samples of VO x indicated no
and a 0.1 percent increase in the lattice parameter. metal-to-semiconductor transition for any composi-
These changes are unambiguously the result of the tion on decreasing the temperature to 77 K [31,
high pressure treatment, since reannealing the sam- 35, 41-43]. Oxygen rich VO shows [31] only a weak
ples at 1 atm pressure at 1570 K gave samples with temperature dependent paramagnetism in the range
the same lattice parameter as the material before 4.3 to 273 K with no evidence of magnetic ordering,
pressure treatment. Loehman, Rao, and Honig [35] in contrast to the findings of Kawano et al. [41]
have found that the vacancies in VO can be reduced who observed definite evidence of antiferromagnetic
by solid solution with TiO. ordering for *=1.15 and 1.26.

31
 The decrease in vacancy concentration on anneal*
ing at high pressure results in slight changes in the
and magnetic properties. The pressure
electrical
annealing of VO does not significantly change the
magnitude of p, the slope of p versus T or Xm. At all
compositions, there is a 10-20 percent decrease in
Xm in the range 4.2-100 K; a decrease in anion
vacancies (caused by pressure anneal) affects the
Xm in an opposite direction to that caused by in-
crease in x. This indicates that xm is more sensitive

to the cation vacancies than the anion vacancies.

The magnitude of a increases after pressure anneal-
ing and VO1.02 changes from n-type to p-type be-
havior.

V2O3: Vanadium sesquioxide, V2O3, exhibits two

Figure 1.5. Variation of the c/ a ratio of V 2 O 3 with temperature
transitions. Because of the dramatic changes in
[63].
physical properties accompanying these phase transi- At the transition temperature we see a drastic change in the ratio. Chromium
substitution markedly affects the c/a ratio. In the Insert we have shown
tions and the unique behavior with respect to pres-
the variation of c/a ratio in various sesquioxides; the ratio is anomalously
sure, temperature and impurity content, this oxide high in V2O3 and low in T12O3.

has been studied extensively in recent years both

from theoretical and experimental points of view. V atom. Neutron diffraction [65] and magnetic sus-
The metal-to-insulator transition exhibited by V2O3 ceptibility studies [66-68] indicate that the anti-
is a field of intense research activity at the present ferromagnetic ordering in V2O3 disappears at the
time (See fig. 2 in the introduction) and several transition point (154 K) where the crystallographic
review articles have recently appeared [44-56] on transition also occurs. The high temperature anomaly
this aspect of the problem. isassociated with a discontinuity in the Xm, but the
At room temperature, V2O3 has the corundum substance remains paramagnetic throughout the tem-
structure with rhombohedral symmetry [57, 58]. perature range, 150 to 1000 K [68].
There is a unique c axis perpendicular to the basal Associated with the phase transitions in V2O3,
plane which contains three identical crystal axes. there occur dramatic changes in the electrical proper-
Near 150 K, a phase transition occurs to the mono- ties.At room temperature, V2O3 is a fairly good
clinic structure [59-64] involving a slight tilting of metal (with the purest samples showing resistivities
the hexagonal c axis of the rhombohedral phase. of the order of 10 -3 cm and a positive temperature
The transition accompanied by discontinuous
is coefficient of p). When the temperature is decreased
changes in the c/a ratio (fig. 1.5) and the unit cell to 150 K (crystallographic transition point), it un-
volume (increase by about 1.4 percent) [63]. There dergoes a transition from the metallic state to an
is also a high temperature anomaly in V0O3 around insulating state with an accompanying increase in
500 K where there is no change in the crvstal param- resistivity by about seven orders of magnitude. This
eters [63]; Kosuge [17], however, finds a DTA transi- transition has been first discovered by Foex [69]
tion at 430 K. Recent neutron diffraction study on and since then confirmed by many workers [37, 38,
V2O3 [65] has confirmed the presence of antiferro- 63, 66, 70-78]. The characteristic metallic resistivity
magnetic ordering in the low temperature mono- in V2O3 shows an anomaly in the high temperature
clinic phase (earlier measurements using various region as well. Both the c axis and basal plane re-
techniques gave contradictory conclusions; see, for sistivities show a rapid increase with temperature
example, reference [53]). According to Moon [65], in the region near 525 K, but keep monotically in-
the antiferromagnetic axis lies in a plane parallel to creasing up to 800 K [76]. Foex et al. [66] on the
the c axis (in the hexagonal and perpendicular
cell) other hand, have noted a maximum at 525 K and
to one of the a axes and makes an angle of about 71° a semiconductor behavior in V2O3 above 525 K.
to the c axis in this plane; the V moments are ferro- Discontinuity in a was noted at the low temperature
magnctically coupled monoclinic (010)
in or crystallographic transition in V2O3 [78, 79]. Above
hexagonal (110) layers, with a reversal between 150 K, a was positive and small and below this tem-
adjacent layers. The ordered moment is 1.2 pu per perature, it changed sign and became very small.

32
 Rh was negative in the entire range of temperature
studied (7-800 K) and did not indicate any anomaly;
a did not indicate anomaly at the high temperature
transition of V2O3 [78].
X-type anomalies are noted in the heat capacities
at the low and high temperature transitions in V2O3
[66, 80]; DTA studies indicate endothermic peaks
i corresponding to the transitions [17]. Anomalous
behavior of V2O3 in the region of the transition point
has been noted in the measurements made by a
variety of techniques like NMR spectroscopy [81-
84], Mossbauer spectroscopy [74], positron annihila-
tion [85], UHF (^10 GHz) dielectric constant [86]
and optical spectroscopy [76, 87].
The on the transition has been
effect of pressure
studied by a few workers [38, 39, 61, 76, 77]. The
transition temperature ( \= Tn) decreases with pres-
sure (~4 K/kbar). Application of pressures greater
than 25 kbar suppresses the transition completely
[77] and V2O3 remains metallic and Pauli paramag-
netic down to 2.2 K without indication of any long
range magnetic order.
All the available data seem to establish that the Figure 1.6. Pressure-temperature-composition (Cr) phase dia-
low temperature transition in pure V2O3 is of first gram (Vi_zCr*) 20 3.

M, I, and AFM insulator phases have been indicated; the metal-insulator

order and the high temperature one is of second phase boundary terminates at a critical point (~530 K) (after [63]).

order.The low temperature transition is sharp and

marked by a hysteresis. T t
is sensitive to stoichio- titanium doping. Three types of phases have been
metry [88] and the magnitude of the discontinuity suggested to be present in V2O3: the metallic (M),
in p seems to depend on sample purity and stress. the insulating (I) and antiferromagnetic insulating

The properties of the metallic state of V2O3 are (AF) phases. Depending on the temperature, pres-
highly anomalous and they change rapidly with sure and dopant concentration, all the three phases
pressure in the direction of making it more metallic. and the transitions between any two (M^I; M^AF;
It, therefore, appears that pure V
Os is near a critical
2 AF^I) can be realized experimentally. The tem-
region and that the application of negative pressure perature-pressure-composition phase diagram for
would induce a transition; doping with chromium (Vi_.Cr.)i0 3 is reproduced in figure 1.6.
has an empirical correspondance with the negative At room temperature and atmospheric pressure,
pressure, and indeed, it is found that a metal -to- pure V2O3 is situated in the metallic phase. As the
insulator transition occurs with Cr doping in this temperature is lowered, the undoped material passes
material. through the M-AF phase surface at ~160 K. Con-
As early as 1949, Mott [89] predicted that an versely, as the temperature is raised, pure V2O8 ap-
abrupt metal-insulator (collective electron-localized pears to pass through the extension of the M-I
electron) transition will occur in an ionic solid when phase boundary at ^550 K. However, the M-I
the interionic separation is forced to pass through a phase boundary terminates at a critical point (fig.
critical value. Since each of the two resistance 1.6), so that the high temperature transition in pure
anomalies in V2O3 accompanied by an anomaly in
is V2O3 reflects a critical behavior. The phase transition
the thermal expansion, it would appear that they is no longer a well-defined, abrupt, first order transi-

may both be metal-insulator transitions of the type tion, but is a gradual change from metallic to in-
envisioned by Mott. The basis for the ideas that the sulating behavior. When a small percentage of Cr
V2O3 transitions are Mott-type transitions is con- ions is substituted for vanadium in V2O3, a definite
tained in the recent work of McWhan and co-workers first order phase transition between the metallic
[62, 63, 84, 90]. These workers have examined the and insulating phases exists, with the transition
resistivity and the lattice distortion of V 2 0 3 as a temperature rapidly decreasing as a function of
function of pressure, temperature, and chromium and chromium doping. At a critical concentration (^3

33
 I n

percent), the M— >1 and M—»AF transition tempera- faults into which extra planes of metal atoms are
tures are equal (~160 K). For Cr dopings greater introduced. Because of the shear planes, metal-metal
than 3 percent, an intermediate metallic state does bonding can occur leading to interesting electrical
not exist and the only observed transition is a direct and magnetic properties. Whenever these metal-
I—>AF transition (at atmospheric pressure). Similar- metal bonds are broken up, anomalies in the physical
ly, at a given temperature (say, 298 K) and Cr- properties occur, but there appears to be no case
concentration (say, 4 percent), I—»M transition can where structural transformation occurs; only a dis-
take place with the application of pressure without continuity in the lattice parameters is noticed.
the intervening AF phase. Doping with increasing Nagasawa and co-workers have grown single crystals
amounts of Ti has the empirical correspondance to of these Magneli phases by the vapor transport
the application of pressure (3.6 kbar/atom %) and method [94-97] and have carried out various meas-
the system tends to become more and more metallic urements.
[79]; at about 7 atom percent Ti, both the transitions V3O5, even though it corresponds to V n 0 2n _i with

in V 2 O 3 are suppressed and the system is metallic in n = 3, is not a Magneli phase since the structure is
the entire range of temperatures as is the case in different (monoclinic). It shows a discontinuity in
pure V2O3 above 25 kbar pressure [62]. the x-T plot around 133 K
[95], but in contrast to
Various theories have been put forward to explain the earlier studies [73] (which showed a semiconduc-
the metal-insulator transitions in oxide materials tor-to-metal transition in the range 150 to 180 K),
([91-93]; for a review of various earlier theories see only a semiconductor behavior was noted in the
but each of them is able to explain the experi-
[53]), range 130 to 300 K [72, 98]. Kosuge [17] does not
mental findings on a specific oxide material and fail observe a DTA peak, or a x-T anomaly. X-ray
to explain the behavior of other oxides. Any discus- studies of Asbrink et al. [99] up to 1270 K, also do
sion of the theories would be outside the scope of not indicate a phase transition.
this review and it would suffice to point out that Magnetic susceptibility and electrical transport
there is still a need for unifying theoretical appro- (on single crystal materials), x-ray, DTA and Moss-
aches to the understanding of metal-insulator transi- bauer studies indicate semiconductor-to-metal tran-
tions. In figure 1.7 we have shown the schematic sitions (on heating; first order) in V4O7 at 250db5 K
band structure of VO
2 3 (following Goodenough) in [17, 94, 100, 101]; in V0 5 9 at 135±5 K [17, 96, 102];
the rhombohedral, nonmagnetic monoclinic and in V Ou
6 at 177 ±2 K [17, 95, 103]; in V0 8 15 at 70 K
magnetic monoclinic structures to illustrate the na- [97, 104, 105]. Detailed studies [17, 94, 103] indicate
ture of changes accompanying the low-temperature that V7O13 paramagnetic (Pauli ?) and metallic
is

transition. in the range 4.2 to300 K. In their recent study pub-

lished in 1973, Kachi, Kosuge, and Okinaka [105]
Vn 0 2 „_i: The Magneli phases, Vn 0 2n -i, (4^n^8), have presented the data on all the V n 02 n-i ( =
have a triclinic structure based upon the rutile struc- 3-9) systems and find that all but V3O5 and V7O13
ture with periodic sheared planes resembling stacking show metal -sinulstor transitions. These workers
have established the phase relationships and struc-
tures of these oxides.
bgeji.j-ri.j — t i c*p It is difficult to rationalize this wealth of experi-
ttH « I

— -iteTCH m "1— c»d

mental data without a proper understanding of the
theory underlying the semiconductor-to-metal transi-
day theory has not yet
tions; unfortunately, present
developed to such sophistication, to satisfactorily
explain the transitions even in simple substances
likeV2O3 and VO2. However, in the V„02n_i series,
two important generalizations may be noted: (i) all
the phases are triclinic and detailed x-ray study on
V4O7 indicate no crystal structure change at 7\, but
only discontinuity in lattice parameters. Probably

monoclinic
the same case may be true for other Magneli phases
as well, (ii) Recent studies [105] show that there is

Figure 1.7. Changes in the d-electron band strurture of V 2 O 3

antiferromagnetic ordering in all the V n 02 n-i phases
accompanying the transition at ~150 K ( After Goodenough). at low temperatures in addition to first order transi-

34
tions in many of them at higher temperatures; in the stabilization of this phase by way of Magneli
these respects, these phases are similar to V2O3. It defects [115, 116] 2 .

appears that the first order transitions in these The on the VO 2 transition has
effect of pressure
Magneli phases are explainable in terms of Good- been examined by a few workers [39, 61, 140]. T t

enough’s qualitative picture ([44, 106, 107]; for a de- increases linearly with pressure at a rate of 0.082 dt
tailed discussion, see [53]) of metal-metal bonding 0.005°C/kbar. The conductivity activation energy
and trapping of the conduction electrons in the in the semiconducting phase decreases linearly with
semiconducting phase and the breaking of these pressure typically at a rate of 1-2 /kbar. Assum- mV
bonds and creation of Fermi surface at T in the t ing intrinsic behavior below T t for V0 2, this indi-
high temperature metallic phase. Like VO V n 02„_i
2, cates that the carrier concentration increases with
oxides also show only a single transition (V2O3 and pressure but no metallic conduction is encountered
T14O7 on the other hand, show two transitions). up to pressures of ~300 kbar at 300 K.
The effect of various impurities on the temperature
VO 2 : Vanadium dioxide, V0 2, exhibits a crystallo- and nature of the transition in VO 2 has been in-
graphic transition at 340 K. The transition is accom- vestigated extensively in the literature. Many ele-
panied by interesting changes in physical properties ments like Ti, Nb, Mo, Tc, Ta, W, and Re, form
(see fig. 2 in introduction). In view of the possible complete solid solutions with VO 2 [113, 116, 120,
practical applications of this material in electrical 121, 133, 141-148] and at appreciable concentrations
switching circuits and in other devices, the crystal stabilize the high temperature rutile from of V0 2

growth and physical properties of this material have at room temperature; the T t of VO 2 is lowered
been extensively studied and reviewed by various appreciably and the nature of the transition (at not
workers in recent years [44-56, 108]. too high impurity concentrations) is changed from
V0 2 is monoclinic at room temperature [101, 109- that of a semiconductor-to-metal to that of a semi-
113] and transforms to a tetragonal rutile structure conductor -to-semiconductor. The same effect is pro-
at 340 K [101, 114-116]. The transition is of first duced by the addition of ions like Fe, Co, and Ni,
order and is accompanied by hysteresis effects and but Al, Cr, and Ge raise the T t appreciably [133,
changes in latent heat and volume [101, 114-119]. 146, 148]. Unfortunately, each system is compli-
Magnetic susceptibility [15, 114, 117, 119-122], cated in itself and no generalizations are possible on
Mossbauer [75, 123] and NMR
[84, 124, 125] studies the effect of impurities on the transition in VO 2

have failed to show any evidence of long range until the detailed mechanism of the semiconductor-
magnetic ordering in V0 2 in the temperature range metal transition in pure VO 2 is clearly understood.
1.7 to 400 K; however, a jump in x is noted at T t
Since long range magnetic order is absent in VO 2,

and x is almost temperature independent both above it might be considered that the Adler-Brooks crystal
and below T The electrical characteristics of VO 2
t. distortion model ([149, 53]) would be applicable to
change from those of a semiconductor to those of a the transition in V0 2 but quantitative agreement
,

metal at T with a large drop in resistivity (by a

t
between theory and experiment is lacking [56, 108,
factor of ~10 5 for pure and single crystalline ma- 134]. Since the metal -metal bonding in V0 2 and
terial) [37, 73, 75, 113, 114, 117, 126-134]. Seebeck other rutile type oxides at low temperatures has been
coefficient [117, 128, 135, 136] and Hall effect [130, established beyond doubt, Goodenough’s approach
137] also show anomalies at T t. Studies of DTA seems to be applicable (for detailed discussion, see
[17, 113, 116], heat capacity [114, 117, 138] as well [53]), but the treatment is only qualitative. Paul
as infrared spectra and other optical properties [130, [108], Hyland [56], and others [150, 151] strongly
139] clearly show the 7
first order nature of the transi- argue for an electron-phonon interaction mechanism
tion in this material, but thermal conductivity does and phonon instability [152] as the basic driving
not show an anomaly at T t [117]. force for the transition in V0 2 In figure 1.8 we have .

Recently, some workers have found evidence for shown the elementary band structure scheme for
the existence of an intermediate triclinic phase of tetragonal and monoclinic VO 2 to illustrate the na-
VO 2 in the range 325 to 340 K by means of NMR ture of changes accompanying the transition.
[125], DTA [116] and x-ray diffraction [115] studies.
The temperature range of stability of this inter- 2
1 16a] J. Solid State Chem. 3: 490
Goodenough, [ (1971), has recently
identified two distinguishable mechanisms of the monoclinic-tetragonal
mediate phase may become vanishingly small for transition ofVO 2 an antiferroelectric-paraelectric transition at a tempera-
:

ture Tt and a change from homopolar to metallic V-V bonding at T t Both

pure V0 2 [101], but impurities like Al, Fe, Cr, Mo, K
T and T / are at 340 in pure VO 2 In the presence of impurities the two
.
•

and hydrogen reduction appear to be effective in

components seem to get separated with T t <T
(see ref. [136], and [148] for
example).

35
 .

hombic [30] whereas V 3 O 7 has a monoclinic crystal

w J {
w symmetry [29, 154, 155] at room temperature and
decomposes at 930 K. No DTA peak was noticed
by Kosuge [17] in the range 130 to 950 K. The other
physical properties are not yet known.
Vanadium pentoxide has a narrow range of homo-
geneity [26]. It is orthorhombic at room tempera-
ture and has a corrugated sheet type structure and
is built up from distorted trigonal bipyramidal co-

(a) (b) ordination polyhedra of oxygens around vanadium,

Tetragonal V0 2 Monoclinic V 2 04 sharing edges to form zig-zag double chains along
[001] and are cross-linked along [100] through shared
corners, thus forming sheets in the xz plane [156-
Figure 1.8. Schematic band structure of VO 2 in the monoclinic 159]. This special type of structure predicts aniso-
and tetragonal phases ( after Goodenough )
tropy in thermal expansion of the lattice parameters
and is observed experimentally [160-162]. V2O5 does
V n Oon+i 5 VeOi 3 is monoclinic at room temperature not show any phase transformations up to the melt-
[16, 18]. Kosuge [17] reported an endothermic peak ing point (~940 K) at one
atmosphere [17, 163].
in DTA at 177 K where a X-T anomaly has also been Minomura and Drickamer [39] have noticed a phase
noted. Recently, Kanazawa [153] has noticed a semi- transition in V02 5 at pressures ~100-105 kbar,
conductor-to-metal transition (on heating) in this associated with a large increase in the resistivity.
material at 149 K with a drop in resistivity by a V2O5 remains semiconducting both below and above
factor of 10 4 . The transition may be first order but the transition. Electrical properties and the mech-
the structure of the low temperature phase is not anism of conduction in V2O5 have been discussed
yet established. by a few workers [164-169]. Small amounts of alkali
In the series V n 0 2n +i, in which V2O5 and V 0i36 and other metals form 'vanadium bronzes’ with
are known members, V4O9 and V3O7 have been re- V2 0 5 These important materials have been discussed
.

cently prepared and characterized. V4O9 is orthor- in detail in the literature [53, 170].

Vanadium oxides

Oxide and description Data Remarks and inferences References

of the study

0
a, A Density % Va- P a Xm
Oxide (cubic, (g/cm 3 ) cancies (300 K) (mV/ (273 K)
rock salt) (Total) (Ocm) °C)

VO
Crystal structure and VO0.86 4.034 5.736 37.0
-
6 .OXIO 4 -10.9 0.5X10 - 3 [31, 35].
physical properties of VO* VO0.99 4.068 5.602 30.8 2.2 X 10~ 3 -4.2 O. 6 XIO - 3
(0.8 <x< 1.25). VO 1.02 4.077 5.583 28.9 3.5X10
-3 - 2.0 O. 6 XIO - 3

^Oi .23 4.133 5.329 21.2 + 22.1 0.8X10-3

36
 Vanadium oxides — Continued
—
Oxide and description Data Remarks and inferences References
of the study

Melting point (VO Z )~2170 K Most comprehensive study on 30

well-characterized samples; con-
tains literature survey up to
1970; High pressure annealing
studies conducted; VO z (0.86 ^
x^ 1.02) is metallic and show
temperature-independent xm
while samples of VO z (1.02 ^x^
1.23) are semiconducting and
show weak temperature-
dependent xm- No metal-to-
semiconductor transition nor
magnetic ordering noticed in any
sample in the range 4.2-300 K
for all x.

Vacancy annealing in VO. High temperature (~1920 K) and A critical value of PAT (>90,000 [36].

high pressure (~56 kbar) pro- kbar. °C) where P is the ap-
duced substantial decrease in the plied pressure and AT is the
vacancies (vacancy In
filling); temperature above ambient at
common with other workers, which the pressure is applied,
difficulties were encountered in seems to eliminate the vacancies
the preparation of pure single completely in TiO. A similar
phase VOi.oo- (but higher) value is predicted
for complete vacancy filling in

VO.

NMR studies of VO. V 51

NMRstudies on single crystals Results indicate that the bulk of [42].

and pressure annealed VO z the temperature-dependent

(x=0.86, 1.02 and 1.23) using magnetization comes from local
cw and spin echo techniques in moments on a minority of sites
fields of 9 -50 kOe in the range whose nuclear resonances are
1.4-300 K. Resonance was ob- unobservable.
servable in all compounds at all
temperatures indicating the ab-
sence of metal-insulator transi-
tion in the observed materials.

Resistivity and Hall VO z (0.82 ^ x ^ 1.0) samples studied An overlapping band model is [43].

coefficient studies. at 4.2, 77, and 300 K. p (300 K) suggested to explain the ob-
-3 -4
isin the range 10 -10 flcm served properties.
with small negative values of
dp/dT; Ru is ~5X10 -4 cm 3 /C
and positive A p/p at 4.2 K. The
samples did not exhibit metal-
insulator transition.

37
 -

Vanadium oxides — Continued

Oxide and description Data Remarks and inferences References
of the study

Seebeck coefficient For VO* samples with a: <1.0, a is The data indicate that electrons [171].
studies onVO*. negative; for *>1.0, a is positive and holes are competing to-
and for * * 1 .0, a ~ 0. The gether for the contribution to a
numerical values are small (
—5 and the consequent complica-
to +20 mV/°C). band structure
tions in the
related to a large concentration
of metal and anion vacancies.

Crystallography and The solubility of TiO in VO is It appears that VOo.8 does not be- [35].

defect chemistry of VO small (~10%). The concentra- long to the same family of cubic
and solid solutions -with TiO. tion of defects are lower than in VO* with (0.9 ^ ^ 1.2) and
pure VO*
any given composi-
at higher disorder in cation sub-
tion. Semiconductor behavior was lattice exists compared to anion
noticed for VO (* ^ 1.0) and its sublattice. The low solubility of
solid solutions in the range 100- TiO in VO is explained in terms
300 K. No metal-semiconductor of the different degree of disorder
transition was noticed for VO or in the two crystal lattices.
in the solid solutions in the
temperature range investigated.

Electronic structure and Mutual solubility of VO and TiO at The observed behavior is explained [172].
solubility of other oxides 1870 K is ~18-20%; in the in terms of the electronic struc-
in VO. oxygen rich phases (*>1.0), ture and valence states of the
solubility is greater (20-25%). metal in these compounds.
Solubility of BeO, CaO, and
MgO are small in VO.

Plasma resonance in VO. Reflectance minima are found in The reflectance minima correspond [173].
the range 3. 8-4.0 eV in VO* to the plasma edges in these
depending on the composition. materials.

Infrared studies of VO*. VOi.od and VOi.u give rise to The band corresponds to the metal- [174].
bands at 1075±15 and 1080±10 oxygen vibrations and results
cm -1 respectively. indicate that the band position is

not much sensitive to the

nature of the cation or the phase
composition.

Band structure of VO. Band structure calculations by the The energy bands in VO seem to be [175].
tight binding method indicate sensitive to the degree ionicity
that the d bands are about 7 eV assumed in the calculation; the
wide, lying below the vanadium density of states at the Fermi
4s band so that conductivity in level is large, suggesting that VO
.VO is primarily due to the d might exhibit some sort of mag-
electrons. The Fermi level falls netism. See also (ref. [9], p. 130)
in the d band. for band structure calculations.
vo
2 3

Crystal structures of the Range 77-160 K: Earlier workers [59, 176] interpreted [63, 64]. j

phases and x-ray studies. Monoclinic; space group, 12 /a; the low temperature monoclinic
Z = 4; a = 7.255±0.003, A; b = distortion in terms of a ortho
5.002 ±0.002 A; c = 5.548 ±0.002; hexagonal cell or c-centered
0 =96.75 ±0.02°; E = 99.97±0.08 monoclinic cell but the present
A». choice in terms of a hexagonal
TEC of this phase is <2X10 -6 cell appears to be the most
K- 1
. easily conceived. Single crystal

38
 Vanadium oxides — Continued
Oxide and description Data Remarks and inferences References
of the study

Range 160-700 K: growth conditions established.

Rhombohedral (pseudo hexa- V 2 O 3 has an unusually high c/a [58, 62, 63].
gonal); space group, R 3 C; Z = 2, ratio (at 298 K); detailed studies
oh =4.9515 ±0.0003 A; ch = indicate that in going to the
14.003 ±0.001 A; c/a =2.8281; monoclinic structure, nearest
V =98.61 ±0.05 A 3 . neighbor V-V distances show a
TEC (/K) at 298 K: ||“ = (20.2± discontinuous expansion while
-6 c = -(
0.3) X 10 ;
8.6 ±0.3) X
||
the average V-O distance re-
io-«. mains unchanged. Contrary to
The c/a ratio (pseudo c/a for the earlier interpretations [45, 76,
monoclinic cell) shows a sharp 177], pair --wise contraction of the
jump at ~160 K and slight basal plane cations does not, in
nonlinear decrease in the region but the oxygen octa-
fact, occur
450—600 K; the 4% Cr doped hedra become skewed up about
samples show the exact opposite the central metal atom and the
behavior. triply twinned monoclinic struc-
AF (mono.—»rhombo.) = —(1.4 ture is a logical consequence of
± 0 1 )%;
. the value is much less the distortion.
for doped samples (4%). With
pressure, volume decreases
gradually with increasing pres-
sure but doped samples give dis-
continuity depending on the
concentration.
Lattice parameters vary smoothly
with the application of pressure;
din (c/a) /rf (In V) = -0.7.
Melting point of pure V 203 ~
2240 K.

Magnetic susceptibility. Range 4.2-1000 K: The ordering of magnetic dipoles [65, 67, 68 ,
~4
magnetic ordering and Xxi = 1.0X10 (cgs units) in VO
2 3 is of special type com- 76, 77, 79,
neutron diffraction studies. (T <150 K) pared to the other transition 178-181].
xxi=2.1X10-4 +1.40/(T+600) metal sesquioxides.
(180° <T <350 K); xxi =2.1 X The estimated latent heat at low
10 _4 +1.78/ (T +600) (580 <T< temperature transition is ~700
1000 K). xxi shows little aniso- cal/mol.
tropy (< 20 %) and is essentially
temperature independent, xxi
shows a jump in going through
T while heating and shows
t

Curie -Weiss behavior; a hystere-

sis of ~12° was noted. T = 155
t

K. A shallow maximum is indi-

cated in xxi-T curve in the range
400—500 K. This seems to corre-
spond to the high temperature
anomaly in pure V 2 O 3 The mag- .

netic moment changes from 2.37

MB to 2.69 mb in going through this
transition (spin only value for
V3+ is 2.83 mb).
were also made
Xxi -T studies
on doped samples. Internal
field value ~175±15 kOe was
obtained in V 2 0 3 at 105 K
using inelastic spin -flip

39
 Vanadium oxides — Continued
Oxide and description Data Remarks and inferences References
of the study

scattering of neutrons. The

ordered moment (calculated) is

1.25 hb- The existence of

antiferromagnetic ordering
in the low temperature phase
is confirmed. The observa-
tions are in accord with a
model in which the vanadium
moments are ferromagnetically
coupled in monoclinic ( 010 )
layers with a reversal between
adjacent layers. The ordered
moment is ( 1.2 ± 0 1 ) mb per V
.

atom. Neutron diffraction study

shows that the magnetic ordering
disappears at 154 K which is the
Neel temperature (Tn). Applica-
tion of pressure decreases the
transition temperature (dT^/dP
= —3.78 K/kbar). Above 26
kbar pressure, the magnetic order
disappears and the material re-
mains paramagnetic down to 4.2 K.

Electrical properties. Semiconductor behavior below T t The low temperature behavior is [38, 63, 71,
(151±3 K); P (125 K) ~ 10 6
usually interpreted in terms of 76-78, 182;
ficm; Eo~0.12-0.18 eV; below intrinsic behavior. According to
40 K, evidence of impurity con- McWhan et al. [63], the proper-
duction with Ea ~0.001 eV. Be- ties of both the high temperature
low T t, a is ~
—3 nV/°C and phases (metallic, M and insulat-
f?n<0.3 cm /C8
(at p~ 10 8
ftcm). ing, I, phase) are anomalous and
Metallic behavior above T <; are modified by the impending
p drops by a factor 10 7 at 7\ while transition in the range 500--600
heating; hysteresis of ~12 K K. The order of the transition
noted, a becomes positive and may be second or higher order
jumps to ~12 mV/ 0 C and shows but can be made first order under
slight decrease with temperature proper conditions (by doping
thereafter, p shows an anomaly with Cr). A generalized picture
(broad maximum) in the range of the transitions in V 2 Q 3 has
500-600 K. No anomalous be- emerged from the work of these
havior in a and Rh in this tem- investigators.
perature region.
Resistance decreases with the
application of pressure:
1 atm: p=227±1.4 T (150 < T<

350 K). 26 kbar: p = 182 ±0.7 T

(200 <T<300K);p= 3.1 ±0.042 T 2

(T<50 K). (d In p/d In V) =30

(basal plane); =16 (parallel to
c-axis).
Rh=2.3X10 -4 cm /C (p-type); 8

no change in Rh at the high

temperature transition, mh = I

0. 2-0.6 cm /V s in the range

!l
2

300-600 K; ra*»50 m; Mean

free path ~2 A.
 Vanadium oxides — Continued
Data Remarks and inferences References

Endothermic peaks in DTA were The thermal properties are showing [17, 62, 76,
noted at 168 and 430 K; no AH up the two transitions in V2O3 80, 183].
value reported. X-type anomaly but there is need for quantitative
was noted in the heat capacity of studies on the AH and AS of
V2O3 at 169 K; AH = 692 cal/mol; transition.
AS for the transition = 4.1 e.u.
McWhan et al. [62] estimate a
value of AS = 2.6 e.u. A nuclear
specific heat measurement in the
temperature range below 0.5 K
indicated a Schottky anomaly
varying with T~ 2 for pure V2O3.

Energy gap of ~0.1 eV is obtained The fundamental absorption edge [76, 87].
from the optical measurements in the antiferromagnetic phase
at 77 K in
pure V2O3. The re- appears to be very soft and
flectivity ofpure V2O3 at 300 K shifts to lower energies on
is small but has the general shape entering the high temperature
characteristics of a metal; plasma insulating phase.
edge is at ~1 eV.

Knight shift (%): This study is a strong evidence for [81-84].

= 1.52 - 18.1/(T +684) (T>150
fc magnetic ordering at low tem-
K). An abrupt change in k is peratures in pure V 2 O 3 From the
.

noted at the high temperature 'NMR-phase diagram’, Ruben-

transition, while the resonance stein [83] concludes that the
signal vanishes at the low- metal-insulator (high tempera-
temperature transition (150 K). ture region) phase boundary is

No anisotropy in k is noted nor not sharp and uniform below the

any observed nuclear quadrupole critical point, but corresponds to
splitting. an inhomogeneous transition. It
Antiferromagnetic state is sup- ispostulated that the high tem-
pressed in pure V2O3 at high perature phase transition is
pressure and low temperatures. produced by an instability in a
V 51
NMR signal is observable normal mode vibration of the
down to 4.2 ( — 1 .0 ±0.2) +
K. k = crystal lattice and that the low-
(0.01±0.005) P (20<P<65 temperature transition (150 K)
kbar and T = 4.2 K). The effect is driven by large magnetostric-
of doping V2O3 with Cr and Al tion by the antiferromagnetic
has also been studied in detail. ordering aided by the presence of
this ’soft’ acoustic phonon mode.
The lattice instability is be-
lieved to be caused by the close
proximity of a van Hove singu-
larity to the Fermi energy in the
metallic state of the crystal.
The pressure dependence of the
Knight shift implies that the d
spin component of the suscepti-
bility (xd) is unusually strongly
dependent on volume with
(d In xd/d InK) =8±5.

Studies of Fe-doped V2O3 in the The calculated Ts was ~200 K. It [ 74 ].

range 4.2-300 K: Magnetic is inferred that the larger dis-
hyperfine splitting was noted be crepancy between T t and Tn
 t

Vanadium oxides — Continued

Oxide and description Data Remarks and inferences References
of the study

low T (~140 K) which disap- (calc) might indicate that mag-

peared above T and the sub- <
netic ordering is not a major

stance was paramagnetic. The cause of the transition.

internal field decreased with tem-
perature (400 and 315 kO e at 4.2
and 131 K respectively) and
abruptly disappeared at T t;

isomer shift showed a jump at T t.

UHF dielectric properties. Wave guide method using a fre- The high value of e indicates the [
86 ]

quency of 9.5 GHz: e~18 (T< relative importance of nonpolar

160 K); e~36 (T>160 K). e
slowly varies with temperature;
in the region of the transition a
jump by a factor of 2
Complex conductivity also
exhibits an anomaly at T
type of bonding in V 2 O 3 and the
transition is accompanied by a
change in the type of chemical
is noted. bonding, electron -energy spec-
trum and consequently the
t. dielectric properties.

Electric field effect on the When the applied field reaches a [184]
transition. critical value (~10 V/cm
4
at
77 K) the current increases
rapidly; this threshold field de-
pends weakly on the sample
thickness. Switching behavior
also is noted in the samples of
pure V 2 O 3 .

Effect of stoichiometry on For low stoichiometric deviations [88]

the low temperature in VO 1 5 +X, both a and c param-
.

transition. eters of hexagonal form at room

temperature, decrease linearly
and c/a is a constant. With large
x (x> 0.015), a decreases more
rapidly than c suggesting a
probable change in the distribu-
tion of defects involved in the
crystals.
The magnitude of the discon-
tinuous change in xm at TV and
Tn become smaller with increas-
ing x; no transition is observed
observed for x =0.034 either in
terms of a change in the crystal
structure or in Xm-

Band structure of VO
2 3. The band structure of the hexa- The model appears to account for [185]
gonal VO 2 examined by
3 lattice is a transition from a distorted,
the tight -binding method. The insulating state to an undis-
stability of the structure in rela- torted semimetallic one, for
tion to the distortions and the certain values of the d-d
splitting of the d bands is interactions.
investigated.
VO
3 5

Crystal structure Monoclinic; space group, C2/c or — (99)

Cc; Z = 4; a =9.98 A; 6 = 5.03 A;

42
 Vanadium oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

c = 9.84 A; 0= 138.8°. X-ray stud-

iesdo not indicate any phase
transition up to ~1270 K.

Physical properties. X-T plot shows an anomaly at Earlier studies [73] might have [17, 72, 95,
~133 K, but DTA does not contained some VO 5 9 impurity; 98, 105].
indicate a peak at this tempera- the cause of x-T anomaly is not
ture. Probably the substance is known.
paramagnetic in the range 77 —
300 K. Semiconductor behavior
in the range 130-300 K; Ea =0A
eV. a data (~280 MV/°C at 273
K) indicates re-type behavior; a
decreases with T.

Magneli phases, V nOin-i Crystal structure and transition Magnetic, electrical, DTA References
temperature and Mossbauer studies

;
phase All phases are triclinic; space group.
Pi; Z—2.

4; V<07 o = 5.502 A; b =6.997 A; X-T anomaly at T t. Semicon- [17, 94, 100,

c = 12.248 A; a =95.09°; 0 = ductor -to -metal transition; Ap = 101, 105,
95.17°; 7 = 109.28°. 7\ = 250± 10 2 at T t ; a shows discontinuity 186].
5 K. Discontinuity in the lattice at T
a is negative in the range
t;

parameters at T no change in
t ;
120-300 K; a above T is ~10-12 t

the crystal structure; the volume mV/°C. Endothermic DTA peak.

change for the semiconductor -to - No magnetic order below T t;

metal transition = + 0.0011 ± Isomer shift and quadrupole

0.0006; the pressure dependence splitting show discontinuities at
of T is — 0.2d=0.1 K/kbar.
( T T decreases by Fe 3+ doping
t ; t

but jump in x remains almost the

same.

5; Vi09 0 = 5.475 A; 6=6.994 A; c = 8.718 X-T anomaly at T t. Semiconductor- [17, 96, 102,
A; a =97.53°, 0 = 112.44°; 7 = to-metal transition at T A <; 105, 186,
108.99°. T = 135 ±5
t K. 10 4 — 10 6 below T = 0 1 -0.2
; Ea t . 187].
eV. a decreases with increase in
T; anomaly at T ; above T t t,

10-20 mV/°C (re-type). Endo-

thermic DTA peak at T No t.

magnetic order below T Isomer t ;

shift and quadrupole splitting

show discontinuities at T<; Fe 3+
doping decreases T < slightly.

6 ; VgOn o = 5.44 A; 6=6.99 A; c = 23.66 A; X-T anomaly at T t. Semiconductor- [17, 95, 103,
a =98.5°; 0 = 120.9°; 7 = 108.9°. to-metal transition at T Ap~ 105, 186].
T = 170-177 K.
t 10 4 ; Ea
below T<=0.12 eV. a is
negative in the range 120-300 K
and goes through a sharp maxi-
mum at T Above T a = 10-13 t. t ,

mV/°C. DTA endothermical peak.

43
 a ±

Vanadium oxides — Continued

Oxide and description Crystal structure and transition Magnetic, electrical, DTA References
of the study temperature and Mossbauer studies

7; VO 7 1, a = 5.43 A; 6 = 7.00 A; c = 15.16 A; X continuously decreases with in- [17, 94, 103,
a =98.9°; /3 = 125.5°; 7 = 108.9°. increase in T. Metallic in the 105, 186].
No transition. range 4.2-300 K; p (300 K)-~
10 -3 Dcm. a is negative and
small in the range 4.2-300 K,
T and
decreases slightly with
below 120 K, nearly constant
(~1 pV/°C). No endothermic
peak in DTA.

8; VgOi5 a = 5.43 A; 6=6.99 A; c = 37.08 A; X-T anomaly T

Semiconductor-
at t. [97, 104,
a =99.0°; /3 = 128.5°; 7 = 109.0°. to-metal transition at T t: Ap ~ 105, 186].
-3
7\ = 70 K. 10; p (200 K) ~10 ftem. a is
negative and drops from —70 to
— 5 /zV/°C at T ; Above T , a is
t t

constant.

The general characteristics of all the Magneli phases, V n 02 n-i are: (i) All have triclinic crystal structure at room
temperature, (ii) Antiferromagnetic ordering is present at low temperatures and semiconductor -metal transitions
are present at higher temperatures, T [105]. Ty is 70, 40, 30, 23, 43, and 7 K respectively, when n is 3, 4, 5, 6 , 7,
t

and 8 V0O3 (n— 2 ), V„ 02 n-i (3<n<8) and VO2 (n = «) make an interesting comparison: n= 2 Tw = Tj; n = 3-8,
.
,

Tat<T,; n = «, 0 = Tff<T (iii) a of all the phases is negative below and above T which shows that the
t. t

predominant carriers are electrons. Above T is ~10-12 pV /°C in all the phases which is characteristic of

metallic conduction. Below T a-T curve is complicated, (iv) DTA [105] gives A H (cal mol -1 ) and AS (e.u.)
t,

values at T as follows: n=4, 142, 0.57; n= 5, 215, 1.59; n= 6 222 1.31; No data for n = 8 V3O5 and V7O13
t , , ;

show no transitions and are semiconducting and metallic respectively in the ranges 77 to 127 K and 4.2 to
300 K.

VO*

Crystal growth. Single crystals of V0 2 are grown Depending on the conditions large [
10 , 28,
from V 2 0 6 at high temperatures single crystals of varying stoi- 133].
under various oxygen partial chiometry can be grown.
pressures.

Crystal structures of the T <340 K: Crystal symmetry changes at the [61, 101 ,
phases and x-ray studies. Monoclinic; space group, P2i/c; transition;volume change is very 109, 111,
Z = 4; density, 4.65 g/cm 3 (obs.); small. Above T both a and ct 112, 115,
4.67 g/cm 3 (cacl.). a = 5.7517 ± parameters increase but the rela- 116, 118,
30 A; 6=4.5378±25 A; c = tive increase in the c parameter 125, 189].
5.3825 ±25 A; /3 = 122.646±96°. is greater. NMR evidence shows
T = 346 K: the triclinic phase formation at
Tetragonal; space group, 325 K. Cr, Al, and Fe are sup-
P4/mnm; Z = 2; = a posed to stabilize this phase.
4.551 ±0.001 A; c = 2.851±0.001 Also see [116a] for structural aspects
A. AV at the transition = 0.02 of V0 2.

0.05 cm 3 /mol.
TEC (350-690 K)/°C:
-9 -8
||
e
: 29.638 XIO -2.930 X10 1+
2.576 X10
-11
1*; ||«: 5.828 X10 -6 -
t+6.946X 10 — 12
-
7.091 XIO * t
2
.

325 < T <340 K: Triclinic, a —

5.80 A; 6 =4.52 A; c = 5.38 A.
a =91.5(5)°; /3 = 122.7(8)°;
7=90.0°.

44
 Vanadium oxides — Continued
Oxide and description Data Remarks and inferences References
of the study

Magnetic properties. Paramagnetic in the range 1.7-400 Jump in x at Tt is noted; the exact [17, 117,
K; x below and above T are cause of this is not understood 120 - 122 ].
almost temperature independent; clearly.
slight anisotropy in x is shown.

X» 1.0X10'" (emu/g) (T<340K);

X-8.5X10" 6 (emu/g)
(T>340 K).

Electrical properties. T <340 K: Semiconductor be- The wide variation in the proper- [39, 61,
havior. p~10 -3 — 10 ftcm; Ea ~ ties of VO 2 in the low and high 120, 128,
0.1-0.65 eV; a~30-1000 n\/°C temperature region are believed 130, 134-
(negative); mhM). 1-1.0 em“ 2 /V s; to be due to the purity, method 137, 140].
n ~10 l8 -10 19 cm" (T <340
fl
3
of preparation etc. Slight aniso-
K); m*~ 1.6-7 m; ap*^2. tropy exists in all the properties.
T>340 K: Metallic behavior Discontinuities at Tt in p, a, and
2-5 (X10 -4 ) ficm; p linearly Rn are noticed by various
0
increases with T; a ^23 /*V/ C workers. A hysteresis of '>-'2° is
_2
(negative); mh~ 1-10 cm /V s; noticed in p-T data. The pres-
-3
n«'*^10 21 -10 23 cm ; m*« 0.5 m. sure effects on T indicate quali-
dT/dP m + (0.082 ±0.005) °C/ tatively different behavior than
kbar; ~dEa /dP~ (0.001-0.002) that encountered in V2O3.
mV/kbar. p decreases with Slight increase in carrier concen-
pressure at 300 K but no metallic tration is noticed with pressure
behavior noted up to 300 kbar. but the effect is small and
superpressures seem to be re-
quired to produce metallic con-
duction in VO 2 at room
temperature.

Optical properties. V0 2 exhibits infrared active phonon The data are consistent with the [130, 139].
modes for T<Tt ( = 341 K) in assumption of the appearance of
the energy range 0.02-0.09 eV. ~10 quasi free electrons per
21

Above T the infrared spectra

t, cm in the metallic state and a
3

show sudden increase in reflec- filled oxygen 2 p band ~2.5 eV

tivity. Reflectivity and trans- below from the partially filled

mission measurements in the
range 0.25-5.0 eV below T indi-
cate prominent absorption peaks
at 0.85, 1.3, 2.8, and 3.6 eV.
Above T t, metallic free carrier
absorption is observed below 2.0
eV, but the same two absorption
peaks near 3 and 4 eV are present
in the high temperature phase.
e. = 5.54 (300 K); 4.17 (355 K).
According to Kawakubo [150], e
of VO 2 measured at 24 GHz in-
creases monotonieally from 22 to
26 in the range 100=300 K and
attaing a high value of 60 within
a few degrees below T< (340 K).
This seems to indicate the onset
of an intermediate ferro- or
anti -ferroelectric phase [151]
possessing a distinct triclinic
structure [115, 125],
bands arising primarily from
t vanadium 3 d orbitals. Transitions
from the filled 2 p bands are re-
sponsible for the high-energy
peaks in optical absorption in
both the high- and low-tempera-
ture phases. In the metallic phase
there is evidence of overlap
among the 3 d bands such that at
least two bands are partially
occupied by the extra d electron
per vanadium ion. In the semi-
conducting phase, a band gap of
~0.6 eV opens up within the 3 d
bands separating two filled bands
from higher-lying empty bands.

45
 Vanadium oxides — Continued
Oxide and description Data Remarks and inferences References
of the study

Thermal properties. DTA of pure VO 2 shows an endo- First order nature of the transition [17, 80,
thermic reversible peak at 340 K. is confirmed. DTA evidence is 113, 116,
Some w'orkers [116] have noticed presented for the existence of a 117, 119,
two peaks at 342 and 346 K with triclinic phase of VO 2 just below 138].
slow heating rates (0.5°/min). the transition.
AH = 750 Cp = 13 cal/
cal/mol;
K) and shows a X-
mol, °C (300
type anomaly at T 0d = 75O K; t ;

k~40-70 mW/cm°C at 300 K

and is independent of tempera-
ture in the range 300-360 K.

Mossbauer studies. No magnetic hyperfine splitting is No long range magnetic order exists [75, 123,
noticed at any temperature in in VO 2 and the absence of quad- 190].
Fe 67 doped VO 2 Isomer shift
. rupole splitting in the high tem-
shows an anomaly at T while the < perature phase indicates shielding
quadrupole splitting goes to zero. of the nucleus by conduction
electrons.

Electron and optical
microscopic study of the
phase transition.
The boundaries between the mono- This is a direct observation of the [115, 191].
clinicand tetragonal phases dur- transition and various domains
ing the transition in VO 2 have formed according to the different
been observed in an electron modes of transformation can
microscope by the diffraction easily be distinguished.
contrast at the interfaces which It appears that the T and the
<

are revealed as fringe patterns. rate of growth of domains are

The growth of transformed regions dependent on the mechanical
from sites of nucleation is ob- strain.
served in micrographs.

Infrared study of VO 2 . Bands at 720 and 1115 cm -1 are These seem to correspond to [174].
noted. metal-oxygen vibrations.

V n 02 n+i phases

v«o 13

Crystal structure and T = 300 K: Monoclinic; space The transition may be first order [16-18,
properties. group, C2/m; a = 11.90 A; fe = but the detailed properties are 153].
3.67 A; c = 10.12 A; /3 = 100.87°. not known at present.
Low temperature structure not
known. DTA endothermic peak
and x-T anomaly at 177 ±2 K;
semiconductor -to -metal transition
at 149 K.
VO4 9

Crystal structure. T = 300 K: Orthorhombic; space The structure appears to be closely [30].
group, Pnma; Z = 4; a = 17.926 =fc related to that of V O The
2 6.

0.004 A; fe =3.631 ±0.001 A; physical properties are not

c= 9.396 ±0.002 A. known at present.

vo8 7
'1

Crystal structure and T = 300 K Monoclinic; space Detailed physical properties are not [17, 29,
properties. group, C2/C; Z = 12; a =21.92 A; known at present. 154, 155].

46
 Vanadium oxides — Continued
l

MagnSli phases, V n 02n-i Crystal structure and transition Magnetic, electrical, DTA References
temperature and Mossbauer studies

6 = 3.68 A; c = 18.34 A; 0 =95.62°.

DTA does not indicate any
transition in the range 130-
950 K.

vo
2 5

Crystal structure and T = 300 K: Orthorhombic; space V2O5 has a corrugated sheet type [157, 162].
magnetic properties. group, Pmnm; Z = 2; density, structure and predicts anisotropy
3.357 g/cm 3
(obs.); 3.37 g/cm 3 in the TEC values; this is ob-
(calc.); = 11.519 ±0.006 A; b =
a served experimentally.
4.373 ±0.002 A; c = 3.564±0.002
A. x = 3.7X10-® cgs/g. TEC
(300-870 K) (X10®/°C): ||“, 2.0;
6 c
|| , 55.4; || , 8.0; average, 21.8;
polycrystalline, 13.0.

Electrical properties.
Range, 77-450 K: Semiconductor; Anisotropy in electrical transport [168, 192].
p~10 Ocm; a~10 pV/°C
3
(nega- properties is understandable be-
tive). p-T plot shows breaks at cause of the peculiar sheet type
250 and 390 K. a goes through a structure of V2O6. The breaks in
maximum at 250 K. Anisotropy p-T plots may correspond to the
in p, Ea and a are noted, po in- change in the mechanism of
creases with T in the range conduction (extrinsic to
350-390 K. intrinsic).

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49
 n

1.4. Chromium Oxides work has shown [51, 54] that Cr0 can be
2 held for

Many binary oxides considerable period of time without decomposition at

are known in the Cr-0 system.
Schonberg [1] described the existence of C^O, but temperatures 1170 to 1770 at pressures of 60-65 K
kbar.
detailed investigations have not yet been carried
out. CrO does not exist in the stable state and at- Cr0 2 has a tetragonal rutile structure and its

tempts have been made to stabilize it in the form lattice constants do not vary with slight changes in
of solid solutions [2]. The known oxides of chromium the O/Cr ratio [48, 51, 52] and the rutile structure

are Cr 2 03Cr0 2 [4], Cr Oi [5], an oxide of the

[3], B 2
exists in the range 300 to 673 K [55, 56]. Magnetic
composition Cr0 2>44 [6], Cr 0i5, or Cr 05 [6-8], a measurements [4, 57-59] and Mossbauer data [60]

nonstoichiometric oxide Cr0 5 [6], Cr Os [8] and

6

2 6
.
2

3
indicate that the oxide is ferromagnetic with T c
~
Cr03 [6-9]. Cr30 4 has been reported by a few workers 395 K. p-T data in the range 80-575 K indicate
that it exhibits a positive temperature coefficient of
[10, 11], but recent work [12] has failed to indicate
the existence of this material as a stable phase. p and is a typical metal [4, 48, 49, 51, 61-64]; dis-
continuities in p and a are noted at T c Optical
Cr 2 03 and Cr0 2 have been extensively investigated .

and heat capacity data [65, 66] are also consistent

in the literature.
with the metallic nature of Cr0 2 .

Cr 2 (>3: Cr rhombohedral (pseudo hexagonal)

2 C>3 is
Cr0 forms solid solutions with V0 2 [67, 68] and
2
and is antiferromagnetic below 308 K. Even though it Mn0 with the associated changes in the physi-
2 [69]
has the same corundum structure as a-Fe 2 03, the spin cal properties.
structure differs and precludes the possibility of
Cr 5 Oi 2 Cr60i 2
: is formed under high pressure condi-
superimposed ferromagnetism below Tn [13-19]. The tions at ~500 K and has orthorhombic symmetry
crystal structure does not change at T n, but dis-
[6, 7]; the substance appears to be nonferromagnetic
continuities in the lattice parameters are noted
but detailed physical properties are not known at
[20]; in particular, the body diagonal c parameter is present.
contracted slightly on heating through T n. Below Cr0 : This oxide is obtained by the decomposition
2 44
T n, x (perpendicular to the [111] direction) is almost of OO3 and ^510 K [6];
at a pressure of 600 bar
temperature independent whilst x parallel to the the structure and other properties have not yet been
[111] direction approaches (but does not become) investigated.
zero at 0 K [14, 21]. Cr 2 03 exhibits magnetoelectric
Cr 6 Oi5 (Cr 2 0 B ) Kubota [8] reported the formation
:

effect below Tn and various workers have studied of Cr 2 0 B by the decomposition of CrOs at high oxy-
this phenomenon [22-27]. Anomalies in p [28, 29],
gen pressures but the structure is not known. On
ultrasonic sound velocity [30-32], Young’s modulus
the other hand, Wilhelmi [6, 7] reported the forma-
[33] and dielectric constant [25, 26, 34] have been tion of orthorhombic Cr 6 0i6 at pressures >1 kbar
noted in Cr 2 03 at ~T n. and 490 K; pertinent physical properties, however,
High pressure x-ray studies [35] indicate no are not known at present.
crystallographic transition in Cr2 0 3 however, T n ;
Cr0 2 .65: This nonstoichiometric oxide reported by
decreases linearly with pressure up to ~13 kbar Wilhelmi is obtained by the decomposition of
[6]
[36]. T also seems to depend on particle size of
Cr0 3 in air at 540 to 570 K. Detailed data are lack-
Cr 2 03 [37] to a small extent. Recently, Kawai and ing.
Mochizuki [38] noticed a transition from insulator Cr 3 Og: This formed by the decomposition
oxide is
to highly conductive state in Cr 2 03 under static
of anhydrous Cr0 3
[8]. It is not very stable and
high pressure conditions (>2 Mbar).
decomposes at 650 K. The crystal structure and
Cr 2 C>3 forms solid solutions with other oxides of other properties are not known.
corundum structure like Al 2 03 [3, 39-41], Fe 2 03 [18, CrOs: Chromium trioxide, CrC>3, is a stable material
42] and Mn 2 0 3 [42] and the nature of magnetic inter- but absorbs moisture. It is orthorhombic and the
actions and other physical properties have been in-
structure consists of linear chains of corner-sharing
vestigated in detail.
Cr0 4 tetrahedra [6, 9, 70]. Electrical transport stud-
Cr0 2 : The dioxide of chromium, Cr0 2, has a number indicate it to be a semiconductor over a wide
ies [71]

of interesting properties which include ferromagne- temperature range. No crystal structure transitions
tism and metallic electrical conductivity. Many at ordinary pressures are known but p studies at
methods have been reported in the literature for the high pressures [72] indicate a first order transition
preparation of Cr0 2 [2, 6, 8, 43-52] but the material at ~ 140-145 kbar pressure and the sample retains
is actually a metastable form and
on heating to will, the semiconductor behavior. Other properties of Cr0 3

~720 K, transform irreversibly to Cr 2 (>3 [53]. Recent have not been investigated in detail.

50
 Chromium Oxides

Oxide and description Data Remarks and inferences References

of the study

Cr203

Crystal structure and
x-ray studies.
Hexagonal; space group, R3C; No change in the crystal structure [6, 20, 35,
Z = 6. T = 291 K: a=4.9575 A; takes place through the transi- 73].
c = 13.5976 A. T = 313K: a = tion region.
4.9605 A; c = 13.5945 A. Discon-
tinuities are encountered in a and
c parameters at ~Tn (308 K);
c axis contracts on heating
through Tn. Pressure also de-
creases c parameter.

X-T data. T = 4.2 K: x=22.4XlO- emu/g 6

X-T plot is typical of an antiferro- [14, 21, 36,
(parallel to [111] direction). The magnetic material. Increase of 74, 75].
sublattice magnetization drops pressure seems to bring about the
from ~1.5 to zero at 7 ’n- Mag- collapse of the antiferromagnetic
netic moment = 2.76 ±0.03 mb- spin structure at a given
Anisotropy in x is shown. Tn = temperature.
308 ±1 K; Tn decreases linearly
with pressure; dTx/dP =
— 1.6±0.3 K/kbar.

Electrical properties. Semiconductor behavior in the The available data indicate that [28, 29, 71,
range 300-1600 K. p~10 5 flcm the conduction is extrinsic below 76-82].
at 300 K; Eo ~0.4 eV (T<1500 1200 K
dominated by impurities
~
K); £a 2.5 eV (T>1520 K). or native defects with hopping of
a — 0.2-0. 4 mV/°C at ~500 K; holes between Cr4+ and Cr 3+

p type; md~ 10 cm /V
2
5
s at sites. Intrinsic conduction sets in
~500 K. at T^ 1500 X.

Dielectric properties. e«*8 (300 K) and the e value at The magnetoelectric effect associ- [25, 26, 34].
zero and high magnetic fields ated with Cr 2 03 below Tn is

and at high frequencies show because of the magnetic ordering

anomalies at Tn. of the Cr 3+ spins.

Mechanical properties.
Young’s modulus « 96 dyn/cm 2 at The anomaly in the Young’s [33, 40].
273 K and shows anomalous modulus in Cr 2 C>3 is quite differ-
variation in going through Tn. ent from the one encountered in
Compressibility ~4. 5 X 10 -4 CoO and NiO and is attributed
-1
(kbar) at 300 K. to the domain phenomena and
differences in the magnetic order.

Optical properties.
Bands are noted at 14 390, 16 610, The data indicate the localized [83].
21 690, 27 030 and 39 220 cm" 1 nature of the electrons in
and are attributed to the crystal Cr2C>3.
field transitions.Well defined
infrared bands are encountered in
-1
region 300-750 cm and are due
to vibrations of the Cr-0 bond.
10 Dq = 16 610 cm -1 ; 5=478
cm -1 .

C 1O 2

Crystal structure and Tetragonal; space group, P4/mnm; Typical rutile structure; TEC [4, 8, 51,
x-ray studies. Z = 2; a=4.421 A; c = 2.916 A. shows high anisotropy and in 52, 55, 56].

51
 Chromium oxides — Continued
Oxide and description Data Remarks and inferences References
of the study

TEC (/°C): T = 303 K: ||‘» fact ||

e
axis is negative. No
-14.84X10-*; a = +18.61 X ||
crystal structure change in going
10"*. T-640 K: - -0.1 X ||
fl
through T«.
10-« a =
; +13.52X10-*.
||

Magnetic properties.
Ferromagnetic; T«~ 392-398 K Typical ferromagnetic behavior [4, 48, 57-
depending on the sample. Mag- exhibited by single and poly crys- 59, 84, 85].
netic moment =2.07 ±0.03 mb- talline samples. The properties of
Specific magnetization = 138.3 Cr 02 are adequately explained
at 0 K. on the basis of Goodenough’s
X^2X10- 4 emu/g. at 500 K. model [48, 84, 85].

Electrical properties. Metallic in the range 80-575 K; Typical metallic behavior; the [4, 48, 49,
p~10 -4 Qcm (300 K); a* —10 electrical properties are ex- 51, 61-64,
pV/K (300 K); exhibits discon- plained in a rational manner by 84, 85].
a at Te Semi-
tinuities in p, . the Goodenough’s model [48,
conductor behavior is not en- 84, 85].
countered above Te contrary to
the expectations. Magnetoresist-
ance effects noted; at 298 K in a
field of 29 kOe (applied parallel
to [001] axis), (Ap/p) = ( — l.Bsfc
0.2)%.

Mossbauer studies of 87
Fe Fe atoms exist as Fe 3+ hyperfine;
A novel study of the transition in [60].
doped CrOj. splitting of the spectra dis- Cr0 2 Te agrees well with other
;

appears at To (397 K). Mag measured values; internal field

neticmoment = 2ps per Cr 4+ drops to zero at T« as expected.

ion at 0 K; internal magnetic
field = 530 kOe.
CnOu

Crystal structure at 300 K. Orthorhombic; space group, Pbcn; [6, 7].

Z = 4; o = 12.044 A; b = 8.212 A;
c = 8.177 A. The structure con-
tains pairs ofCrOg octahedra
joined by sharing edges; by
sharing corners, the pairs of
octahedra are linked with CrCh
tetrahedra to form a three di-
mensional frame work. Trivalent
and hexavalent Cr atoms seem to
be present.
Cr«Oi6 (C^Os)

Crystal structure at 300 K. Orthorhombic; space group, Cmcm Detailed structural and other data [6-8]
or C2cm or Cmc2; Z = 4; a = are lacking.
8.47 A; b = 12.90 A; c = 10.08 A.
Kubota [8] reports that C^Og has
a high value of p (~10 10 ftcm)
at 300 K.
CrO,

Crystal structure at 300 K. Orthorhombic, space group, C2cm; CrOg has a chain structure. [6, 9, 70].

£ = 4; a -4.789 ±0.005 A; 6-
8.557 ±0.005 A; c = 5.743 ±0.004 A.

52
 Chromium oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

The structure consists of

linear chains of comer-sharing
CrO, tetrahedra.

Electrical properties. Semiconductor behavior; p~10 - 5

Detailed data are, however, lacking [71, 72].
10 6 ficm, p studies at high pres- on Cr0 3 at present.
sures indicate a transition at
~140-145 kbars with consider-
able decrease in the value of p but
C 1O 3 remains semiconducting up
to very high pressures.

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[61] Kubota, D., and Hirota,
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34, 3043 (1963).
[73] Newnham, R. E., and de Haan, Y. M., Z. Krist. 117, tion in MnO at ~100 kbar to a phase which is
235 (1962). tetragonal or of lower symmetry. Bartholin et al.
[74] Corliss, L., Hastings, J. M., Nathans, R., and Shirane,
G., J. Appl. Phys. 36, 1099 (1965). [34] found that the Tn increases with P up to ~3
[75] Samuelson, E. J., Hutchings, M. T., and Shirane, G., kbar.
Physica 48, 13 (1970).
[76] Chapman, P. R., Griffith, R. H., and Marsh, T. D. F., Electrical properties of pure 35-41] and doped
[9,
Proc. Roy. Soc. (Lond.) 224A, 419 (1954).
[77] Fischer, W. A., and Lorenz, G., Z. Phys. Chem. (N.F.)
(with Li or Cr) [9, 42-44] MnO
have been examined
18, 308 (1958). in detail. MnO is unique among the transition metal
[78] Hagel,W. C., and Seybolt, A. U., J. Electrochem. Soc. monoxides in that there maximum in the
108, 1146 (1961).
is a p versus
[79] Crawford, J. A., and Vest, R. W., J. Appl. Phys. 35, po 2 plot indicating a transition from p to n type
2413 (1964). semiconducting behavior at ~1370 K; changes in
[80] Vaisnys, J. R.’, J. Appl. Phys. 38, 2153 (1967).
[81] Cojocaru, L. N., Z. Phys. Chem. (N.F.) 64, 255 (1969). sign of ph and a have also been noted [5, 35, 38-40]
[82] Subba Rao, G. V., Wanklyn, B. M., and Rao, C. N. R.,
to corroborate the resistivity data. The electron
J. Phys. Chem. Solids 32, 345 (1971).
[83] Subba Rao, G. V., Rao, C. N. R., and Ferraro, J. R., mobility in MnO is higher than the hole mobility
Appl. Spec. 24, 436 (1970) and references therein.
at high temperatures (p£/p^«10 at ~1450 K) [45,
[84] Rao, C. N. R., and Subba Rao, G. V., Phys. Stat. Solidi
(a) 1, 597 (1900). 46] and the defect structure seems to involve doubly
[85] Honig, J. M., in Modern Aspects of Solid State Chemistry,
ionized cation vacancies at high temperatures and
Ed. C. N. R. Rao, (Plenum Press, New York, 1970).
at low oxygen partial pressures [5, 9, 35-37, 41, 42,
45, 46].The charge carriers are localized in pure
1.5. Manganese Oxides and doped MnO and at low enough temperatures
(<700 K) hopping type of conduction occurs by
Detailed phase relation studies of the Mn-0 system holes in the 3d-band with a small Ea whereas the
[1-5] have shown that MnO, Mn 304 M^Oa,
and , dominant mechanism of conduction is by holes in
MnOa are the stable solid oxides. All the oxides show the oxygen 2p-band [9, 47, 48]. The EMF data on
interesting crystallographic and magnetic transitions MnO at high temperatures [10] indicate second or
and have been widely investigated in the literature. higher order transitions within the homogeneity
region.
MnO: MnO shows slight deviations from stoichio- Optical properties of MnO have been studied in
metry (<2%) at high temperatures (~1400 K) the literature [49-51]; the absorption edge appears
[5-10]. It is cubic with the rock salt structure at to be ~3.8 eV. Far infrared antiferromagnetic
room temperature and undergoes a trigonal distor- resonance studies [52-54] show that the resonance
tion as well as a volume contraction on cooling to frequency at 27.5 cm -1 is dependent on temperature
~118 K and changes from a paramagnetic to an and impurity content.
antiferromagnetic state [6, 11-15]. The structure in MnOforms solid solutions with other transition
by
the antiferromagnetic phase has been examined metal monoxides having the rock salt structure [55,
a few workers and detailed x m T
[11, 15, 16-24] 56] and the physical properties show variations with
measurements made. The magnetic moments in the composition.

54
 M 113 O 4 : M 113 O4 has a tetragonal structure at room involves a shift in the symmetry center of the struc-
temperature and can be considered as a distorted ture (characteristic of a diffusionless, but probably,
spinel because of the Jahn-Teller distortion at the first-order transition).
Mn 3+ sites [57]; the ionic formula is probably very Mn2 C>3 behaves as a semiconductor in the range
close to Mn 2+ [Mnj! + O corresponding to a 'normal’
] 4 400 to 1000 K [85, 86]. It decomposes at high tem-
spinel. Preparation of Mn 04 in both polycrystalline
3 peratures.
and single crystal forms has been reported in the Trivalent cations can be doped successfully into
literature [6, 58-65]. The degree of tetragonal dis- Mn 03 2 and the structural and magnetic ordering
tortion in Mn 304 decreases with increase in T and aspects have been examined by Geller and co-work -
a rapid structural transition to cubic phase takes ers [80-84] and by Hase et al. [87].
place at ~1435 K
The high temperature
[66, 67]. Mn0 Mn0 2 : 2 apparently exists only in the rutile
cubic form can not be preserved by quenching and modification and found in nature as pyrolusite [6].

the thermodynamic parameters indicate the first An orthorhombic modification has been reported
! order nature of the transition [10, 66, 67]. in the naturally occurring samples, but detailed data
II

Mns 04 is ferrimagnetic below 43 K which is the are lacking; laboratory preparation of the orthor-
curie temperature [65, 68, 69]. At 33 K a rearrange- hombic form has, however, not been successful [6].
ment of the moments occurs such that the chemical Mn0 2 is always associated with slight nonstoichiom-
and magnetic unit cells become identical. Measure- etry [6, 88, 90] and decomposes above 800 K to
ments of C p [70] in the range 20-49 K show that Mn 0 2 3 .

there are no anomalies except for a peak at T c . The usual wet chemical methods of preparation
The material is a semiconductor [71-73] and has a of Mn0 2 result in nonstiochiometry and water of
higher resistivity than the analogous material Fe 3 C> 4 . hydration and are less characterized [6, 88, 89].
Mn 04 3 forms complete series of solid solutions Atomic or molecular oxygen is evolved on heating
with Fe 304 and C03O4 [67, 74]. these 'disperse’ forms of Mn0 2 and serve as good
Mn 03 2 : The common form of manganese sesquioxide oxidizing agents in organic chemical reactions; most
is the a-modification which is closely related to the probably the oxygen is present in the lattice
'active’
bixbyite, (Mn, Fe) 2 03 structure, [6]. 7 -Mn 2 03 having as defects or adsorbed on the surface. The activity
a structure nearly identical to that of Mn 304 has 'seems to depend on the particle size and the method
been reported [6, 75], but detailed data are lacking. of preparation etc.
Moore et al. [6] have noted that 7 -Mn 2 03 transforms No crystal structure transitions are known in
to the a -modification either by heating in vacuum Mn0 2. It is antiferromagnetic below 92 K [90-94]
for 48 h at ~770 K or by keeping at room tempera- and has a screw-type spin structure such that the
ture for one year. spins, aligned parallel in the c plane, screw along the
Among the transition metal sesquioxides, a-Mn 03 2 c axis; the magnetic unit cell is as large as 7 times
is the only oxide which does not possess a corundum the chemical unit cell.

structure and instead, it assumes a deformed cubic Mn0 2 has a low resistivity (~0.H2 cm at 300 K)
C-type rare-earth oxide structure [76-78] possibly and shows anomalous temperature dependence in
as a result of the large Jahn-Teller distortion associ- the range 4 to 300 K [90]. Anomalies in p and C p
ated with the Mn 3+ ion [79, 80]. Geller and co- have been noted at Tn [90, 94, 95]. Bhide and
workers [79-84], employing x-ray diffraction, x-T Damle [96] reported Mn0 2 to be ferroelectric with a
and Mossbauer studies have shown that a-Mn 2 03 T c K
and Samokhvalov [97] finds a (UHF)
of 325
undergoes a crystallographic transition (cubic to dielectric anomaly at around this temperature; how-
orthorhombic) at 302 K, a paramagnetic-antiferro- ever, the anomaly does not correspond to that of a
magnetic transition at 80 K and another magnetic typical ferroelectric material. Ferroelectricity in
K. Crystal struc-
transition (of the Neel type) at 25 Mn0 2 is doubtful since no other relevant data are
ture of a-Mn 2 03 does not change below 300 K and available in the literature.
x-ray data at 6.5 K show no additional lines or sym- Solid solutions, (Mn 1 _ Cr a.)0 2 have been reported
a: ,

metry change implying that the transition at 25 K by Siratori and Iida [98].

55
 Manganese oxides

Oxide and description Data Remarks and inferences References

of the study

MnO
Crystal structure and T = 296 K: Cubic; space group, The cubic lattice distorts to [6, 11-15,
x-ray studies. Fm3m; Z = 4; a =4.4457 ±0.0002 rhombohedral structure at T on t 25, 33].
A. T ~i K: Rhombohedral; o = cooling; slight volume changes
4.4316 ±0.0003 A; a=90.624± also occur. TEC also touches
0.008°. T (= Tn) = 118±2 K.
t maximum atT t. The structure of
TEC (/°C): 64X10- 9 at ~TN . the high pressure form is not
High pressure x-ray studies at known.
300 K indicate a phase transition
at ~100 kbar to a tetragonal or
lower symmetry phase.

Magnetic properties.
x (122 K)= 83Xl0-« emu/g; In the antiferromagnetic state the [11, 15, 16-
-6
X (4.2 K)=79X10 emu/g. magnetic moments are arranged 24, 34].
Typical antiferromagnetic be- in ferromagnetic sheets parallel
havior with Tn = 118±3 K. to (111) planes and the direction
Tn increases with pressure; of magnetization in neighboring
(dTn/dP) =0.3X10 -3 deg/bar. In planes is Neutron
antiparallel.
the presence of a magnetic field, diffractionshows the persistence
below Tn, the direction of anti- of short range magnetic order
ferromagnetism is modified which above Tn. The magnetic transi-
leads to an increase in x- tion appears to be first order.

Electrical properties. Pure MnO: The data on pure MnO can be in- [5, 9, 35-
p (300 K)~10 16 ftcm in stoichio- terpreted as due to hopping of 37, 42, 45,
metric MnO. Semiconductor be- charge carriers with a band gap 46-48, 99].
havior up to ~1500 K; Ea ~l.Q of ~2.2 eV or with a band con-
eV; a (500 K)~400 pV/ K; duction for electrons with a
Changes from p- to n-type be- smaller band gap. The change
havior as a function of po a (at from p- to n-type behavior is due
~10“ 12 atm), at ~1370 K; a to the greater mobility of elec-
changes sign at this temperature; trons compared to holes at high
(Md/md) * 10. temperatures and low oxygen
partial pressures and due to the
Li doped MnO: cation vacancy defects. In doped
p~10 -3 -10 -1 ficm; £a ~0.7 eV; materials, conduction is always
Mh =0.007 cm /V s (400-700 K);
2
extrinsic at ordinary temperatures
Md = (calc.)~0.03 cm /V s; m* = 2
and mainly occurs by hopping;
7 mo K. p decreases with
at 700 intrinsic conduction seems to set
pressure and no transitions are in at very high temperatures.
indicated up to 200 khar.

Optical properties. Dq = 1010 cm -1 B = 601 cm -1

; ; Optical data indicate the localized [49-54].
Absorption edge is at ~3.8 eV. nature of the charge carriers in
Far infrared antiferromagnetic MnO.
resonance is at ~27.5 cm -1 at
2 K; the frequency decreases
with rise in T and varies with the
impurity content.

Mossbauer studies of 67
Fe Tn = 116.9 K. Magnetic hyperfine The magnetic transition appears to [26].
doped MnO. splitting noted below Tn. Internal be first order but no tempera-
magnetic field is maximum (170 tures hysteresis is noted in the
kG) at 90 K and decreases to 97 transition.
kG at 4.2 K.

56
 Manganese oxides=C©ntinued

Oxide and description Data Remarks and inferences References

of the study

NMR studies of MnO. The 66 Mn NMR frequency shifts Guenther et al. [32] speculate that [21, 30-32].
are found to be temperature de- weak ferromagnetism may exist
pendent and proportional to x* in MnO at very low
magnetic field dependence also is temperatures.
noted. Hyperfine coupling con-
stant = — (81.5±2.5)X10 -4
cm -1 .

= -1
Mechanical properties. Compressibility 6.48 X10“ 7 bar . The discontinuous changes in the [14, 15, 27,
Elastic moduli (measured at 30 elastic moduli, Young’s modulus 29].
MHz): Cn = (1.768 ±0.006) X10 12 and internal friction are taken as
dyn/cm 2 Cu = (6.8±0.1) X 10 u
; strong evidence for a first order
dyne/cm 2 (at T>Tn). At Tn, magnetic transition in MnO.
Cu drops by ~19% and greater
decrease is shown by Cu. Young’s
modulus (at Tn)=2X10 u
dyn/cm and internal friction « 20
X 10~ both the properties show
3
;

anomalous behavior near Tk.

M113O4

Crystal structure and T = 300 K: Tetragonal; space MmO* can be considered as a dis- [6, 58-67].
x-ray studies. group, I4i/amd; Z = 4; 0 = 5.762 torted spinel because of the
A; c = 9.463 A. T, = 1435 K. Jahn -Teller distortion at the
T>T Cubic; a = 8.42 A.
( : Mn 3+ sites;the ionic formula can
be written as Mn 2 + /[Mn 2 8 + 04 ]
.

The transition is first order and

the high temperature phase can-
not be quenched to room
temperature.

Magnetic properties. Ferrimagnetic below 43 K (To); a The observed ferrimagnetism is [60, 65, 68,
rearrangement of the spin mo- consistent with the spinel struc- 69].
ments occurs at 33 K such that ture. 1/x-T behavior is of the
the magnetic and chemical unit Neel type above Tc and con-
cells become identical, xm (290 sistent with the Yafet-Kittel
K)~12XlO -3 emu; Magnetic model.
moment = 5.27 mb below To.

Electrical and thermal Semiconductor behavior; p (300 K) Detailed electrical data are lack- [10, 66, 67,
properties. ~10 7
ficm; a«0.2 mV/°C in the ing; Mna0 4 has a higher value of 70, 71-73].
range 500-900 K (p- type); AH = p than FesCh. The enthalpy and
— (5.9±0.7) kcal/mol; AS = Cp data indicate that the transi-
(4.2 ±0.5) et at T<; Cp shows an tion is first order.
anomaly at T t.

Infrared spectra. Bands at 474 and 550 cm -1 are The data are correlated with the [100].
noted. spectra of other oxide spinels.
MniOs

Crystal structure and T = 298 K; Orthorhombic; space Earlier workers concluded that [76-84],
x-ray studies. group, Pbca; Z = 4; a =9.414 A; only cubic structure exists in
6=9,424 A; c = 9.405 A. T< = MnjOs; this oxide does not have
302 K. T = 314 K: Cubic; space a corundum structure and in-
group, Ia3; Z = 16; a =9.414 A. stead has a distorted C-type rare-
earth oxide structure. The transi-

57
 1

Manganese oxides — Continued

Oxide and description Data Remarks and inferences References
of the study

tion appears to be first order but

detailed data on other properties
are lacking.

Magnetic properties. Xm (100 K)~7X10 -3 emu. Para- Geller et al. [82] proposed a mag- [79-84, 101,
magnetic —antiferromagnetic netic structure in the antiferro- 102].
transition, Tni, at 80 K and magnetic phase. Chevalier et al.
another magnetic transition at [102] find that the low tempera-
25 K (Ts 2 ). No crystal structure ture (25 K) transition is at 50 K
transition below 300 K up to 4 K; and is of second order.
Both the low temperature phases
are antiferromagnetic. Tni and
Tn 2 are greatly affected by
impurities.

Optical and electrical Band at ~20,000 cm -1 is ascribed Detailed electrical data on single [85, 86,
properties. to the spin allowed transition. crystal material are lacking. 103].
Infrared bands are in the range
320-670 cm -1 and are ascribed to
the stretching and bending vibra-
tions of the Mn-O bond. Semi-
conductor behavior in the range
400-1100 K: p (200 K)~7X10 3
Qcm; p (500 K)~50 £2cm; Ea =
0.6 eV.

M 11 O 2

Crystal structure and T = 298 K: Tetragonal; space No crystal structure transitions are [6, 33, 88-
x-ray studies. group P42/mnm; Z = 4; a =4.3980 known and it is very difficult to 90, 104,
±0.0002 A; c = 2.8738 ±0.0002 A. prepare exactly stoichiometric 105].
TEC (300-670 K) (X107 /°C); MnC> 2 .

c = a =67.
1
69 With pressure, c
; ||

axis expands at low pressures,

then passes through a maximum
(at ~40 kbar) and ultimately
contracts; a axis, on the other
hand, decreases smoothly with
pressure. The compressibility is

low at low pressures and then

increases at pressures beyond the
maximum in c axis.

Magnetic properties. Antiferromagnetic with Tn= 92±2 The characteristic screw structure [90-94].
K. x (100 K) «36X 10 -6 emu/g; is exclusive to MnC> 2 .

X (300 K) —32X10 -8 emu/g.

Curie-Weiss Law is satisfied
above 150 K. A screw type spin
structure exists below Tn and the
magnetic unit cell is 7 times the
chemical unit cell.

Electrical and other Resistivity is low; p (4.2K) ~2.6X The anomalous p-T behavior is not [90, 94, 96].
properties. 10" 2 ficm; p (300 K)»l.lXl0~ k clearly understood; Mn 02 may
ficm. Anomalous T dependence be classified as a degenerate
in the range 4-300 K. Anomalies semiconductor [57]. The magnetic

58
 Manganese oxides — Continued
Oxide and description Data Remarks and inferences
of the study

in p and Cp noted at Ts- Ferro- transition may be classified as

electricity with a Tc~325 K second order. The details of the
reported. ferroelectric behavior are not
understood and ferroelectricity is

doubtful.

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[68] Jacobs, I. S., J. Phys. Chem. Solids 11, 1 (1959). are the oxygen deficient ferrous oxide (wiistite),
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Solids 7, 351 (1958).

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[76]
(1966). material is unstable below 840 K
with respect to
[77] Hase, W., Kleinstuck, K., and Schulze, G. E. R., Z. decomposition into Fe 3 0 4 and Fe metal; the metasta-
Krist. 124, 428 (1967).
[78] Norrestam, R., Acta Chem. Scand. 21, 2871 (1967). ble phase can, however, be retained by quenching i

[79] Geller, S., Cape, J. A., Grant, R. W., and Espinosa, [1, 2, 7-10]. The thermodynamics and the defect
G. P., Phys. Letters 24A, 369 (1967).
[80] Grant, R. W., Cape, J. A., Geller, S., and Espinosa, structure at high temperatures has been examined
G. P., Bull. Am. Phys. Soc. 13, 462 (1968). [4, 11-20].The deviation from stoichiometry in '

[81] Geller, S., Grant, R. W., Cape, J. A., and Espinosa,

G. P., J. Appl. Phys. 38, 1457 (1967). wiistite due
is to cation vacancies, with each cation
[82] Grant, R. W., Geller, S., Cape, J. A., and Espinosa, vacancy requiring the presence of two Fe 3+ ions to
G. P., Phys. Rev. 175, 686 (1968).
[83] Geller, S., and Espinosa, G. P., Phys. Rev. Bl, 3763 maintain charge balance; thus, Fei_ x O may be re- i

(1970). garded as a solid solution of Fe 2+ and cation vacan-

[84] Geller, S., Acta Cryst. 27, 821 (1971).
[85] Drotschman, C., Batterien 18, 686 (1964); Chem. Abstr. cies in FeO. The average structure at room tempera-
62, 8472g (1965). ture is cubic [7-10] and the material is paramagnetic.
[86] Subba Rao, G. V., Wanklyn, B. M., and Rao, C. N. R.,
J. Phys. Chem. Solids 32, 345 (1971).
Magnetic ordering into antiferromagnetic state oc- ;

[87] Hase, W., Bruckner, W., Tobsisch, J., Ullrich, H.-J., curs at 198 K accompanied by a change from cubic
and Wegerer, G., Z. Krist. 129, 360 (1969).
to rhombohedral structure. Below Tn, the magnetic
[88] Wadsley, A. D., and Walkley, A., Rev. Pure & Appl.
Chem. 1, 203 (1951), and references therein. moments are arrayed in ferromagnetic sheets parallel
[89] Malinin, G. V., and Tolmachev, Yu. M., Russ. J. Phys. to (111) planes and the direction of magnetization
Chem. (English Transl.) 43, 1129 (1969).
[90] Rogers, D. B., Shannon, R. D., Sleight, A. W., and in neighboring planes is antiparallel; the magnetic :

• Gillson, J. L., Inorg. Chem. 8, 841 (1969). axis in Fei_ x O is perpendicular to the ferromagnetic
[91] Bizette, H., J. Phys. Rad. 12, 161 (1951).
sheets [9, 10, 21].
[92] Bacon, D., Usp. Fiz. Nauk. 8, 335 (1963).
[93] Yoshimori, A., J. Phys. Soc. Japan 14, 807 (1959). Detailed studies employing x-ray and neutron
[94] Ohama, N., and Hamaguchi, Y., J. Phys. Soc. Japan diffraction techniques of the quenched phases of
30, 1311 (1971).
[95] Kelley, K. K., and Moore, G. E., J. Am. Chem. Soc. Fei_ x O indicate defect cluster formation [10, 18, 22-
65, 782 (1943). 24]; it appears that the oxygen sublattice is continu-
[96] Bhide, V. G., and Damle, R. V., Physica 26, 33 (1960).
ous and the defect cluster is a region in which there
[97] —
Samokhvalov, A. A., Sov. Phys. Solid State (English
Transl.) 3, 2613 (1962). are vacancies in cation sites and interstitial ions in
[98] Siratori, K., and Iida, S., J. Phys. Soc. Japan 15, 210 some tetrahedral sites. The results are in agreement |

(1960).
with a model which assumes that the average defect
'

[99] Minomura, S., and Drickamer, H. G., J. Appl. Phys.

34, 3043 (1963). cluster contains about 4 vacancies and 2 interstitials
[100] Hafner, S., Z. Krist. 115, 331 (1961).
in powder samples and 13 vacancies and 4 inter-
[101] Banks, E., Kostiner, E., and Wertheim, G. K., J.
Chem. Phys. 45, 1189 Q966). stitials in single crystalline samples. Order-disorder
[102] Chevalier, R. R., Roult, G., and Bertaut, E F., Solid transitions have been noted in Fei_ x O at high tem-
State Commun. 5, 7 (1967).
Subba Rao, G. V., Rao, C. N. R., and Ferraro, J. R.,
peratures [19].
[103]
Appl. Spec. 24, 436 (1970). The cubic lattice parameter of Fei-zO shows varia- ;

[104] Bradt, R. C., and Wiley, J. S., J. Electrochem. Soc.

tion with the stoichiometry and generally, a increases
109, 651 (1962).
[105] Kirchner, H. P., J. Am. Ceram. Soc. 52, 379 (1969). with increasing Fe content [8]. Magnetic cluster

60
 formation [22] also affects the spin structure and transition is commonly Verwey
referred to as the
directions in Fei_ x O below T n,
but Tn is almost transition and detailed investigations have been car-
unaffected by variation in x [21]. This behavior is ried out to understand the nature of the transition.
indicative of the existence of defect clusters of cation Magnetic properties of Fe 3 0 4 are not affected
vacancies by virtue of which the remaining part of below the Verwey transition, but x shows aniso-
the cation sublattice intact thereby not weak-
is left tropy [41, 43-46]. Fe 3 0 4 has a low resistivity at room
ening the antiferromagnetic interaction; random temperature and the ordering of the ions below T t

vacancies, on the other hand, would be expected to (119 K) appears as a sudden increase of p by a factor
weaken the antiferromagnetic interaction and lower of >90 and also causes an anisotropy in p [41, 43].
1

the Tn. Verwey et al. [39, 40] have explained this observation
Stoichiometric FeOi.oo lies outside the phase field as due to the fast electron exchange in Fe 3 0 4 which is
under ordinary pressure conditions [24], but under inhibited below T because of the ordering process.
t

high pressure conditions and in the presence of ex-
cess metallic iron, the cation deficient structure of
wiistite might not be formed; Katsura
have indeed successfully synthesized FeOi.oo from
Many workers [47, 48] have proposed that this
phenomenon is similar to a metal-semiconductor
et al. [25] transition, but the actual electrical behavior above
T is more complex and does not correspond to the
t

FeOo.95 and Fe at a pressure of 36 kbar and at typical metallic behavior. Semiconductor behavior
1040 K. Hentschel [26] has recently concluded on is noted in the range 80 to 119 K and 119 to 250 K;

the basis of x-ray and Mossbauer data that FeOi.oo
is formed as a metastable intermediate in the de-
composition of wiistite at relatively low tempera-
tures (~500 K).
Resistivity measurements
Fei_;rO indicate that p decreases with temperature
as well as the oxygen content. Low oxygen content
samples are p type as evidenced by the a data; a
p is essentially constant in the range 250 to 1700 K
showing slight maxima and minima at 350 and ~850
K respectively [43, 49]; the low value of p and con-
stancy over a wide temperature range (250 to 1700
[4, 13, 14, 27-29] on K) seem to indicate that Fe 3 0 4 can be classified as a
degenerate semiconductor above room temperature
[35, 50-53]. Discontinuities in a, Rh and mh have
also been noted at T [53-56].
t

p - to n-type transition is noted at higher oxygen Mossbauer studies of the ordering transition in
content or with higher po 2 in the system. The defect Fe 3 0 4 have been reported by many workers in the
structure is interpreted as due to doubly ionized literature [57-67], Careful studies on untwinned
cation vacancies. crystals of Fe 3 0 4 have revealed that the Mossbauer
Anomalous behavior of TEC [30], Cp [31] and spectrum is composed of five components below T t

UHF dielectric constanthave been noted at

[32] corresponding to a tetrahedral Fe 3+ site, two octa-
Tn in Fei-xO. High pressure x-ray studies [33] do hedral Fe 3+ and two octahedral Fe 2+ sites. One
not indicate a transition up to several hundred would expect, on the basis of the Verwey mecha-
kilobars. nism, a three component spectrum of equal intensity
Solid solution formation of Fei_xO with MnO and (due to octahedral Fe 2+ and Fe 3+ and tetrahedral
MgO has been reported in the literature [8, 34]. Fe 3+ sites). In order to explain the observed spec-
trum, it is proposed [64, 65] that the Verwey-order-
Fe30 4 This oxide is encountered in nature as the
: ing is not entirely correct and the unit cell must at
magnetic oxide of iron or magnetite; it can also be least be doubled to enable the different sites to con-
prepared in the laboratory and has a narrow range tribute to the hyperfine component. This is cor-
of homogeneity [1-3]. Fe 3 0 4 has the cubic inverse roborated by the recent studies employing neutron
spinel structure [35] at room temperature where diffraction [68] and electron microscopy [69].
Fe 3+ ions occupy all the A sites and one-half the B Several properties of Fe 3 0 4 exhibit discontinuities
sites, while the Fe 2+ ions occupy the other half of at T among them
t ; are TEC [70], saturationmag-
the B sites. The material is ferrimagnetic with T n~ netization [41], magnetostriction [70], Young’s mod-
858 K [36-38]. ulus and internal friction [71], elastic constants and
On cooling to 119 K, Fe 3 0 4 undergoes a crystallo- sound wave velocity [72], magnetocaloric effect [73]
graphic transition to an orthorhombic modification and NMR relaxation [74, 75]. However, T deter- t

[39-44]. This has been explained by Verwey et al. mined by different techniques differ slightly, possibly
2+
[39, 40] as due to the ordering of the octahedral Fe due to slight nonstoichiometry or sample purity
and Fe 3+ ions into perpendicular rows with the [66]. Discontinuities in the ultrasonic sound velocities
associated reduction in crystal symmetry. This have been noted near Tn in Fe 3 0 4 [76]. High pres-

61
 m m

sure studies [47, 77] indicate that T t decreases where- that of a pure antiferromagnet; above TM , the crys-
as Tn increases in a linear fashion. tal exhibits weak ferromagnetism with canted spins
forms solid solutions with Mn304 and C03O4
Fe3C>4 lying in the (111) plane. On application of a suffici-
giving spinel type structures [34, 78]. ently large magnetic field in the 2-direction below
T m, a field induced first order spin-flip transition is

Fe20s: Iron sesquioxide, Fe2C>3 (hematite), exists in observed.The Morin transition in Fe 2 03 has been
several modifications: a-Fe 2 03, the most stable form examined by a variety of experimental techniques
having a corundum structure [1, 2, 4], 0-form (sup- like neutron diffraction [100, 107, 108], static mag-
posedly metastable) possessing a cubic bixbyite netization [106, 109-113], AFMR [110, 114, 115],
structure [79, 80] and the 7-modification having a Mossbauer spectroscopy [102, 116-120], NMR [121],
tetragonal structure which is metastable at all con- ultrasonic attenuation [122], Cotton-Mouton effect
ditions of temperature and pressure [2, 79, 81-84]. [123] and neutron scattering [124-127]. The
inelastic
The structure of 6-Fe203 is not well established and effect of pulsed magnetic field has also been studied
even its composition is open to doubt (a better de- [128].
scription might be 5-FeOOH) [85-88]; the c-form Several theoretical approaches have been attempt-
having a monoclinic structure has been recently ed to gain an insight into the mechanism of the
characterized [89] and a high pressure form of Fe 2 03 Morin transition [113, 128, 129-132]. The effect of
having a hypothetical perovskite structure has been pressure on the transition indicates that T in-

deduced from shock wave experiments [90]. creases in a linear fashion; (dTu/dP) = +3. 6°/kbar
[133-135]. Tm
depends on the particle size, the
also
7-Fe 2 0 3 7-Fe 2 03 has a tetragonal structure and
: method of preparation and the purity of the sample
consists of three spinel blocks stacked on top of [136, 137]. The effect of doping Fe203 (with impuri-
each other; the unit cell has the formula Fe 6 40 96 ties) on Tm has been studied by a few workers;

instead of Fe 7 20 9 6 to be expected with a spinel com- Al 3+ Ga 3+ Cr 3+ Sc 3+ Ti 4+ and Sn 4+ ions seem to

, , , , ,

pound. The eight vacancies are distributed among the lower Tm (broadening the range of existence of weak
octahedral spinel sites in an ordered manner [79, 83, ferromagnetism) [112, 138, 139] while Rh 3+ raises

91]. The material is ferrimagnetic [91, 92] and trans- the Tm considerably [140-142].
forms to <*-Fe 2 0 3 above ~670 K [2, 79, 81, 92-94]; Electrical properties of pure [143-146] and doped
the transition occurs gradually and it is easy to [147-150] Fe203 have been examined by various
control the conversion. Goto [95] investigated the workers in the literature. The material is a semi-
phase transformation of y-Fe203 up to 33 kbar conductor in the entire temperature range investi-
pressure and up to 570 K. The rate constant prim- gated (200 to 1600 K). Highly pure Fe 2 C>3 shows
arily depends on the thermo-dynamic parameter some what complex behavior with different activa-
PA V where A V (~7%) is the volume difference 700K, 700 to 950K,
tion energies in the region 300 to
between a - and 7-modifications. and 950 to 1600 K
whereas impure Fe 2 03 shows
linear variation of lnp with 1/T in the range 400 to
e-Fe 2 0 3 : The monoclinic e-Fe 2 03 has a dark brown 1500 K with Ea^T.O eV. Anomalies in p and a at
color and is ferromagnetic with T ~485
c to 500 K T and Tn
t have not been noted, but n-type Fe 2 C>3
[89, 96]. It decomposes to a-Fe 2 C>3 above 770 K. samples show a sign reversal in Rn at ~Tn while
Ph goes through a minimum around this tempera-
a-Fe 2 C>3: This is the most stable sesquioxide of iron ture. Because of the ease with which the valence
and has a very narrow range of homogeneity [1-4, state of Fe can be changed by slight impurities, it is
97]. It has a rhombohedral structure [98] and is highly improbable that the conduction is intrinsic
antiferromagnetic with a high Neel point (Tn~960 in Fe 2 0 3 .

K) [99-104]; discontinuities in the lattice parameters High pressure x-ray studies do not indicate any
are noted at Tn [105]. Of special interest in Fe203 is phase transition but recent resistivity studies
[151],
the magnetic transition which takes place at ^263 K at ultrahigh pressures seem to indicate a transition
(T m) and is usually referred to as the Morin transi- from the insulating phase to a highly conducting
tion [106] and has been extensively studied in recent state (at ^2 Mbar pressure) [152].
years. Below T and in the absence of magnetic Solid solutions of Fe2C>3 with Mn 03
2 [153-157],
field, the Fe 3+ spins are aligned along the (111) or z Cr 2 0 3 [158], Ga 2 0 3 [159, 160], and ln 2 0 3 [160-162]
axis of the crystal and the magnetic structure is have been examined in detail in the literature.

62

Oxide and description
of the study
Fei_*0
Crystal structure and
x-ray diffraction studies.
Magnetic properties.
Electrical properties.
TEC and UHF dielectric
constant studies.
Iron oxides
Data Remarks and inferences References
T = 300 K: Cubic; space group, At ordinary pressures, FeO is [1, 2, 7, 8,
Fm3m; Z = 4. a varies from always nonstoichiometric due to 10, 18, 19,
4.2886 to 3012 A with in-
4. the cation vacancies. Studies on 22-25, 33].
creasing Fe content in Fei_x O quenched high temperature
(Feo.8*0 to Feo. 950 ). For FeOi.oo phases (Fei_x O is unstable below
synthesized at high pressure, a = 850 K) indicate defect cluster
4.323 ±0.001 A. T = 198
t K. formation. Below T , the t
Below T t, the structure is rhombohedral distortion varies
rhombohedral. The rhombohedral with the stoichiometry but T t
distortion is sensitive to the Fe itselfremains unaffected.
content; at 90 K, a «60° for high Hentschel [26] found evidence for
Fe content Fei_ x O and « 59.04° the formation of intermediate
for low Fe content sample. High stoichiometric FeOj.oo in the de-
pressure x-ray studies do not composition of wiistite at rela-
indicate any phase transition up tively low temperatures.
to several hundred kilobars
pressures.
Antiferromagnetic below 198 K The spins in FeO are perpendicular [9, 10, 21,
(= Tn) and the magnetic mo- to the (111) plane unlike in NiO 22].
ments are arrayed in ferromag- and MnO which also show anti-
netic sheets parallel to (111) ferromagnetism and have rock
planes and the direction of salt structure above Tn.
magnetization in neighboring
planes is antiparallel; the mag-
netic axis is perpendicular to the
ferromagnetic sheet, xm obeys a
Curie-Weiss law; xm =3.56/
(T+136). Magnetic cluster for-
mation is noted anologous to the
cationic defect clusters which
affect the spin structure and spin
directions below Tn. Tn is not
much affected by variation of x
in Fei-zO.
Semiconductor behavior (100-1100 Unusually low resistivity exhibited [4, 13, 14,
K); p (300 K) «0.05 ficm; p de- by Fei_ x O compared to other 3 d 27-29].
creases with increase in the oxy- transition metal monoxides and
gen content in Fei_x O. Three controlledby stoichiometry;
distinct regions in lnp-T behavior: p-T behavior is extrinsic.
Ea = 0.008 eV (<100 K); Ea =
0.3 eV (125-175 K); Eo =0.07
eV (200-1100 K). The samples
are p-type but high oxygen con-
tent samples are n-type. The de-
fect structure is of the doubly
ionized cation vacancy type.
TEC and UHF (~10 GHz) dielec- [30, 32].
trie constant data indicate
anomalies at Tn. TEC (186 K) =
41X10~ 8 /°C; e« = 12.7.
63
 t t t t t

Iron oxides=Centinued

Oxide and description Data Remarks and inferences References

of the study

FeiO«

Crystal structure and T = 295 K: cubic; space group, The substance is an inverse spinel. [40-43, 47,
x-ray data. Fd3m; Z = 8; a =8.394 ±0.0005 A. The Verwey transition in FegC^ 70].
T« = 119 K. T = 78 K: Ortho- changes the symmetry
lattice
rhombic; space group, Imma; from cubic to orthorhombic and
a=5.912 A; 6 = 5.945 A; c = causes an ordering of the Fe 2+
8.388 A. TEC (128-295 K): 7.7X and Fe 3+ ions on the B sites
10 _6 /°C. TEC is negative near which are randomly distributed
T — 20 X 10 -6 /°C) with a peak
( ( above the transition temperature.
at T T decreases with pressure;
t. The octahedral ferric ions lie
(dT /dP)= t
— (0.46 ±0.02) along the orthorhombic a axis
K/kbar. and the ferrous ions along the 6
axis in alternate rows that are
mutually perpendicular.

Magnetic properties. Ferrimagnetic; Tn«860 K. x does The magnetic behavior is unaffected [36-38, 41,
not show anomaly at T t (119 K) at the ordering transition. The 43-46, 77].
but anisotropy behavior noted magnetic moment corresponds to
with or without a magnetic field. the spin-only value (since FegO*
(Aff /Mo) =0.026 at TN Mag- . is an inverse spinel), the contri-

netic moment = 4 mb* Tn in- bution from the Fe 3+ ions must

creases with pressure; ( dTn/dP ) vanish and the entire net mo-
= (2.05 ±0.10) K/kbar. ment must be due to the Fe 2+
ions.

Electrical properties. Below T (119 K) semiconductor The electrical properties of FegC^ [39-41, 43,
behavior; Ea increases from 0.03 are a little bit complex; some 49, 53-56].
to 0.15 eV just below T<. At Tt workers [47, 48] assume that it

(on heating), p drops by a factor exhibits a semiconductor-metal

of 10 2 to the order of 10 -2 flcm. transition at T (119 K). How-
Above T t, p continues to de- ever, the p-T behavior above T
crease (with Ea ~ 0.06 eV) and in indicates that of a typical de-
the range 250-1700 K, p is es- generate semiconductor. The
sentially constant ('~4X10 -8 maxima and minima andat 350
12cm) with a slight maximum at 860 K in the p-T plot may be
~350 K and a minimum at spurious and requires confirma-
~Tn. tion by a detailed investigation
a (500 K) « —60 mV/°C. R h , on well-characterized, stoichio-
however, is +ve. At 300 K, metric FeaCh. The abrupt drop
Rh ~5 X 10 -4 cm /C; mh~0.1 3
in p at T is explained as due to
t

cm /V s. a shows discontinuities
2
the rapid electron exchange be-
at T and Tn. Rh and mh de- tween the octahedral Fe 2+ and
crease with T below T and t Fe 3+ ions; this is inhibited below
remain constant or show an in- T ( because of the ordering
creasing trend above T t . process.

Mttssbauer studies. Careful results on untwinned crystals Mossbauer studies have provided [57-67].
of FeaO« indicate that the spectrum the most direct evidence of the
can be resolved into five indi- electron exchange and ordering
vidual components corresponding process in FegO* at T t<

to a tetrahedral Fe 2+ two octa-

,

hedral Fe ,+ and two octa-

hedral Fe 2+ sites. The lines below
T t are broadened. The results are
interpreted in terms of a modi-

64
 Iron oxides — Continued
Oxide and description Data Remarks and inferences References
of the study

fied Verwey model consisting of

twice as large as the unit cell
originally proposed. The relaxa-
tion time of the electron hopping
is estimated to he 1.1 ±0.2 ns.

Mechanical properties. Young’s modulus drops by ''-'30% These observations indicate that [71, 72, 76].
at 108 K; internal friction ex- the 119 K transition is of first

hibits a peak at ~95 K. At 300 order.

K, = 6.75 X 10 cm/s; is —
cl 5

3.69 X10 cm/s. Both cl and cs

5

along [100] axis show sharp in-

creases of 7.5 and 0.2% respec-
tively at 119 K. cl also exhibits
an anomaly at 130 K where there
is an easy axis change in FejCX

from the [100] to the [111] axis.

cl and cs also go through a
minimum at ~Tn.

Magnetocaloric effect. The temperature change of a sam- [73].

ple upon applying magnetic field
has been examined through Tt in
FejO*. AT is negative below T t

and reaches a maximum at T<;

AT passes through zero and be-

comes -fve. The sign reversal
shifts to lower temperatures as
the applied field gets stronger.

Infrared spectra. A band at 595 cm -1 is noted and [163].

correlated with the bands noted
in other oxide spinels.
-FesOj

Crystal structure and Tetragonal; space group P4j; Z= The structure consists of three [79, 83, 91,
properties. 32; a =8.33 A; c = 24.99 A. spinel blocks stacked on top of 92—95].
7 -FejOa is ferrimagnetic and each other; the unit cell has
transforms to a -modification cation vacancies arranged in an
above 670 K. AF~7% and high ordered manner.
pressure studies indicate no
abrupt transition at any given P
and T. Detailed physical prop-
erties not known.
FesOj

Crystal structure and Monoclinic; Z = 20; a = 12.97 A; Detailed properties not known. [89, 96].
properties. 6 = 10.21
A; c = 8.44 A; 0 =95.33°.
Ferromagnetic; Tc~485-500 K.
Transforms to a -form above
770 K.
•FejOj

Crystal structure and T = 300 K: Rhombohedral Typical corundum structure as- [98, 105,
x-ray studies. (pseudo-hexagonal); space sumed by many transition metal 151, 160].
group, R3c; Z = 6; a = 5.0351 ± sesquioxides and a-AljOj.

65
 m

Iron oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

0.0003 A; c = 13.750 ±0.001 A.

Discontinuities in lattice param-
eters noted at Tn (»960 K).
High pressure studies do not
indicate any phase transitions up
to several hundred kilobars.

Magnetic properties. Antiferromagnetic; Tn~960 K. The superimposed weak ferro- [99-104,

-6
X~1.7-2.3X10 emu/g. Mag- magnetism in the range 260-960 106-113,
netic moment = 2.45 mb- Above K is characteristic of only 133-137].
263 ±2 K (Tm), Fe203 exhibits a-Fe 2 03 and the mechanism
weak superimposed ferromag- which causes the Morin transition
netism due to slight canting of is the change in the spin-

the spins in (111) plane. The direction from parallel to per-

spin -flip transition has been pendicular to the c-axis. The
observed in the presence of a observed pressure dependence of
magnetic field. Careful neutron T can be explained if we as-
ji

diffraction studies show that the sume a change in sign of the

transition is spread over a 25-30° total magnetic anisotropy energy.
range, centered at 261 K. Tm de-
pends on the particle size and
stoichiometry of the sample. T
increases with pressure;
(dT u/dP) =3.6 ±0.3 K/kbar.

Electrical properties Semiconductor behavior; p (300 K) The conductivity behavior ap- [143-150].
(200-1600 K). ~10 3 -10 6 ficm. Pure Fe2C>3 shows pears to be extrinsic or con-
a three-region behavior with trolled by native defects in the
various Ea values in the range entire temperature range investi-
300-1600 K; usually p type be- gated. The reason for the sign
havior but some samples show reversal of Rh is not exactly
change of sign of a on heating. known.
Impure or doped samples exhibit
linear lnp-T plots with Ea ~1.0
eV. Both p- and n-type samples
can be obtained by doping. For
n-type Fe2C>3, at 1000 K, p~l-10
12cm; a~ — (400-700) pV/K;
Ph~T0 -2 cm 2 /V s. Rh changes
sign at Tn.

Mossbauer studies Characteristic six -line spectra noted Results indicate that Fe 20 3 in the [102, 116-
(100-1050 K). below Tn. Anomalies in isomer form of fine particles exhibit 120].
shift and quadrupole splitting superparamagnetic behavior.
noted at ~T m. The electric field
gradient shows an abrupt in-
crease at ~Tn. The temperature
dependence of the internal field
is in agreement with the pre-

dictions of the molecular field

theory.

Optical properties. Absorption hands noted at 1.4, 1.9, The 0.7 eV peak observed by [164-166].
2.4 and 3.2 eV. Morin [164] ob- Morin seems to be associated
served a band at 0.7 eV which with donor levels. The higher

66
 Iron oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

increases strikingly as Ti is energy hands are ascribed to the

added. Infrared hands noted in crystal field transitions [166].
the range 285-560 cm -1 and are
associated with the metal
oxygen vibrations.

References [29] Seltzer, M. S., and Hed, A. Z., J. Electrochem. Soc.

117, 815 (1970).
[30] Foex, M., Compt. Rend. (Paris) 227, 193 (1948).
[31] Mainard, R., Boubel, M., and Fousse, H., Compt.
[1] Darken, L. S., and Gurry, R. W., J. Am. Chem. Soc. Rend. (Paris) 266B, 1299 (1968).
67, 1398 (1945). [32] —
Samokhvalov, A. A., Sov. Phys. Solid State (English
[2] A. E. Vol, Ed., Hand Book of Binary Metallic Systems: Transl.) 3, 2613 (1962).
Structure and Properties, Vol. II (English Transl.), [33] Clendenen, R. L., and Drickamer, H. G., J. Chem.
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68
[148] LegsofF, H., Kersey, Y., and Horne, R. A., J. Chem. antiferromagnetic behavior below T n [16-19]. CoO
Phys. 31, 1141 (1959).
[149] Nakau, T., J. Phys. Soe. Japan 15, 727 (I960). is semiconducting at all temperatures and discon-
150] van Daal, H. J., and Bosnian, A. J., Phys. Rev. 158, tinuities in p, a,and Rn are exhibited at the N6el
736 (1967).
[151] Lewis, G. K., Jr., and Drickamer, H. G., J. Ghem. temperature by pure and Li-doped CoO [20-22],
Phys. 45, 224 (1966). Similarly, anomalies in C p [23-26], k [25, 27], elastic
[152] Kawai, N., and Mochizuki, S., Phys. Letters 36A, 54
(1971). wave velocity [27, 28-30], elastic constants, internal
[153] Geller, S., Grant, R. W., Cape, J. A., and Espinosa, frictionand Young’s modulus [27-29, 31] and an
G. P., J. Appl. Phys. 38, 1457 (1967).
[154] Chevalier, R. R., Roult, G., and Bertaut, E. F., Solid [25]have been noted at ^Tn in CoO. The continuous
State Commun. 5, 7 (1967). nature of the transition as indicated by k, C p and
[155] Grant, R. W., Geller, S., Cape, J. A., and Espinosa,
G. P., Phys. Rev. 175, 686 (1968). neutron scattering experiments [9, 23-27] seem to
[156] Hase, W., Bruckner, W., Tobsisch, J., Ullrich, H.-J., infer that the antiferromagnetic—^paramagnetic tran-
and Wegerer, G., Z. Krist. 129, 360 (1969).
[157] Geller, S., J. Appl. Phys. 42, 1499 (1971). sition in CoO is of the order greater than unity. CoO
[158] Cox, D. E., Takei, W. J., and Shirane, G., J. Phys. was one of the first compounds to be studied by
Chem. Solids 24, 405 (1963).
[159] Marezio, M., and Remeika, J. P., J. Chem. Phys. 46, Mossbauer spectroscopy and many workers have
1862 (1967). examined the spectrum as a function of temperature
[160] Prewitt, C. T., Shannon, R. D., Rogers, D. B., and
Sleight, A. W., Inorg. Chem. 8, 1985 (1969). [32-39]. Below Tn, a six-line pattern indicating mag-
[161] Schneider, S J., Roth, R. S., and Waring, J. L., J. netic hyperfine splitting is seen; this disappears in
Res. Nat. Bur. Stand. (U.S.), 65A (Phys. and Chem.),
No. 4, 345-374 (July-Aug. 1961). the paramagnetic state. The Neel temperatures ob-
Geller, S., Williams, H. J., and Sherwood, R. C., J.
[162] tained from Mossbauer studies agree excellently with
Chem. Phys. 35, 1908 (1961).
162] Hafner, S„ Z. Krist. 115, 331 (1961). those obtained by other techniques.
164] Morin, F. J., Phys. Rev. 93, 1195 (1954). Effect of pressure on the magnetization and mag-
165] Bailey, P. C., J. Appl. Phys. 31, 39S (1960).
166] Subba Rao, G. V., Kao, C. N. R., and Ferraro, J. R., netic ordering temperature of CoO has been in-
Appl. Spec. 24, 436 (1970). vestigated by a few workers [40, 41]; the results
indicate that Tn increases with increasing pressure
1.7. Cobalt Oxides and decreasing volume. X-ray diffraction [8] and
resistivity [42] studies do not indicate any high pres-
In the Co-0 system, CoO and C 03 O 4 are the stable sure transitions in CoO up to pressures of ~250
oxides which have been investigated in detail. Al- kbar.
though many workers have reported the preparation According to Ok and Mullen [37, 43], there exist
and properties of a sesquioxide, Co 2 Og, characteriza- two forms of cobalt monoxide, CoO (I) and CoO (II).
tion with respect to stoichiometry and method of Both have cubic rock salt structure at room tem-
preparation seems to be still in doubt and many a perature but CoO (II) has a lesser density and the
time, hydrated forms of the oxides are obtained. lattice has ^25 percent vacancies. CoO (II) can
Cobalt monoxide, CoO, has a narrow range of only be prepared at room temperatures and is very
homogeneity [1-4]. It has a cubic rock salt structure reactive with atmospheric oxygen at ordinary tem-
at room temperature and is paramagnetic [5-8]. Be- peratures. The two forms show different Mossbauer
low 289 K, it becomes antiferromagnetic followed patterns and their Neel temperatures differ. CoO (II)
by a crystal distortion to tetragonal symmetry [5-7, transforms to CoO (I) above ' —'573 K with a trans-
9] and the tetragonality increases with decrease in formation rate that increases with temperature; bn
temperature. Detailed x-ray diffraction studies [10] the other hand, the transition is not complete on
at low temperatures indicated that a rhombohedral heating CoO (II) in an argon atmosphere up to
deformation is superimposed on the tetragonal dis- ~1270 K for several hours and generally CoO (I,

tortion and at 123 K, the true symmetry is mono- II) is obtained which can be treated as a mixture of
clinic. The magnetic structure in the low tempera- forms I and II in varying amounts. Ok and Mullen
ture phase of CoO has been examined by various point out that pressures of ~10 kbar are not
workers [11-13]. Although a number of non-collinear sufficient to transform II—*1 at 300 K in an inert
spin-axis structures are possible in CoO [12, 14], atmosphere. These authors indicate that the usual
available experimental evidence points to a collinear chemical methods of preparation of CoO yield al-
structure [10, 13, 15] with the moments tipped out of ways CoO (I, II).

the {111} planes 7.85° toward the c axis. It should be mentioned that the Mossbauer spec-
The transition in CoO has been studied by a tra of the oxides reported by Ok and Mullen [37]
variety of techniques in recent years. x m T data on differ nontrivially with the work of others; complete
powder and single crystalline CoO indicate typical characterization of CoO (I) and CoO (II) is less

69
unequivocally established [43]. Further detailed work manent moment as a consequence of the splitting of
is urgently needed. the 3d levels by the octahedral cubic field. At ~40 K,
Optical properties of CoO have
been examined by C 03 O undergoes a transition to form an ordered
4

many workers over a wide energy range (0.02-26.0 antiferromagnetic state [58]; the magnetic structure
eV) [44-53]. Studies in the UV region have pro- is due to antiferromagnetic ordering of spins in the

vided an understanding of the density of states in A sites of the spinel structure [60] and each Co2+
CoO [44, 45, 49, 50, 52]; some of the bands observed ion in an A site is surrounded by four nearest neigh-
in the far infrared region have been ascribed to the bors with oppositely directed spins, xm -T curve fol-

antiferromagnetic resonance [19, 46, 47, 53] but the lows a Curie-Weiss law with a deviation at high
resonance frequencies are insensitive to temperature temperatures in the range 90-500 and the ab- K
[53]. normally low value of xm in C03O4 is ascribed to the
Small amounts of Li and Ti can be incorporated fact that the material is a 2-3 spinel in which Co 8+
in CoO and a great deal of work has been carried give no contribution to the magnetic moment [61,

out on these doped materials [3, 20-22, 50, 54, 55]. 62].
Generally, doping with Li decreases the resistivity C 03 O 4 is a semiconductor [42, 63, 64] at ordinary
compared to the pure stoichiometric material. CoO and at high pressures [42]; however, detailed studies
forms solid solutions with other metallic oxides like on single crystal materials have not been made.
MnO, FeO, NiO and MgO [24, 51, 56, 57]. The Mossbauer studies on C 03 O 4 have been reported by
magnetic, electrical, optical and thermal properties a few workers [38, 39, 65]. Above Tn ( = 33±1 K),
show variations depending on the composition of the two quadrupole split lines corresponding to A and B
solid solution. site Fe 3+ are noted while below Tn the A site Fe 8+

C 03 O 4 is a normal spinel and has the ionic structure spectrum is magnetically split due to the antiferro-
Co 2 + [Co 3+ 2 04;
]
it is cubic [58, 59] and paramagnetic magnetic Co 2+ sublattice. NMR studies [66, 67] of
but not ferrimagnetic, although it crystallizes in the C 03 O 4 fully confirm the spinel structure and different
magnetite structure. The Co 3+ ions have zero per- oxidation states of cobalt ion at the A and B sites.

Cobalt oxides

Oxide and description Data Remarks and inferences References

of the study

CoO

Crystal structure and T = 290 K: Cubic, space group, The low temperature structure (at [5-7, 10].
x-ray study. Fm3m; Z = 4; a =4.260 A. T = and below 123 K) is shown to be
250 K: Tetragonal; a =4.263 A; strictly monoclinic and not
c = 4.247 A. T = 123 K: Mono- tetragonal.
clinic;space group, C2/m; Z = 2;
a = 5.18±0.03 A; 6 =3.01 ±0.05
A; c = 3.01±0.07 A; /3 = 125.55±
0.01°. X-ray studies conducted in
the range 210-330 K indicate the
change in crystal symmetry at
284 ±1 K which is recognized as
the Tn.

Magnetic susceptibility in the Xm~ 10 -3 cgs units; slight aniso- The calculated values of xm on the [16-19, 41].
range 90-500 K and the tropy noted. Tn =287.25 K and basis of Kanamori’s theory [19]
effect of pressure. Tn increases with pressure; are in agreement with the ex-
(dTu/dP) =0.6d=0.03 K/kbar. perimental values.

70

Oxide and description
of the study
Electrical properties.
Optical reflectance spectra
(range 1-26 eV).
Infrared spectra
(100-300 cm" 1
) 222, 233, 243, 250, 260, and 297
Mossbauer studies of 57 Fe
doped CoO at ordinary and
high pressures.
Thermal properties.
Cobalt oxides — Continued
Data Remarks and inferences References
Pure oxide: p~10 7 -10 n flcm in the Typical semiconductor behavior in [1, 3, 20-
range 200-300 K; p(1300 K)~ the temperature range investi- 22, 42, 68].
0.5 ficm; pd (1300 K)~0.4 cm 2 /V gated. Band and polaron theories
s; Ea
changes at Tn and slightly have been applied to explain the
depends on the stoichiometry. mechanism of conduction in pure
Li doped CoO (0.05-0.15%): and doped CoO and the weight
p~0.5 ficm; a~ + 500 pV/K; of experimental evidence seems
p D = 0.25 cm /V s (1200 K); to point out the validity of band
2
pd~ 6 cm /V s (300 K); Rn i9
2
model in this oxide.
+ ve; and Rn show discontinui-
p
ties at Tn. ph is constant in the
range 200-1500 K (~0.1 cm 2 /V
s); p type behavior,
p decreases with pressure but no
transition occurs up to 250 kbars.
Optical reflectance spectra give The low energy bands are inter- [44, 49, 50,
bands at and 17.5
5.5, 7.5, 12.6 preted as the exciton transitions [52].
eV. The observed bands at 0.97 whereas the higher energy hands
and 2.28 eV are attributed to may be due to the transitions in
4 —
T lc *T, and 4 T -»«T lff (P)
ff lff
the conduction band. The data
respectively [49]. show the localization of the d
electrons in CoO and the 2 p hand
of oxygen seems to lie ~8.5 eV
below the vacuum level.
Prominent bands are at 146, 215, The data are in agreement with the [19, 45-49,
theoretically predicted values 53].
cm -1 Most of the bands are pre-
. using time-dependent molecular
sumed to be the antiferromag- field theory.
netic resonance modes but tem-
perature variation in the range
2-300 K shows the band to be
insensitive.
1 atmospheric pressure: The hyper- Quantitative features of the spectra [32-40, 43].
fine splitting disappears at Tn seem to differ for various investi-
( 291 K); Isomer shift, screening gations but the general agreement
parameter and magnetic hyper- with the values of Tn is
fine field show discontinuities at excellent.
Tn. High pressures: Tn increases
with pressure; ( d \nTn/d \nV ) =
— 3. Isomer shift and screening
parameter show small changes on
the application of pressure. Ok
and Mullen [43] report different
values of Mossbauer parameters
for CoO (I) and CoO(II).
Dilatometric study shows that the The discontinuous nature of the [24-27, 69].
expansion passes
coefficient of transition indicates that it is
through a sharp maximum at probably of a higher order
292 K
for CoO; TEC at 292 K= transformation.
3.0Xl0 -8 /K. Cp and k show
anomalies at Tn; Cp (290 K) =32
cal/mol, K.
71
 Cobalt oxides — Continued

Oxide and description Remarks and inferences References

of the study

Mechanical properties. Sound velocities in various crys- [28, 29, 31].

tallographic directions change dis-
continuously above Tn by 10-
20%. Elastic moduli (X10 11
dyn/cm 2 ) (300 K): cn=26.17±
0.03; C 12 = 14.5zt0.2; C 44 = 8.32ifc
0.02. During phase transition, Cn
and C 12 exhibit jumps. In the
region of the transition. Young’s
modulus increases rapidly from
6.3 to 17X10 11 dyn/cm, with in-
crease in temperature and the
moduli are approximately step
functions of temperature; on the
other hand, the internal friction
in CoO falls from 91 to 2
(X10 -4 ) at Tn for a constant
-7
strain amplitude of 10 . In-
creasing the strain amplitude has
little effect on the Young’s

modulus and internal friction.

C03O4

Crystal structure and T = 300 K: Cubic; a = 8.0835 A; The crystal structure does not [58, 59, 61,
magnetic properties. space group: Fd3m (T>Tn); change through Tn but
in going 62].
F43m (T < Tn). Tn =40 K. xm the space group changes. The low
(100 K) =1.4X10- 2 xm (300 K) ;
value of xm is believed to be due
= 0.71X10~ 2 The Co 2+ moment
. to the absence of permanent
below Tn is 3.02 mb- moment of Co 3+ and the mag-
netic structure is due to the anti-
ferromagnetic ordering of the
spins of Co 2+ ions on the A sites
of the spinel structure.

Electrical properties. Semiconductor; p~10 -10 4

3
f2cm; [42].

p decreases with P and a mini-

mum is noted at 215 kbars in the
p-P plot. Detailed data not
available.

Mossbauer studies. Tn is found to be 33 ±1 K; above Tn obtained from Mossbauer work [38, 39, 65].
Tn, two quadrupole split lines are than that reported by
is less

observed corresponding to A and Xm-T measurements. The be-

B spinel sites whereas below Tn, havior of ultrafine particles of
the A site Fe 3+ spectrum is mag- C03O4 towards Mossbauer spectra
netically split due to the anti- isinteresting and needs further
ferromagnetic Co 2+ sublattice. detailed study.

72
 Cobalt oxides —Continued

Oxide and description Data Remarks and inferences References

of the study

Above Tn, the spectra of the

ultrafine particles (diameter =
100 A) of C 03 O 4
found to be is

identical to that of the bulk

material. Below Tn, the fine par-
ticles display superparamagnetic
behavior and the B site spectral
broadening is enhanced. The
anisotropy constant estimated
from the superparamagnetic -
antiferromagnetic transition is

4X10 4 erg/cm 3
. Effective 0 d =
185 K.

NMR studies of 59
Co in the The Co signal is identified with the The T-independent shift (1.5%) is [66, 67].
paramagnetic state. Co 3+ ions at the B sites and the interpreted as the second order
T-
line shift is separated into chemical shift due to the mixing
dependent and T-independent of the low-lying excited state;
terms; the line shapes are studied the T-dependent shift is at-
and the thermal relaxation time tributed to the hyperfine coupling
is estimated to be ~1.5X10
-5 between the Co nuclear spin and
s.

the electron spins on the Co 2+

ions at the A sites in C 03 O 4 The .

super -exchange mechanisms are

examined and it is concluded
that 2 % fractional spin density in
the Co 3+ e g orbital mainly con-
tributes to the super -exchange.

Diffuse reflectance Absorption bands at 0.81 and 1.85 It is concluded that the forbidden [49].
spectral studies. eV are noted. These are attrib- band widths in CoO and C 03 O 4
uted to Co 2+ at A sites ( 4A 2 — are almost identical.
4
T 2) and Co 3+ at B sites QTig—*
4
Ai g ) transitions respectively;
corresponding Dq values are 0.08
and 0.19 eV.

Infrared spectral studies. The prominent bands are at 570 The spectra have been discussed in [48, 70, 71].
and 665 cm -1 ; other bands are at relation to other oxide spinels and
350, 460 and 635 cm -1 . and co valency effects.

C02O3

Crystal structure and phase Low -spin phase (with t 2ff e s° The high -spin phase appears to be [72].
transition configuration) is obtained at the stable phase at atmospheric
high pressures. This phase has pressure.
corundum structure (a =4.782 A
and c = 12.96 A). The low-spin
phase transforms to the high-
spin corundum phase ( 2s e s2 )
around 670 K
(a =4.8882 A,
c = 13.34 A).

73
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74
 1.8. Nickel Oxides [50] indicate that the samples of NiO remain semi-
conducting and that the d electrons are localized.
Nickel monoxide, NiO, is the only stable oxide in Even though it is definitely known that the d
the Ni-0 system. Earlier literature [1, 2] contains electrons in NiO are localized, the detailed mecha-
reports of the existence of some 25 different oxides nism of electrical conduction is not yet understood;
of nickel including Ni 3 04 , Ni 2 0 3 and Ni0 2 and
, the various properties of this material have been
Kuznetsov [3] has recently suggested that all the reviewed in several articles [51-56]. The available
higher oxides and oxide solid solutions are merely data on transport properties indicate that: (a) be-
partial hydroxide decomposition products. Detailed tween 200 to 1000 K, the predominant conduction
studies made shown that the
recently [4-6] have mechanism is the motion of holes in a band with an
monoxide is the only material known in the Ni-0 m* = 6 m; (b) the carrier concentration in lightly
system and slight deviations from stoichiometry are doped samples is thermally activated with an accep-
allowed [4-7]. The possibility of synthesizing Ni 3 0 4 tor ionization energy of 0.3-0.4 eV; (c) Li acceptors
at high pressure has been pointed out [8]. are always self-compensated by donors; (d) hd
NiO one of the extensively studied transition
is («0.5 cm 2 /V s at 300 K) decreases with rise in T
metal oxides. In the paramagnetic state it has the and ph is proportional to hd in the range 300 to 600
fee rock salt structure [9-17] and as the temperature K and (e) intrinsic conduction is observable at
is lowered through T (~523 K), there is a trigonal T> 1000 K in the more highly compensated samples.
distortion in the unit cell [9-14, 16, 17] and the It appears that small polaron hopping by 3d-holes
material becomes antiferromagnetic [11-13, 18]; in (with low Ea ) contributes little to the total con-
addition, there an isotropic volume contraction
is ductivity at ordinary temperatures (100-1000 K)
associated with the magnetic behavior. In the anti- whereas the major contribution is from the holes in
ferromagnetic state, the spins are ferromagnetically the oxygen 2p-band of NiO. We may note here that
alligned in sheets parallel to (111) planes and anti- until 1963 was generally taken for granted that
it

parallel to those in adjacent sheets [11-13, 18]. This charge -transfer in doped NiO involved activated
magnetic structure is characteristic of all the transi- mobilities.Since then the weight of the evidence
tion metal monoxides and is explained as due to the seems to have shifted in the other direction; for
antiferromagnetic superexchange through the p orbi- example, the studies of Bosman and Crevecoeur [42]
tals of the intervening oxygen anions [19]. Below T n, are in favor of the band regime. Since most of the
the unit cell contracts along the [111] axis perpen- studies have been on doped or nonstoichiometric
dicular to the ferromagnetic sheetsand the crystal NiO, we have to view the various claims with some
becomes rhombohedral; the distortion from cubic is, caution. Needless to mention, there is continuing
however, small and the rhombohedral angle increases need for careful experimental studies on pure NiO.
from 90° at Tn to 90.06° at 300 K [17]. x-T data Optical absorption measurements have been car-
definitely indicate the antiferromagnetic behavior ried out on pure and doped NiO from far infrared
of NiO [20]. Magnetic anisotropy and antiferromag- through x-ray frequencies [44, 57-68] and the results
netic domains in NiO have been studied by a few indicate that the d electrons are localized. There is
workers [13, 19, 21-24]. a peak at 0.24 eV which begins to broaden and de-
Pure, stoichiometric NiO is green in color and the crease in energy above 400 K and disappears above
reported black and grey colors are due to slight devia- 600 K [58, 63]; it appears to be connected with anti-
tions from stoichiometry or the presence of impuri- ferromagnetism since the band vanishes just above
ties [25-27].Stoichiometric NiO is a good electrical Tn and moves towards lower energies with decrease
insulator (p^l0 13 flcm) but the p decreases drastic- in sublattice magnetization by either increase of
ally by slight changes in the stoichiometry or by temperature [58] or dilution with MnO or CoO [59].
lithium doping at small concentrations. Electrical The main feature in the optical spectrum of NiO is

properties of pure and doped NiO have been in- the absorption edge at ~3.8 eV [57, 58, 64, 67].
vestigated by various workers for the past few years Infrared studies show restrahlen bands at ^0.05 eV
[4, 5, 28-48]. Discontinuities in p, E0 a and jRh are , the antiferromagnetic resonance peak is at 0.04 eV
encountered at Tn', Rh changes sign from positive below Tn [46, 69-71]. The band structure that em-
to negative values at around Tn, but the exact cause erges from the optical absorption, electroreflectance
of this behavior is not understood. Measurements in [72] and photoemission [73] studies is consistent
the range 10 to 1300 K and at various dopant con- with the theoretically calculated band structure of
centrations (up to 40% [49]) and at high pressures NiO [74-76].

75
 Moiibauer studied of 67
Fe doped NiO have been NiO forms solid solutions with other oxides of
reported in the literature [77, 78] and accurate value rock salt structure and the properties
[59, 66, 84, 85]
of Tn obtained. Digcontinuitiei in k, C p am. Young’s, are slightly modified depending on the nature of the
modulus and internal friction and TEC have been oxide.
noted in pure and Li doped NiO [79-83],

Nickel oxides

Oxide and description Remarks and inferences References

of the study-

NiO

Crystal strucrure, T—> 0 K: Rhombohedral; a =4.1705 The rhombohedral distortion is [9-17].

x-ray studies. A; a =90.075°. T = 298 K: o small and the transition at Tn
Rhombohedral; a =4.1759 A; appears to be second order.
a =90.058°. T = 525 K: Cubic;
space group, a=
Fm3m; Z = 4;
4.177 A. Slight volume change at
Tn (523 K). High pressure stud-
iesup to several hundred kilobars
do not reveal any phase transi-
tion. TEC (/K): 7.93X10“®;
0d = 9OO K.

X-T studies and observation x(Tn) =11.7X10“® emu/g. The
of the magnetic domains by antiferromagnetic T (twin) and
optical and neutron S (spin -rotation) walls studied.
diffraction. Crystals with only T or S walls
can be produced; these can be
displaced by the application of
small mechanical stress or mag-
Magnetic field de-
netic fields.
pendence of x also is noticed.
The antiferromagnetic-paramag- [11-13,
netic transition appears to be of 19-24].
order greater than unity and
slight magnetic order has been
noticed above Tn by neutron
diffraction. The anomalous x in
(111) at higher magnetic fields is
caused by spin rotation.

Electrical properties. Pure NiO: p (300 K)~10 13 ftcm; At very low temperatures, im- [4, 5, 28-
pap 0s “ 1/4
(po 2 . 10-M atm.; purity conduction is noticed 50].
1170-1473 K); p«por 1/6 (po«, whereas in the range 100-1000 K
10-2-10+3 atm; 1320 K); p« 3 d holes contribute to conduction
Po»~
lli
(pog^lO -1 atm; 1070- (only a small part of the total <r )

1373°K). The data are inter- by hopping of the small polarons.

preted in terms of the singly and Major part of the conductivity
doubly ionized cation vacancies; comes from the holes in the oxy-
the conduction is of p type. Im- gen 2p band in pure and slightly
purities in the range 100-500 doped NiO. The high tempera-
ppm seem to affect the intrinsic ture Hall data anomalies are sug-
electrical properties. Ea ~ 0.9 eV gested to be due to the forma-
(200-500 K); above Tn, Ea drops tion or small phase separation of
to 0.6 eV and increases to 1.0 eV n type Ni 3 0, or small regions of
at 1000 K; Range 10-100 K, Ea ~ metallic Ni in the samples.
0.004 eV. mh~ 0.5 cm a /V s, at 200
K and hole like behavior; no
striking temperature variation in
the range 200-400 K but mh
gradually decreases with rise in
T. Above 400 K, rapid decrease
isshown and at ~600 K, mh re-
verses sign, a ^0.5 raV/K at
~200 K and above 300 K, has

76
 Nickel oxides —Continued

Oxide and description Data Remarks and inferences References

of the study

the same slope as log p as a

function of T. Doped NiO: p~l
12cm at 300 K and E a is much

smaller than in pure samples; Ea

varies with dopant concentration
and slightly with T. p h and a
behave in a qualitatively similar
manner as the undoped samples.
Application of pressure decreases
p but thesample remains semi-
conducting up to the highest
pressures measured (~500 kbar).
Neutron irradiation seems to in-
crease p and decrease a of pure
NiO.

Optical properties The main features are (i) anti* Most of the observations are con- [44, 57-72].
(0.03-26 eV). ferromagnetic resonance peak at sistent with other body of data
eV observed in NiO below
'**'0.04 and the band picture that
Tx (and which disappears above emerged is in reasonable agree-
Tx), (ii) restrahlen peaks in the ment with the theoretical pre-
vicinity of 0.05 eV, peak at (iii) a dictions. The peak at 0.24 eV
0.24 eV which begins to broaden appears to be connected with
and decrease in energy above antiferromagnetism in NiO.
400 K and disappears at ~600
K, (iv) absorption edge at ~0.38
eV and (iv) several high energy
peaks in the range 5-18 eV con-
nected with interband transitions.
eo»12; e«»5.

Mossbauer studies of 67 Fe An electric held gradient which The order of the transition in NiO [77,-78].
doped NiO (4.2-550°K). appears at the 67
Fe nucleus below appears to be greater than unity.
Tx grows as T decreases. The
internal magnetic held is maxi-
mum (216 kG) at ^300 K and
decreases to ~55 kG at 4.2 K.
Tx is found to be 524 K and the
direction of spins of Ni* + is

found to be close to <112>.

Thermal and mechanical Cp shows a X-type anomaly at Tx; Striking anomalies are noted inspite [79-83].
properties. maximum value of Cp = 65 cal/ of the negligible volume change
mol. aid and k also show anoma- and only smooth variation of the
Tx. Large increase in
lies at lattice parameter at Tx in NiO.
Young’s modulus noted at ~Tx
(Maximum value = 8.5 X10 -11
dyn/cm2 ). Elastic wave veloc-
ity also increases at ~Tx in NiO.

77
 —

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78
 1.9. Copper Oxides as hydrogen-like series of narrow- lines at the ab-
sorption edge and towards the long-wavelength re-
Phase equilibrium studies [1-3] on the Cu-0 sys-
gion (yellow series). Similar series of lines (called the
tem indicate that Cu 2 0 and CuO are the only stable
green, blue-green and blue series) also appear near
oxide phases in the solid state; both have narrow-
the other interband transitions [23-25] and are due
ranges of homogeneity. Frondel [4] has reported the
to the optical excitation of the excitons in Cu 2 0.
existence of a tetragonal nonstoichiometric oxide of
Detailed investigation of these excitonic spectra con-
the formula (Cu 2 + i_2 xCu+2z)Oi_*, x= 0.116, but de-
tributed to the understanding of the photoconduc-
tails are not know-n.
tivity and band structure of Cu 0 2 [23, 26].
Cu 0: Cuprous
2 oxide, Cu
2 0, has a cubic structure

[5] and no phase transformations are known up to CuO: Cupric oxide, CuO, has a monoclinic structure
the melting point [3, 5]. Because of the extensive [27, 28] and has considerable covalencv associated
use of Cu 0
2 as a barrier layer photoelectric cell, wdth the Cu-0 bond [28]; no phase transformations
many workers have successfully grown single crystals are known at ordinary pressures. CuO is a semi-
of the oxide [6, 7]. CU O 2 has considerable covalency conductor [29, 30] and resistivity studies at high
associated with theCu-0 bond and exhibits plastic pressure [29] seem to indicate a phase transition;
behavior above 870 K [5, 8]. The material is a semi- however, detailed data are lacking.
conductor and the bulk and surface resistivities and CuO forms solid solutions with PdO [31, 32] and
f
photoconductivity have been examined by several PtO’ [33]having a tetragonal structure and with
workers [9-18]. Optical absorption studies [19-22] MgO, NiO and CoO having cubic rock salt structure
indicate several reflection bands with an absorption [32]; the lattice constant-composition curve extrapo-
edge, corresponding to the optical energy gap, of lated to pure CuO suggest the existence of a
~2.02 eV. Cu 2 0 exhibits the interesting phenomena tetragonal or cubic metastable (crypto-) modification
of exciton spectra at low temperatures which appear of CuO [31-33].

Copper oxides

Oxide and description Data Remarks and inferences References

of the study

Cu 0 2

Crystal structure and Cubic; space group, Pn3m; Z — 2; Cu 0 2 has an unusual structure de- ]5, 8].

x-ray studies. a =4.268 ±0.001 A. TEC (120- scribed as two interpenetrating

470 K), /°C): 2X10-0. Melting and identical frame works of
point ~1510 K. copper and oxygen atoms which
are not cross connected by any
primary Cu-0 bonds. Consider-
able convalency is associated with
the Cu-0 bond.

Electrical properties. Semiconductor (300-670 K); p (400 The conductivity behavior in Cu 2 0 [9, 15].

K)~2X10 3
flcm; Ea = 0.26 eV; is complicated by surface and

a (400 K)~+l mV/°C; mh photoconductivity effects.

(300 K)«0.08 cm 2 /V s. Cu 2 0
may be nearly an ionic conductor
and extrinsic hole conduction
can occur by activated hopping.

Elastic properties by pulse Room temperature values of elastic [34].

echo technique constants (XlO 12 dyn/cm 2 ): Cn =
(4.2-300 K). 1.165 ±0.005; ci 2 = 1.003 ±0.04;
= 0.121 ±0.003. Limiting low-
c4 4
temperature values (~4.2 K)
(XlO 12 dyn/cm 2 ): Cn = 1.211±
= 1 .054 ±0.04; C44 =
0.005; Ci 2

79
 ±

Copper oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

0.109 ±0.003. 0d = 181 K; com-

possibility (300 K) = 0.946 X
10“ 6 cm 2 /kg.

Optical properties and Reflectivity bands at 2.67, 3.85, The data are discussed in terms of [14, 19-
band structure. 4.64 and 5.00 eV are noted. the band structure of CU 2 O. 26].
Energy gap is estimated to be
2.02 eV. €o = 7.60; €» = 6.46. Ex-
citon spectra are noted at the
band edge at low 3temperatures.
CuO
Crystal structure and Monoclinic; space group, C2/c; The structure can be described in [3, 27, 28].
x-ray studies. Z = 4; = 4.6837 ±0.005 A; b =
a the following manner: the build-
3.4226 ±0.0005 A; c = 5.1288 ing elements are the oxygen co-
0.0006 A; /3= 99.54 ±0.01°. TEC ordination parallelograms, which
(293-973 K, /°C) «6.5XlO-«. form chains by sharing edges.
[010]
Each copper atom is coordinated Such chains traverse the structure
to four coplanar oxygen atoms in the [110] and [110] directions,
situated at the corners of an al- the two types of chains alternat-
most rectangular parallelogram; ing in the [001] direction. Each
the oxygen atom is coordinated to type of chain is stacked in the
four copper atoms situated at the direction with a separation
corners of a distorted tetra- between the chains of ~2.7 A;
hedron. each individual chain in a group
Estimated ionic character of stacked chain of [110] type is
40%; hence the bonding in CuO linked to each chain in the two
appears to be predominantly adjacent groups of [110] type by
covalent. corner sharing.

Electrical properties.
p (296 K)~2-4X10 Slcm at 20 The high pressure data seem to [29, 30].
kbar pressure. High pressure indicate a solid -solid phase
studies indicate no transition up transition in CuO but detailed
to 450 kbar at 300 K or up to studies are yet to be made.
419 K at 17 kbars; however, at
391 K, p shows discontinuous
drop at 187 kbar or 462 kbar at
360 K. a data indicate p type be-
havior. Detailed data are lacking.

References [7] Brower, W. S., Jr. and Parker, H. S., J. Cryst. Growth
8, 227 (1971), and references therein.
[8] Vagnard, G., and Washburn, J., J. Am. Ceram. Soc. 51,
88 (1968).
[1] Roberts, H. S., and Smyth, F. H., J. Am. Chem. Soc. [9] Toth, R. S., Kilkson, R., and Trivich, D., Phys. Rev.
43, 1061 (1921). 122, 482 (1961).
[2] Gadalla, A. M. M., and White, J., Trans. Brit. Ceram. [10] O’Keeffe, M., and Moore, W. J., J. Chem. Phys. 35,
Soc. 63, 39 (1964). 1324 (1961); 36, 3009 (1962).
[3] Pranatis, A. L., J. Am. Ceram., Soc. 51, 182 (1968). [11] Campbell, R. H., Kass, W. J., and O’Keeffe, M., in
[4] Frondel, C., Am. Mineral. 26, 657 (1941). Mass Transport in Oxides, Nat. Bur. Stand. (U.S.),
[5] Suzuki, T., J. Phys. Soc. Japan 15, 2018 (1960). Spec. Publ. 296 (1968), p. 173.
[6] Toth, R. S., Kilkson, R., and Trivich, D., J. Appl. [12] Young, A. P., and Schwartz, C. M., J. Phys. Chem.
Phys. 31, 1117 (1960). Solids 30, 249 (1969).

80
[13] Zielinger, J. P., Tapiero, M., Roubaud, Mme. C., and
1. 10. Zinc Oxides
Zouaghi, M., Solid State Commun. 8, 1299 (1970).
[14] Kuzel, R., and Weichman, F. L., Canad. J. Phys. 48,
1585 (1970); 48, 2643 (1970). ZnO is the stable oxide of zinc and it has the
[15] Kuzel, R., Cann, C. D., Sheinin, S. S., and Weichman,
F. L„ Canad. J. Phys. 48, 2657 (1970). wurtzite (hexagonal) structure at room temperature.
[16] Fortin, E., Zouaghi, M., and Zielinger, J. P., Phys. No
It is piezoelectric. phase transformations are
Letters 24A, 180 (1967).
[17] Zouaghi, M., Caret, A., and Eymann, J. 0., Solid State known in ZnO in the range 4.2 to 890 K. At high
Commun. 7, 311 (1969). pressures, it transforms to the rock salt structure at
[18] Zouaghi, M., Tapiero, M., Zielinger, J. P., and Burgraf,
R„ Solid State Commun. 8, 1823 (1970). room temperature.
[19] Balkanski, M., Petroff, Y., and Trivich, D., Solid State Yannerberg has reported a cubic form of zinc
[1]
Commun. 5, 85 (1967).
[20] Tandon, S. P., and Gupta, J. P., Phys. stat. solid! 37, 43 peroxide, Zn0 2 (a = 4.871 ±0.006 A), but apparently
(1970). no other studies on this material are available in
[21] Dahl, J. P., and Switendick, A. C., J. Phys. Chem. Solids
27, 931 (1966). the literature.
[22] —
Smirnov, V. P., Sov. Phys. Solid State (English Transl.) Because of the technical importance, single crys-
7, 2312 (1966); 8, 2020 (1967).
[23] Gross, E. F., Sov. Phys. Uspekhi (English Transl.) 5, tals ofZnO have been grown by a variety of tech-
195 (1962). niques including hydrothermal, flux growth, travel-
[24] Deiss, J. L., Daunois, A., and Nikitine, S., Solid State
Commun. 7, 1417 (1969); 8, 521 (1970). ing vapor phase reaction and oxidation
solvent,
[25] Forman, R. A., Brower, W. S., Jr., and Parker, H. S., methods parameters and thermal ex-
[2-7]. Lattice
Phys. Letters 36A, 395 (1971).
[26] Elliot, R. J., Phys. Rev. 108, 1384 (1957); 124, 340 pansion coefficients have been determined by various
(1961). workers in the range 4.2 to 890 K [7-13]. ZnO is a
[27] Tunell, G., Posnjak, E., and Ksanda, C. J., Z. Krist.
0 90, 120 (1935).
semiconductor and the electrical transport properties
[28] Asbrink, S., and Norrby, L.-J., Acta Cryst, 26B, 8 (1970). and optical characteristics have been examined in
[29] Minomura, S„ and Dnckamer, H. G., J. Appl. Phys. 34,
3043 (1963). detail in the literature [6, 14-18],
[30] Zuev, K. P., and Dojgintsev, V, D., Izv. Akad. Nauk High pressure x-ray diffraction [19, 20] and optical
SSSR, Neorg. Mater. 4, 1498 (1968).
[31] Schmahl, N. G., and Minzl, E., Z. Physik. Chem. (N.F.) studies [21] indicated that ZnO transforms from
47, 142 (1965). hexagonal to cubic structure at pressures '--'100-125
[32] Schmahl, N. G., and Eikerling, G. F-, Z. Physik. Chem.
(N.F.) 62, 268 (1968). kbar at 300 K (Bates et al. give a value 670 K).
[33] Muller, O., and Roy, R., J, Less-Comm. Metals 19,
Studies of Bates and co-workers [20] indicate that
209 (1969).
[34] Hallberg, J., and Hanson, R. C., Phys. stat. solidi 42, NH 4 C1 acts as a catalyst in the formation of the
305 (1970). high pressure phase and the transformation is slug-
gish. The cubic phase does not revert back to the
wurtzite structure even after prolonged standing
(several weeks) at room temperature; however, at
^390 K, it reverts within three weeks time.

Zinc oxides

Oxide and description Data Remarks and inferences References

of the study

ZnO

Crystal structure and Range, 4.2-890 K; Hexagonal; Reeber [9] has summarized all the [9, 11, 12].
x-ray studies. space group, P6amc; Z = 2; 6 d = earlier crystal data on ZnO.
370 K. T = 297 K: a = 3.2497 dh Slight anisotropy in TEC values
0.0009 A; c = 5.206 ±0.0009 A. is evident.
TEC (300-890 K; °/C)i a -
||
=®
6.05X 1O“ 8 +2.20X 10 J+2.29X
10= 18 *»; = 3.53 X 10 =e H=2.38 X
1
1®

=#
10 t+9.24X10 =ls t 1 (t in § C).
Ibach [12] and Reeber [9] find
that in the range 4.2=300 K, a
goes through a minimum at 93 K.

81
 Zinc oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

Pressure transition High pressure x-ray study shows T t The 4:4 coordination of the [19-21].
to be 673 or 300 K at pressures wurtzite phase of ZnO
changes to
~105-110 kbars. Cubic phase; 6:6 coordination in the rock salt
space group, Fm3m; Z = 4; a = phase; the latter phase is denser.
4.28 A. AH = 785 AS =
cal/mol;
-2.5 e.u.; dP/dT = 42.5 X10~ 3
bar/°C; AV = —2.55 cm 3 /mol.
High pressure optical absorption
indicates transition at 125 kbars
at 300 K. Absorption edge is at
3.14 eV ( = E 0 at 1 bar);
,

d(AE g )/dP = 0.6-1.9X10-" eV/

bar (wurtzite); = 1.9X1O -0
eV/bar (rock salt).

Electrical properties.
Pure undoped crystals have p~l- Eg is ~3 eV but donor levels of [14-18].
100 ficm but doping increases the ~0.3 eV below the conduction
p by a factor '"-•'10. The p of band always create charge car-
sintered and unsintered speci- riers thermally and contribute to
mens behave differently with to the conductivity.
respect to temperature. Inter-
stitial metal atoms appear to
play a dominant part.

Hutson [16] obtained the following In the range 150-900 K, T de-

transport parameters at 300 K: pendence of mh has been ex-
a«1.7 mV/K; mh = 180 cm 2 /V s; plained by the optical mode
n c =2 X 10 16 cm -3 m* =0.5 m;
;
scattering; however, below 150 K,
trip* = 0.27 m; a?* = 0.85; «o = 8.5; ionized impurity scattering and
e» = 3.73; 0 d =92O K. phonon -drag effects play a
significant role.

References [11] Khan, A. A., Acta Cryst. 24 A, 403 (1968).

[10] [12] Ibach, H., Phys. Stat. solidi 33, 257 (1969).
[1] Vannerberg, N. G., Arkiv Kemi 14, 119 (1959). [13] Kirchner, H. P., J. Am. Ceram. Soc. 52, 379 (1969).
[2] Weaver, E. A., J. Cryst. Growth 1, 320 (1967). [14] Hahn, E. E., J. Appl. Phys. 22, 855 (1951).
[3] Kleber, W., and Mlodoch, R., Krist. Tech. 1, 245 (1966); [15] Hutson, A. R., Phys. Rev. 108, 222 (1957).
Chem. Abstr. 69, 46561m (1968). Hutson, A. R., in Semiconductors, Ed. N. B. Hannay
[16]
Hirose, M., and Kubo, I., Japan J. Appl. Phys 402
[4] 8, (Reinhold Publ. Corp., New York, 1959), p. 541.
(i969).
[17] Seitz, M. A., and Whitmore, D. H., J. Phys. Chem.
[5] Cleland, J. W., in Mass Transport in Oxides, Nat. Bur.
Solids 29, 1033 (1968).
Stand. (U.S.), Spec. Publ. 296, (1968), p. 195.
Nielsen, K. F., J. Cryst. Growth 3-4, 141 (1968). [18] Hideo, H., and Kasae, K., Nippon Kagaku Zasshi 90,
[6]
Heller, R. B., McGannon, J., and Weber, A. H., J. 112 (1969); Chem. Abstr. 70, n821z (1969).
[7]
Appl. Phys. 21, 1283 (1950). [19] Class, W., Iannucci, A., and Nesor, H., Norelco Reporter
[8] Abrahams, S. C., and Beinstein, J. L., Acta Cryst. 25B, 13, 87 (1966); 13, 94 (1966).
1233 (1969). [20] Bates, C. H., White, W. B., and Roy, R., Science 137,
[9] Reeber, R. R., J. Appl. Phys. 41, 5063 (1970). 993 (1962).
Sirdeshmukh, D. Ef., and Deshpande, V. T., Curr. Sci. [21] Edwards, A. L., Slykhouse, T. E., and Drickamer, H. G.,
(India) 36, 630 (1967). J. Phys. Chem. Solids 11, 140 (1959).

82
j

II. Oxides of 4 d Transition Elements

II. 1. Yttrium Oxides indexed on a hexagonal basis but a monoclinic sym-

metry could not be ruled out.
The fully oxidized form, Y2O3, is the only solid The C-type structure of Y2O3 is relatively loose
oxide of yttrium [1-3]; substoichiometric yttrium and is of lower density compared to the B- (mono-
oxide, Y0 i. 5_ x , has, however, been reported by a clinic)and A- (hexagonal) type structures (usually
few workers [4-6]; with x = 0.009, the oxide possesses adopted by rare earth sesquioxides). One would,
intense green color and is paramagnetic in nature, therefore, expect that application of pressure should
but the crystal structure is the same as that of favor the denser structures. Accordingly, Hoekstra
stoichiometric Y2O3. Miller and Daane [5] report a and Gingerich [11], Hoekstra [12] and Prewitt et al.

higher lattice parameter and a lower density for [13] noticed that C—*B conversion occurs in Y2O3 at
YO1.491 compared to YOi.soo* A monoxide, YO, was ^25 kbar and at ~T270 K. The high pressure phase
reported [7] as an impurity in Y metal on the basis can be quenched and the reversibility of the phase
of x-ray pattern, but it is likely to have been a sur- transformation has been confirmed by heating the
face film; the existence of YO as a bulk phase has B-form in air at ^1270 K or annealing in air at
not been reported. ambient pressure and ^1170 K for several hours
Y2O3: Y02 3 has a cubic C-type rare-earth oxide [11, 12]; from the observed pressure -temperature
structure at room temperature and 1 atmospheric data, the enthalpy and entropy changes accompany-
pressure and can be described as a modified fluorite ing the C—>B transformation in Y2O3 have been
phase having one anion in four missing to balance estimated [1, 14].

the tri valent cationic charge with a slight readjust- Electrical properties of Y2O3 have been examined
ment of the positions of the remaining ions. The by a few workers [15-22], Y2O3 exhibits p-type semi-
resulting unoccupied anion sites may be considered conduction with considerable ionic contribution to
as forming nonintersecting strings along the four the total conductivity. The ionic conductivity has
(111) directions of the cubic cell [1-3]. been ascribed to the anionic migration [17, 18, 20-
A hexagonal (H) form of Y2O3 at high temperatures 24] but the contribution is smaller the larger the
(~2650 K) has been reported by Foex and Traverse temperature and is less than 1 percent above 1500 K;
[8].This H-form of Y2O3 is closely related to the impurities in slight amounts seem to play a dominant
A-type rare-earth oxide structure. The C—>H trans- role in ionic conduction [18, 24].
formation has been found to be reversible [8] and the Y2O3 forms solid solutions with oxides of the type
two modifications are usually observed to coexist MO (M = Sr [25]), 2 03 M
(M = B [26], Al [27], Sc
over a remarkably extended range of temperatures. [28, 29], La [30] and Nd [30]) and 2 (M = Ti M0
Noguchi et al. [9] report a crystal structure transi- [31, 32], Zr [9, 31, 33-36], Hf [37-42], Ce [23],
tion (probably C—>H) at ~2550 K. Mehrotra et al. Th and Re [45, 46]) and their properties
[43, 44]
[10]have reported a high temperature transformation have been examined extensively. Some of the TI1O2-
inY2O3 which is reversible and occurs over the range Y2O3 solid solutions exhibit 100 percent ionic con-
670 to 1170 K. The high temperature phase has been ductivity and are used as solid electrolytes [47, 48].

83
 Yttrium oxides

Oxide and description Data Remarks and inferences References

of the study

Y2O3

Crystal structure (including T = 300 K, 1 atm pressure: Cubic The cubic structure of Y2O3 is the [1-3, 8,
high temperature high (C-type); space group, Ia3; Z= usual structure type adopted by 10-12].
pressure x-ray studies. 16; a = 10.604 A. High tempera- the heavy rare earth oxides. It is

ture phases. T = 1170 K: Hexa- remarkable that the structure

gonal (A-type?); a =9.80 A; change on heating is to that of a
c = 10.17 A. T = 2603 K: Hexa- lower symmetry and is due to
gonal (H-type); a =3.805 A; c = the changes in coordination and
6.085 A. Cubic-monoclinic (B- increase in density. The pressure
type) transition at ~25 kbar transition does not go through
and at ~1270 K. High pressure the corundum phase and the de-
phase is monoclinic; space tailedmechanism has been dis-
group, Z = 6; a = 13.91 A±
C2/m; cussed by Prewitt et al. [13].
= 3.483 ±0.003 A; c =
0.01 A; b
8.593±0.008 A; = 100.15± /3

0.05 A.A H (estimated) ~2 kcal/

mol; AS (estimated) ~1.5 e.u.
Melting point = 2959 ±20 K
[49].

Electrical properties Semiconductor; p (970 K)~10 7 Y2O3 at low temperatures can be [15-24].
(300-1500 K). J2cm; Ea ~
1 eV; a (900 K)~2 considered to be almost an in-
mV/°C; p-type to n-type change sulator having a very high re-
at low oxygen partial pressures. resistivity. Impurities exert a lot
Considerable ionic conductivity of influence in the ionic conduc-
below 1000 K; above 1500 K, tivity of the material; purest
pure electronic conduction. sample has a very low ionic
contribution. The p- to n-type
change Y2O3 may be due to
in
loss of oxygen and creation of
anion vacancies at high
temperatures.

Dielectric and infrared eo=9.77; e«, = 3.58. Several bands [50-53].

-1
studies. in the region 300-560 cm are
noted;weak bands in the region
800-1070 cm -1 also exist. The
bands are attributed to metal-
oxygen vibrations.

Heat capacity studies Cp (1300 K) =31.17±19 cal/deg The cause of the Cp anomaly at [54, 55].
(300-1800 K). mol. An anomaly has been noted 1330 K is not known.
at 1330 K with a AH = 310 cal/
mol; AH (estimated, by extra-
polation) = 249 ±66 cal/mol;
AS =0.19±0.05 e.u.

References [3] Paton, M. G., and Maslen, E. N., Acta Cryst. 19, 307
(1965).
[1] Brauer, G., Progr. in the Science and Technology of [4] Haefling, J. A., Schmidt, F. A., and Carlson, O. N.,
Rare Earths Ed. L. Eyring (Pergamon, Oxford), 1, J. Less-Comm. Metals 7, 433 (1964).
152 (1964); 2, 312 (1966); 3, 434 (1968). [5] Miller, A. E., and Daane, A. H., J. Inorg. Nucl. Chem.
[2] Fert, A., Bull. Soc. Franc. Mineral Crist. 85, 267 (1962). 27, 1955 (1965).

84
 6] Miller, A. E., Thesis,Iowa State Univ. of Sci. and Tech. [43] Wimmer, J. M., Bidwell, L. R., and Tallan, N. M.,
1964; Nucl. Sci. Abstr. 20, 880 (1966). Nucl. Sci. Abstr. 19, 42896 (1965).
[7] Huber, E. J., Jr., Head, E. L., and Holley, C. E., Jr., [44] Subbarao, E. C., Sutter, P. H., and Hrizo, J., J. Am.
J. Phys. Chem. 61, 497 (1957). Ceram. Soc. 48, 443 (1965).
[8] Foex, M., and Traverse, J.-P., Compt. Rend. (Paris) [45] Roy, R., McCarthy, G. J., Muller, O., and White, W. B.,
261, 2490 (1965). Nucl. Sci. Abstr. 20, 36784 (1966).
[9] Noguchi, T., Mizuno, M., and Yamada, T., Bull. Chem. [46] Roy, R., Kachi, S., McCarthy, G. J., Muller, O., and
Soc. Japan 43, 2614 (1970). White, W. B., Nucl. Sci. Abstr. 20, 13260 (1966).
[10] Mehrotra, P. N., Chandrashekar, G. V., Rao, C. N. R., [47] Wimmer, J. M., Bidwell, L. R., and Tallan, N. M.,
and Subbarao, E. C., Trans. Faraday Soc. 62, 3586 J. Am. Ceram. Soc. 50, 198 (1967).
(1966). [48] Patterson, J. W., Bogren, E. C., and Rapp, R. A.,
[11] Hoekstra, H. R., and Gingerich, K. A., Science 146, J. Electrochem. Soc. 114, 752 (1967).
1163 (1964). [49] Noguchi, T., and Kozuka, T., Solar Energy 10, 203
[12] Hoekstra, H. R., Inorg. Chem. 5, 754 (1966). (1966).
[13] Prewitt, C. T., Shannon, R. D., Rogers, D. B., and [50] McDevitt, N. T., and Davidson, A. D., J. Opt. Soc.
Sleight, A. W., Inorg. Chem. 8, 1985 (1969). Amer. 56, 636 (1966).
[14] Westrum, E. F., Jr., Progr. in the Science and Tech- [51] Goldsmith, J. A., and Ross, S. D., Spectrochim. Acta
nology of Rare Earths, Ed. L. Eyring (Pergamon, 23A, 1909 (1967).
Oxford) 3, 459 (1968). [52] Subba Rao, G. V., Rao, C. N. R., and Ferraro, J. R.,
[15] Noddack, W., and Walch, H., Z. Elektrochem. 63, 269 Appl. Spec. 24, 436 (1970).
(1959); Z. Physik. Chem. (Leipzig) 211, 194 (1959). [53] Nigara, I., Ishigame, M., and Sakurai, T., J. Phys. Soc.
[16] Neuimin, A. D., and Pal’guev, S. F., Chem. Abstr. 59, Japan 30, 453 (1971).
941 7g (1963). [54] Pankratz, L. B., King, E. G., and Kelley, K. K., U.S.
[17] Tare, V. B., and Schmalzried, H., Z. Physik. Chem. Bur. Mines, Rept. Invest. No. 6033, 1962.
(NF) 43, 30 (1964). [55] Holley, C. E., Jr., Huber, E. J., Jr. and Baker, F. B.,
[18] Tallan, N. M., and Vest, R. W., J. Am. Ceram. Soc. Progr. in the Science and Technology of Rare Earths
49, 401 (1966). Ed. L. Evring (Pergamon, Oxford), 3, 343 (1968).
[19] Zyrin, A. V., Dubok, V. A., and Tresvyatskii, S. G.,
Chem. Abstr. 69, 62562t (1968). II. 2. Zirconium Oxides
[20] Chandrashekar, G. V., Mehrotra, P. N., Subba Rao,
G. V., Subbarao, E. C., and Rao, C. N. R., Trans. The oxygen in a -zirconium (hexagon-
solubility of
Faraday Soc. 63, 1295 (1967).
[21] Subba Rao, G. V., Ph.D. Thesis, Indian Institute of al, a = 3.231 A, c= 5.148 A)
is appreciable and with

Technology, Kanpur, India, 1969.
[22] Subba Rao, G. V., Ramdas, S., Mehrotra, P. N., and
Rao, C. N. R., J. Solid State Chem. 2, 377 (1970).
[23] Subba Rao, G. V., Ramdas, S., Tomar, M. S., and
Rao, C. N. R., Ind. J. Chem. 9, 242 (1971) and refer-
enccs therein.
increasing oxygen content, the c-axis of the metal
elongates, the change being marked around ZrOo .3
[1]; the a axis passes through a maximum around
ZrOo. 25 The Zr 3 0 phase (a = 5.629 A, c = 5.197 A)
-

[24] Etsell, T. H., and Flengas, S. N., Chem. Rev. 70, 339 is completely ordered, the compositions richer than
(1970).
[25] Lopato, L. M., Yaremenko, Z. A., and Tresvyatskii, Zr 3 0 being analogous to Zr 3 0 [1]. Electrical and
S. G., Dopovidi Akad. Nauk Ukr RSR, 1493 (1965). mechanical properties of the solid solutions of oxygen
[26] Levin, E. M., Phys. Chem. Glasses 7, 90 (1966).
Bondar, I. A., and Toropov, N. A., Izv. Akad. Nauk in Zr have been measured and Zr 6 0 phase with a
[27]
SSSR, Ser. Khim. 212 (1966). decomposition temperature of 1200 K has been iden-
[28] Hajek, B., Petru, F., Kalalova, E., and Dolezalova, J.,
Z. Chem. 6, 268 (1966). tified in addition to the more stable Zr 3 0 [2]; both
[29] Trezebiatowski, W., and Horyn, R., Bull, Acad. Polon. Zr 6 0 and Zr 3 0 are reported to be semiconductors.
Sci., Ser. Sci. Chim. 13, 311 (1965).
[30] Andreeva, A. B., and Keler, E. K., Zh. Prikl. Khim. 39, Both the Zr 6 0 and Zr 3 0 phases have been examined
489 (1966). by electron microprobe and electron microscopic
[31] Collongues, M. R., Queyroux, F., Perez, M., Jorba, Y.,
and Gilles, J.-C., Bull. Soc. Chim. France 4, 1141 techniques and the ordered nature of the latter phase
(1965). confirmed [3]. The structures of the solid solutions in
[32] Ault, J. D., and Welch, A. J. E., Acta Cryst. 20, 410
(1966).
the composition range 11-28.5 atomic percent oxy-
[33] Rouanet, A., Compt. Rend. (Paris) 267C, 1581 (1968). gen have been examined by x-ray, neutron and elec-
[34] Takahashi, T., and Suzuki, Y., Deuxiemes Jour. Int. des
[1, 4, 5]. The compositions
tron diffraction techniques
piles a Combustible, Bruxelles 378 (1967).
[35] Strickler, D. W., and Carlson, W. G., J. Am. Ceram. in the range 15-25 atomic percent oxygen can be de-
Soc. 48, 286 (1965). scribed in terms of a one -dimensional long-period
[36] Duwez, P., Odell, F., and Brown, F. N., J. Electrochem.
Soc. 98, 356 (1951). superstructure with a periodicity which increases
[37] Volchenkova, Z. S., and Pal’guev, S. F., Trans. Inst. with oxygen content [4]. The superstructure can be
Elektrokhim. Akad. Nauk SSSR, Ural. Flilial 5, 133
expressed in terms of the stacking sequence of octa-
(1964).
[38] Robert, G., Deportes, C., and Besson, J., Deuxiemes hedral interstitial sites in the lattice of a-Zr with
Jour. Int. des piles a Combustible, Bruxelles 368
(1967).
ABCABC ... in ZrO* (0.25 <x< 0.33) and ABAB . .

[39] Komissarova, L. N., Wang, C. S., and Spitsyn, V. I., inZrO„ (0.33 <j<0.40) respectively; Zr 3 0 exhibits
Izv. Akad. Nauk SSSR Ser. Khim. 1, 3 (1965). an intermediate structure with ABC BC AC AB
[40] Caillet, M., Deportes, C., Robert, G., and Vitter, G.,
Rev. int. Hautes Temp. Refract. 4, 269 (1967). stacking with 9 layers period [5].

[41] Besson, J., Deportes, C., and Robert, G., Compt. Rend. An
examination of chemically thinned single crys-
(Paris) 262, 527 (1966).
tals of zirconium by electron diffraction during an
[42] Duclot, M., Vicat, J., and Deportes, C., J. Solid State
Chem. 2, 236 (1970). isobaric treatment with O 2 at 5 X 10
-4
torr at 670 K
85
revealed superstructure patterns due to Zr 2 0 [6]. haviour of evaporated films of Zr0 2 has been in-
Zr 2 0 crystallizes in the hexagonal system with a = vestigated by electron microscopy and diffraction
16.16 A and c= 5.148 A. Six oxygens form a ring and [29]. As mentioned earlier, the mechanism of the
a total of four such rings form the supercell. Zr0 2 has been
monoclinic-tetragonal transition of
The most stable oxide of zirconium is the import- examined by several workers [10-14, 21-24]. The
ant ceramic dioxide, Zr0 2 which normally crystal- kinetics of this transition with particular reference to
lizes in the monoclinic structure (P2i/c) possessing its martensitic nature have been studied by Suk-j
4 Zr0 2 units in the unit cell [7-9]. The monoclinic harevskii et al. [30]. The mechanism of the transition
structure reversibly transforms to a tetragonal struc- has also been studied with single crystals [31].
ture around 1420 K and to a fluorite type cubic Preparation of finely-divided samples of the meta-
form at very high temperatures around 2500 K stable phases of Zr0 2 has been described by several
[10-14].Zr0 2 melts at 2995±20 K [15]. workers [10, 11, 21, 32-34]. Zr0 2 prepared by de-
Oxygen equilibria over nonstoichiometric Zr0 2 composition of alkoxides is cubic at room tempera-
(with oxygen deficiency) have been examined by ture and transforms to the metastable tetragonal
Aronson and others [16] in the 1100 to 1400 K range phase around 570 K which then transforms to the
at 10
-12 -10~ 20
atm The compositions of
pressures. monoclinic phase in the range 580 to 670 K [32].

the oxide in the 1670 to 2170 K range at 1-10

-6
atm Occurrence of the metastable tetragonal phase in
have been investigated exhaustively by Carniglia et high surface area. (small crystallite size) samples of
al. [17] who find the ZrOo-^-Zr boundary to be x = Zr0 2 has been examined by Garvie [33] and the
-6
0.014 at 2070 K and 3.5 XlO atm of oxygen. A kinetics of transformation of the metastable phase
black form of Zr0 2 has been prepared by heating to the monoclinic phase have been investigated by
hydrated Zr0 2 in argon or vacuum; this has a tetra- Dow Whitney [34] and Surkarevskii et al. [30]. The
gonal structure [18, 19]. Amorphous hydrated Zr0 2 low temperature metastable cubic and tetragonal
prepared by precipitation methods has been shown phases possess lattice parameters identical to those
to possess short range order [19]. of the corresponding high temperature phases [11,
The phase transitions of Zr0 2 have been investi- 21]. Thin evaporated films of Zr0 2 also exhibit the
gated extensively by several workers. Although there cubic structure at room temperature as shown by
were some inconsistencies and uncertainties in the electron diffraction [29]; the cubic form transforms
earlier literature [20] recent studies have clearly to the tetragonal and monoclinic forms on heating.
established the transition temperatures [21] and Electrical conductivity measurements of Vest and
there appears to be no doubt regarding the mono- co-workers [35, 36] have clearly shown that Zr0 2 is a
clinic-tetragonal and tetragonal-cubic transitions semiconductor, the sign of the majority carriers de-
mentioned earlier [10-14]. The monoclinic-tetragonal pending on the oxygen partial pressure and tempera-
transition shows appreciable hysteresis similar to ture; some evidence of ionic conduction in tetragonal
martensitic phase transitions [22] and is predomin- Zr0 2 has been presented. Electrical conductivity of
antly athermal [22, 23]; the formation of the cubic the tetragonal phase has been measured by other
form is reversible [22]. Anomalous intensity changes workers [37, 38] as well. Electrical conductivity
in the x-ray pattern are noticed prior to the mono- measurements have been employed to study the
clinic-tetragonal transition (in the 1200 to 1370 K monoclinic-tetragonal transformation under pressure
range) and hybrid crystal formation has been no- [26].

ticed [24]; orientation relationship between the mono- Phase equilibria, phase transitions, defect chem- !

clinic and tetragonal phases has been established. istry, electrical propertiesand other aspects of solid
The tetragonal-cubic transition around 2550 K (ob- solutions of Zr0 2 with a variety of oxides have been
served by x-ray studies in vacuum), is undoubtedly reported in the literature [39]. Solid solutions like
accompanied by partial reduction of Zr0 2 and the Zr0 2 -CaO [39, 40] are well-known solid electrolytes.
phase boundary between the cubic and tetragonal Typical of the solid solutions investigated are Zr0 2 -
forms is affected by the stoichiometry or oxygen MgO [41, 42], Zr0 -SrO [43], Zr0 -MnO [44], Zr0
2 2 2- I

deficiency [17, 25].The lattice dimensions of mono- R 0 where R = Sc, Y, or a rare earth [10, 39, 45-
2 3

and tetragonal Zr0 2 decrease with increase in

clinic 54], Zr0 2 -Ce0 2 [55], Zr0 2 -Ge0 2 [56], Zr0 2 -Ti0 2 [57-
oxygen deficiency, but the phase does not appear to 59] and Zr0 2 -Hf0 2 [60-62]. The monoclinic tetragonal
be significantly affected. transition of Zr0 2 is markedly affected in such solid
Pressure induced monoclinic-tetragonal transition solutions; as can be expected the cubic phase is I

of Zr0 2 has been reported [26-28]. Polymorphic be- stabilized in many of the solid solutions.

86
 Zirconium oxides

Oxide and description Data Remarks and inferences References

of the study

rO

Crystal structures of the The room temperature mono-

stable The monoclinic structure can be [7-9].
monoclinic, tetragonal and clinicphase has the P2i/C space considered to be a distorted
cubic phases of Zr02 by O
group with 4 Z 1 2 in unit cell: fluorite structure. Detailed
x-ray diffraction. a = 5.1454 ±0.0005 A; b = atomic positions in the mono-
5.2075 ±0.0005 A; c = 5.3107± phase as well as structural
clinic
0.0005 A and /3 =99°14'±0°05\ rearrangements in polymorphic
The Zr-0 distances vary from transitions to tetragonal and
2.05 to 2.28 A (for the near cubic phases have been dis-
neighbors) and there is a strong cussed. The structures of ZrC>2
tendency to twin in the (100) and HfC>2 have been compared.
direction and polymorphism can
be understood in terms of the
(fluorite type) layers parallel to
(100).
The tetragonal phase (D4®-P42/ The lattice dimension of the cubic [11-13].
nmc) has dimensions: a = 3.64 A phase will be a function of stoi-
and c = 5.27 A at 1520 K with 2 chiometry which in turn will
molecules in the cell. The depend on the temperature and
fluorite type cubic phase has oxygen partial pressure.
o*5.26 A at the transition
temperature.

Phase transitions by The phase transition temperatures The transitions of HfC>2 and ZrC>2 [11-14,
x-ray diffraction. reported by different workers are similar. 21-25].
vary to some extent. The
ranges are: monoclinic—tetra-
gonal, 1320-1490 K; tetragonal—*
cubic, ~2 550-2650 K.
There is considerable thermal The transition is martensitic in [14, 22-24].
hysteresis in the monoclinic- character.
tetragonal transition just like in
the transition of HfC> 2 For .

example, the tetragonal—mono-

clinic transition (on cooling) has
been reported in the range
1320-1170 K.
Coexistence of monoclinic and The thermal hysteresis in the [24].

tetragonal phases as well as hy- monoclinic-tetragonal transition

brid crystal formation have been arises from the differences be-
observed in the range 1370-1490 tween the forward and reverse
K. The orientation relationship transitions (i.e., heating versus
between the two phases is found cooling) The pretransformation
in terms of the parallelism of the region is between 1200 and
(100) and (010) planes of the 1370 K.
tetragonal phase; the b axis of the
monoclinic phase is similar to the
c axis of the tetragonal phase.

Stoichiometry and its The tetragonal-cubic transition At ~2670 K and 10 -8 torr of oxy- [25].
relation to the tetragonal- temperature found by x-ray gen, the composition will be
cubic transition. diffraction (in vacuum) varies ZrOi. 96 o*o. oo 2 » At ~2670 K and
widely due to the changes in the 2 X 10 -3 torr of oxygen, the
stoichiometry of Z 1 2 For a O . composition will be ZrOi.gge.

87
 -
Oxide and description
of the study
Metallographic observations.
High pressure studies.
Kinetics of monoclinic
tetragonal transformation.
Zirconium oxides — Continued
Data Remarks and inferences References
composition of ZrOi, 97 the ,
tetragonal-cubic transformation
temperature corresponds to cross-
ing of the (tetragonal Z O2 +
1
cubic ZrOj)-(cubic ZrOj) phase
boundary.
The stoichiometry of ZrOi as a ZrC>2 is nearly stoichiometric at [16, 17, 25]
function of temperature and 1270 K and 1 atm po a The
.
oxygen partial pressure has been Zr02_*-Zr phase boundary is at
investigated and the cubic- x =0.018 at po t »3.5X10“ # atm
tetragonal transition temperature and T« 2070 K.
is significantly lowered in sam-
ples containing a-Zr and Zr02.
ZrC>2 is oxygen-deficient over the Lattice thermal expansion is not
entire temperature range of 1370- affected by the oxygen deficiency
2170 K at /?oj<1 atm. In the although the dimensions of the
1670-2170 K range, oxygen de- monoclinic and tetragonal phases
ficiency is given by log x » decrease; the monoclinic -tetra-
- 0.890[ (0.400 Xl0-«)/T]- gonal transition is not signifi-
[
(logP)/6] where x is in ZrC> 2 -*, cantly affected. No change in
T is K and p is in atmospheres Young’s modulus and strength of
of oxygen. ZrC>2 is noticed due to oxygen
defciency in sintered samples.
The monoclinic-tetragonal phase Based on these observations the [23].
transition has been examined on transformation has been shown
a vacuum hot -stage microscope to be diffusionless and
(up to 1570 K). In the 1320- athermal as in martensite
1420 K range, the platelet sub- transformations.
structure within ZrC>2 grains
forms rapidly. Photomicrographs
and motion pictures were taken
through the transformation.
Monoclinic Z O
2 reversibly trans-
1 dT/dP of the transition has been [26-28].
forms to the tetragonal form at reported to be — 0.01°/bar in
298 K on application of pressures [27] and -0.003°/bar in [26].
greater than 37 kbar. The tetra-
gonal phase cannot be retained at
ambient conditions.
M artensite (monoclinic^tetragonal) Transformation velocity decreases [30].
transformations in ZrC>2 show no with decreasing temperature in
principle difference between isothermal runs; the energy of
athermal and isothermal kinetics. activation is 150 kcal/mol.
At a certain supercooling, the
transformation velocity increases
sharply and the transformation
becomes athermal. In the tetra-
gonal-monoclinic transition, a
change in the kinetics of dif-
is observed.
fusionless transition
This phenomenon has also been
studied with the metastahle tetra-
gonal phase prepared by decom-
position of the oxychloride.
88

Oxide and description
of the study
Thermal expansion.
Heat of transition.
Superplasticity
Infrared spectra.
Neutron induced
transformation.
Metastable cubic and
tetragonal phases and their
phase transitions.
Zirconium oxides — Continued
Data Remarks and inferences References
Thermal expansion of the lattice There is a critical Zr-0 distance [14, 63].
parameters up to 1370 K have above which the monoclinic
been reported. The monoclinic- structure is no longer stable.
tetragonal transition occurs
around 1370° and the reverse
transition occurs at much lower
temperatures (980-1250 K).
Thermal expansion data for the The data are probably applicable [64].
tetragonal phase are: a =3.5882 + up to 2270 K. At 1420 K, a =
-5 = 5.275 A and
4.50 X10 1 within O.OOI3 A; 3.639 A and c at
c = 5.188 2 +7.57X10 -5 t within 1970 K, a=3.678 A and c =
0.0022 A where t is in degrees 5.339 A.
centigrade between 1150 and
1700 °C.
Thermal expansion data for mono- The monoclinic -tetragonal transi- [65].
clinic ZrC>2 have been measured tion is accompanied by a con-
in detail along the three axes and traction of 3.42%.
found to be highly anisotropic.
The monoclinic -tetragonal transi- [66].
tion is associated with an
enthalpy change of 1420 cal/mol.
Enhanced plasticity during the [67].
monoclinic -tetragonal transition
has been studied.
Cubic phase gives one band at 490 [52, 68].
cm -1 Monoclinic phase shows
.
several bands as expected.
The monoclinic -cubic transforma- Impurities stabilize the high [69].
tion by neutrons depends on the symmetry phase.
method of preparation.
Finely divided samples of Z1O2 Cubic phase lattice parameter from [10, 11, 21,
prepared by the decomposition of electron diffraction is ~ 5.07 A. 29, 32, 33,
alkoxides, oxychloride and other Thin evaporated films of Z1O2 52, 70].
salts give rise to the metastable (as shown by electron diffrac-
cubic and tetragonal phases. The tion) also exist in cubic form and
metastable cubic form prepared the transformation to tetragonal
from alkoxides transforms to the and monoclinic form is affected
metastable tetragonal form by annealing, oxygen pressure
(~570 K), and then to the mono- etc. The cubic lattice parameters
clinic form (580-670 K). The are around 5 A, the actual value
temperatures of transformation varying with annealing.
seem to vary with the method of
sample preparation and some
workers have reported cubic-
monoclinic transitions. The lat-
tice parameters of these low tem-
perature cubic and tetragonal
forms agree with those of the
high temperature phases. The
metastable tetragonal phase pre-
89
 Zirconium oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

pared by precipitation of alkaline

aqueous solution or low -tempera-
ture calcination of zirconium
nitrate has been found to be
stable at room temperature due to
the small crystallite size (or
large surface area).
The kinetics and mechanism of No induction period was seen in the [34].
transformation of the metastable kinetics.
tetragonal phase to the mono-
clinicphase have been studied
and the kinetic data have been
interpreted in terms of Avrami’s
equation and order -disorder
theory.
The cubic-tetragonal transformation [29].
in thin films is monotropic while
the tetragonal-monoclinic trans-
formation exhibits the nucleation
and growth mechanism.

Electrical properties. Electrical properties have been re- There is considerable disagreement [35, 36, 39].|
ported by several workers. Mono- regarding the ionic transport
clinic Zr 02 is an amphoteric numbers in monoclinic and tetra-
semiconductor at 1270 K
and at gonal Z 1O 2 and the available data
high oxygen pressures (1-10 -6 have been nicely reviewed by
atm), the predominant defects are Etsell and Flengers [39]. There is

ionized Zr vacancies which give no doubt that ZrC>2 is a mixed

rise to low mobility holes. The
defect structure of tetragonal
ZrC>2 has been examined by
measuring the temperature and
oxygen pressure dependence of
conductivity and the electronic
conductor. The conductivity
minima have been reported at
-
IO 9 and 10~ 16 atm at 1270 K
for the monoclinic phase. For the
tetragonal phase the minima are
reported at 10 -4 10 -6 and 10 -7
,

transference number. At high atm at 1570 K. The minima are

temperatures and low po 2 ZrC>2 , at higher oxygen pressures at
is an n-type semiconductor (due higher temperatures.
to ionized oxygen vacancies).
Tetragonal ZrC>2 is a mixed elec-
tronic and ionic conductor. The
conductivity change accompany-
ing the monoclinic-tetragonal
transition is isothermal and the
rate of change depends on
thermal and sample history.

90
 References [36] Vest, R. W., and Tallan, N. M., J. Am. Ceram. Soc. 48,
472 (1965).
[37] Anthony, A. M., Guillot, A., and Nicolau, P., Compt.
[1] Holmberg, B., and Dogerhamm, T., Acta Chem. Scand. Rend., Ser. A 262B, 896 (1966).
15, 919 (1961). [38] McClaine, L. A., and Coppel, C. P., J. Electrochem. Soc.
[2] Kornilov, I. I., Glazova, V. V., and Kenina, E. M., 113, 80 (1966).
[4] Dokl. Akad Nauk SSSR 169, 343 (1966). [39] Etsell, T. H., and Flengers, S. N., Chem. Revs. 70, 339
[3] Ericson, T., Osteberg, G., and Lehtinen, B., J. Nucl. (1970).
[5]
f Materials 25, 322 (1968). [40] Subbarao, E. C., in Non-Stoichiometric Compounds, Ed.
[6]
Fehlmann, M., Jostsons, A., and Napier, J. G., Z. Krist. L. Mandelcorn (Academic Press, New York, 1964).
[7] 129, 318 (1969). [41] Grain, C. F., J. Am. Ceram. Soc. 50, 288 (1967).
Yamaguchi, S., J. Phys. Soc. Japan 24, 855 (1968). [42] Viechnicki, D., and Stubican, U.S., J. Am. Chem. Soc.
[8]
[9] Steeb, S., and Rickert, A., J. Less Common Metals 17, 48, 292 (1965).
429 (1969). [43] Noguchi, T., Okubo, T., and Yonemochi, O., J. Am.
McCullough, J. D., and Trueblood, K. N., Acta Cryst. Ceram. Soc. 52, 178 (1969).
[10]
12, 507 (1959). [44] Bayer, G., J. Am. Ceram. Soc. 53, 294 (1970).

[11]
Adam, J., and Rogers, M. D., Acta Cryst. 12, 951 (1959). [45] Thornber, M. R., Bevan, D. J. M., and Graham, J.,
Smith, D. K., and Newkirk, H. W., Acta Cryst. 18, 983 Acta Cryst. 24B, 1183 (1968).
[12] (1965). [46] Spiridonov, F. M., Popova, L. N., and Popilskii, R. Y.,
Kuznetsov, A. K., Keler, E. K., and Fan, F. K., Zh. J. Solid State Chem. 2, 430 (1970).
[13]
[14] Prikl. Khim. 38, 233 (1965). [47] Isupova, E. N., Glushkova, V. B., and Keler, E. V.,
Boganov, A. G., Rudenko, V. S., and Makarov, L. P., Izv. Akad. Nauk SSSR Neorg Mater. 4, 399 (1968).
[15] Dokl. Akad Nauk SSSR, 160, 1065 (1965). [48] Collongues, R., Queyroux, F., Jorba, M. P. Y., and
Smith, D. K., and Cline, C. F., J. Am. Ceram. Soc. 45, Gilles, J. C., Bull. Soc. Chim. France 1141 (1965).
[16]
249 (1962). [49] Rouanet, A., Compt. Rend. 267C, 1581 (1968).
[17] Teufer, G., Acta Cryst. 15, 1187 (1962). [50j Takahashi, T., and Suzuki, Y., Deuxiemes Jour. Int.
Ruh, R., and Corfield, P. W., J. Am. Ceram. Soc. 53, des Piles a Combustible, Bruxelles, 378 (1967).
[18] Mazdiyasni, K. S., Lynch, C. T., and Smith, J. S.,
126 (1970). [51]

[19]
Noguchi, T., and Kozuka, T., Solar. Energy 10, 203 J. Am. Ceram. Soc. 50, 532 (1967).
(1966). [52] Glushkova, V. B., and Koehler, E. K., Mat. Res. Bull.
[20] Aronson, Electrochem. Soc. 108, 312 (1961); Kof-
S., J. 2, 503 (1967); see also, Sci. Ceram. 4, 233 (1967),
[21] stad, P., and Ruzicka, D. J., ibid. 110, 181 (1963). CA, 70, 60405r.
[22] Carniglia, S. C., Brown, S. D., and Schroeder, T. F., [53] Davtyan, I. A., Glushkova, V. B., and Keler, E. K.,
[23] J. Am. Ceram. Soc. 54, 13 (1971). Izv. Akad Nauk SSSR Neorg Mater. 2, 890 (1966).
Livage, J., and Mazieres, C., Compt. Rend. 261, 4433 [54] Strickler, D. W., and Carlson, W. G., J. Am. Ceram.
[24] Soc. 48, 286 (1965).
(1965).
[25] Livage, J., Doi, K., and Mazieres, C., J. Am. Ceram. [55] Casselton, R. E. W., Phys. stat. solidi (a) 1, 787 (1970).
Soc. 51, 349 (1968). [56] Lefevre, J., and Collongues, R., Bull. Soc. Chim. France
[26] Weber, B. C., J. Am. Ceram. Soc. 45, 614 (1962). 1959 (1966).
[27]
Ruh, R., and Rockett, T. J., J. Am. Ceram. Soc. 53, 360 [57] Ksendzov, Y. M., and Prokhvatilov, V. G., Zhur Fiz.
(1970). Khim. 31, 321 (1957).
[28] Wolten, G. M., J. Am. Ceram. Soc. 46, 418 (1963). [58] Keler, E. K., and Andreeva, A. B., Ognewpory 25, 320
[29] Fehrenbacher, L. L., and Jacobson, L. J., J. Am. Ceram. (1960); CA, 51, 15237d; CA, 48, 6798h.
Soc. 48, 157 (1965). [59] Shakhtin, D. M., Levintovich, E. V., Pivovar, T. L.,
[30]
Patil, R. N., and Subbarao, E. C., Acta Cryst. 26A, and Eliseeva, G. G., Izv. Akad. Nauk SSSR Neorg.
[31] 535 (1970). Mater. 4, 1603 (1968).
Nicholson, P. S., J. Am. Ceram. Soc. 54, 52 (1971); see [60] Gavrish, A. M., Susharevskii, B. Y., Krivoruchko, P. P.,
[32]
also Ruh, R., and Garrett, H. J., ibid. 50, 257 (1967). and Zoz, E. I., Izv. Akad. Nauk SSSR Neorg. Mater.
[33] Dow-Whitney, E., J. Electrochem. Soc. 112, 91 (1965). 5, 547 (1969).
[34] Yahldiek, F. W., and Lynch, C. T., Proc. Intern. Conf. [61] Ruh, R., Garret, H. J., Domagala, R. F., and Tallan,
[35] on Sintering and Related Phenomena, Ed. G. C. N. M., J. Am. Ceram. Soc. 51, 23 (1968).
Kuczinski, (Gordon and Breach, New York, 1966). [62] Stansfield, O. M., J. Am. Ceram. Soc. 48, 436 (1965).
Kulcinski, G. L., J. Am. Ceram. Soc. 51, 582 (1968). [63] Grain, C. F., and Campbell, W. J., U.S. Bur. Mines
El-Shanshoury, I. A., Rudenko, Y. A., and Ibrahim, Rept. Invest. 5982 (1962).
I. A., J. Am. Ceram. Soc. 53, 264 (1970). [64] Lang, S. M., Sci. Tech. Aerospace Rept. 2, 2065 (1964).
Sukharevskii, B. Ya., Alapin, B. G., and Gavrish, A. M., [65] Filatov, S. K., and Frank -Kamenetskii, V. A., Soviet
Dokl. Akad. Nauk SSSR 156, 677 (1967). Phys. -Cryst. 14, 696 (1970).
Grain, C. F., and Garvia, R. C., U.S. Bur. Mines Rept. [66] Coughlin, J. P., and King, E. G., J. Am. Chem. Soc. 72,
Invest No. 6619, 19 (1965), CA,
63, 5027A. 2262 (1950).
Mazdiyasni, K. S., Lynch, C. T., and Smith, J. S., [67] Hart, J. L., and Chakladar, A. C. D., Mat. Res. Bull.
J. Am. Ceram. Soc. 48, 372 (1965); ibid. 49, 286 (1966). 2, 521 (1967).
Garvie, R. C., J. Phys. Chem. 69, 1238 (1965). [68] White, W. B„ Mat. Res. Bull. 2, 381 (1967).
Dow-Whitney, E., Trans. Faraday Soc. 61, 1991 (1965). [69] Adam, J., and Cox, B., J. Nucl. Energy 17, 435 (1963).
Vest, R. W., and Tallan, N. M., and Tripp, W. C., [70] Mazdiyasni, K. S., and Brown, L. M., J. Am. Ceram.
J. Am. Ceram. Soc. 47, 635 (1964). Soc. 53, 43 (1970).
 II. 3. Niobium Oxides argued [32, 33] that this oxide should exhibit a
semiconductor-metal transition anologous to V0 2 .

Phase relations in the Nb-0 system have been The available data are all on polycrystalline samples
examined and reviewed over the past vears by many and may not be Rao et al. [28] have studied
reliable.
workers [1-12]. In addition to the well-established the transitions in Nb0
and its solid solutions with
2

monoxide, dioxide and pentoxide, several suboxides V0 2 Nbi_ x F x0 2 (0<x^0.05), and clearly estab-
,

as well as a homologous series of oxides of the lished that the transitions are from semiconducting
formula, Nb3 n+ i0 8n _ 2 (n =5 to 8), are known. Nio- to metallic state; vibration mode softening and c-axis
bium sesquioxide, Nb 2 03, is rot known, but the data Nb-Nb pairing have been shown to be important
of Nakayama et al. [13] seem to indicate the forma- factors in the mechanism of the transitions. De-
tion of this material as a hexagonal-tvpe oxide. tailed studies on single crystal samples are, however,
necessary to draw definitive conclusions.
Suboxides: The suboxides NbO x (Nb 6 0), NbO y
Solid solutions of Nb0 2 with Ti0 2 [30, 34, 35],
(Nb 4 0) and NbO z (NboO) form only by the oxida-
V0 2 [28, 29, 34, 36, 37], Cr0 2 [34], and Mo0 2 [34,
tion of niobium metal or by ageing niobium which
37] have been examined in the literature to elucidate
is supersaturated with oxygen in definite ranges of
the metal-metal bonding and the nature of the
temperature fnd oxygen pressure. NbC)* and Nb0 2
transition. It may be noted that in some of these
are tetragonal while NbO y is orthorhombic [11].
solid solutions, there would be change in cation
Detailed physical properties of these suboxides are
valencies.
not known.
NbO: Niobium monoxide is easily made by the
Homologous series, Nb 3n+ i0 8n _ (5^n^8):
2 Stud-
oxidation of the metal and has a narrow range of
ies by Norin and Magneli [38] indicate that in the
homogeneity (0.982^x^1.008 in NbO x [1, 11, 14-
)

~25
composition range between Nb0 2 and Nb 0 2 5 there
17]. It has a cubic rock salt structure with
exist several nonstoichiometric oxides shown by
percent vacancies in the lattice which are ordered
Gatehouse and Wadsley [39] (and in many later
[1]. Nophase transformations are known in this
papers) to belong to the general homologous series
material; high temperature, high-pressure studies
of the formula Nb3n+i0 8ra _ 2 (rc = 9 would be Nb 2 Os if
[18, 19] indicate no change in the vacancy concentra-
it formed, but H-Nb 0 2 5 actually has a slightly differ-
tion up and at 1920 K. It appears that
to 77 kbar
ent structure). In addition, oxides Nbi 2 0 2 g (Nb0 2 .4 n)
the nature of bonding in the ordered NbO structure
and Nb
4 70ii 6 2 464 ) (Nb0
have also been reported
is significantly different from that in the disordered
[40, 41]. All these oxides have structures similar to
vacancy structures of TiO and VO. Detailed re-
but different from, the basic high temperature
sistivity studies by many workers [14-16, 20-22]
(monoclinic) structure of H-Nb 0 2 5 [42]. Physical
indicate the metallic behavior of NbO in the range
i

properties of these systems have not been investi-

2 to 900 K. The material becomes superconducting
gated in detail.
at ~1.5 K [20]. Solid solution formation and the
solubility of other monoxides in NbO have been
Nb 0 2 Niobium pentoxide, Nb 2 0 5 has a narrow
5 : ,
examined by Gel’d et al. [23].
homogeneity range [1, 43] and the stable phase is

Nb0 2 : Niobium dioxide has a distorted rutile struc- the high-temperature (H) form. The polymorphic
ture with a narrow homogeneity range at room behavior of this oxide has been examined by various
temperature [11, 12, 15, 24-29] and exhibits a first workers over the past many years; however, a de-
order transition at ~1070 K transforming to a tailed picture is far from clear at the present stage
(perfect) rutile phase [26-29]. Discontinuities in x and several metastable phases of Nb 2 05 are being
and p have been noted at T but the material is t , reported from time to time and several reports are
paramagnetic with no magnetic ordering in the range contradictory in nature.
300 to 1200 K [30]. Reports of the electrical proper- There are at present eight crystalline modifica-
ties are conflicting: Janninck and Whitmore [31] tions of Nb 2 05 known and many of them can be
and Roberson and Rapp [21] reported an apparent grown by vapor trar sport methods. Schafer et al. ||

semiconductor-to-metal transition at T <, but Sakata [44] have reviewed various preparation methods of
[27] finds semiconductor behavior throughout the the Nb 2 Os polymorphs while Wadsley and Andersson
range 300 to 1270 K with a ten-fold jump in a at T t . [42] elucidated the structural relationships involved
Metal-metal bonding in the low temperature phase and pointed out that many new modifications are
of Nb0 2 has been established [26, 27] and it may be feasible and may be discovered in future.

92
 The low-temperature form, TT-Nb 2 0 5 first re- , at 1070 K without first going into the B-form. The
ported by Frevel and Rinn [45]; is hexagonal and detailed mechanism is not known but probably im-
can be best prepared by the oxidation of Nb0 2 in purities play a significant role.
air at 590 K for 24 h [44]. Holtzberg et al. [46] and B-Nb 2 05 is the densest of all the polymorphs of
Shafer and Roy [47] obtained this (5) phase by care- niobium pentoxide [55-57] and obtained as char-
fully heating the niobic acid hydroxide gel or amor- acteristic plate-like crystals having monoclinic sym-
phous Nb 2 05 at 770 to 870 K or at low temperatures metry by vapor transport methods [44]. Polycrystal-
for prolonged periods of time. This metastable form line material can be obtained easily by the oxidation
[49]
has also been realized by vapor transport reactions of Nb0 2 in air (24 h heat treatment at 590 and at
with Nb 2 0 5 [48] and by rapid-quenching of the melt 1120 K) [44]. This polymorph is depicted as the
The TT form transforms continuously into
. high-pressure phase by Wadsley and Andersson [42]
T-Nb 2 05 on heating at 870 to 1073 K [50]; annealing and thermal studies by Schafer et al. [44] indicate
at 1670 K results in the high temperature (H) it to be thermodynamically stable at low tempera-

polymorph [49]. tures.

The orthorhombic T-Nb 2 0 5 has been obtained by DTA studies indicate a B—>H
endothermic con-
Brauer [1], Holtzberg et al. [46] (y-form) and Shafer version at 1230 K but isothermal experiments in
[50]
and Roy [47] (Ill-form), by heating the hydroxide NbOCh and Cl 2 atmospheres reveal that the transi-
gels or amorphous Nb 2 0 5 at 870 to 1073 K. It is tion is reversible and occurs at lower temperatures
also produced by the oxidation of Nb or Nb alloys (T/=1020 K; Tr — 920 K) with AH~2 kcal/mol.
below 1270 K [51] or Nb0 2 at 870 to 1070 K in air The tetragonal M-Nb 2 Os has been first reported
Under hydrothermal conditions (170 atm, 600-
. by Brauer [1] and can be obtained by heating either
650 K), amorphous niobic acid also changes to T- the amorphous or T form at 1170 to 1220 K for
Nb 2 0 5 [47]. Single crystals of the T-form can be some hours or for shorter periods at higher tempera-
obtained either by vapor transport or quenching the tures [46, 58]. Single crystals have been grown by
supercooled melt [52]. vapor transport [59] which indicate the true sym-
The T-form changes to the B-form on heating by metry to be tetragonal rather than monoclinic [57].
an exothermic irreversible process and DTA scan This phase transforms to H-Nb 0 2 5 continuously on
indicates a T t of 1090 K; heating to higher tempera- heating at 1170 K.
tures,however, leads to the formation of M and H Monoclinic N-Nb 2 Os can be prepared by vapor
forms of Nb 2 05 However, Goldschmidt
. [53] con- transport and also by the thermal decomposition
cluded from his x-ray data that T-M3 conversion of Nb0 F 2 [48, 60-62]. It has a needle-like habit
-
is time -dependent and that the T form transforms and F ion appears to stabilize the structure. Trans-
slowly to H modification even at room temperature. formation to H-Nb 2 05 takes place slowly on heating
The detailed crystal structure of the T-Nb 0 2 5 is to 1170 to 1270 K [44].
not known at present but it appears that TT and T P-Nb 2 05 has been obtained by Schafer et al. [48]
modifications are closely related since TT —>T process and Lavers et al. [56] by vapor transport in the range
is continuous and TT may be a less ordered form of 1020-1120 K. Water vapor and chloride ions seem
-
T-Nb 2 0 5 and it is likely that substitution of F or to have stabilizing effect on this phase [44]. This
-
(OH) for O 2- is necessary for their stability [42]. tetragonal modification has an idealized V 2 0 5 struc-
On the other hand, these two phases may well be ture and transforms to H-Nb 2 0 5 on heating at 1120
members of a family with complex compositions K; the process is endothermic and irreversible [44].
and large unit and not true polymorphs of
cells Gruehn [63] has reported the formation of R-Nb 2 Os
Nb 0
2 5 [54]. Schafer and co-workers noticed the by vapor transport. It has a monoclinic symmetry
'memory’ effect in T-Nb 2 Os [42]. Thus, the sample and is supposed to have a simple structure compared
prepared by heating Nb0 2 in air at 770 to 870 K is to all other polymorphs. Thermochemical behavior
converted to the B-form sharply at 1090 K whereas is not known at present.
the T-Nb 2 0 5 obtained by reaction of Nb0 2 with Cl 2 The stable H-Nb 2 C>5 is easy to obtain and all

(9-10 h, 540 to 570 K and further heating at 770 K other forms of the niobium pentoxide transform to
for 15 min in air) exhibited a slow T—»B transition thispolymorph on heating in air to ~1370 K. The
and not to completion even after heating for 165 h same result is obtained on heating the amorphous
at 1120 K. On the other hand, T-Nb 2 0 5 obtained by forms of Nb 2 05 or the oxidation of Nb, Nb alloys
wet-precipitation-and-ignition methods transformed or Nb0 2 Nb 2 C>5 [64]
or slow cooling of the molten
to a mixture of M and H forms after heating for 16 h or under hydrothermal conditions (170 atm, 1350

93
 T

K) [47]. The detailed crystal structure of this mono- Schafer and co-workers [44] reported the formation
clinic modification has been worked out by Gate- of several modifications of Nb 05 under nonequilib-
2

house and ^ adsley [39, 42]. rium conditions from the NbO x phases (Ox i tc ,
Several metastable phases of Nb 0 2 5 have been Oxvi); the powder x-ray data are almost identical
reported in the literature whose identity is not very to the initial NbO^ phases from which they are ob-
well established. Reisman and Holtzberg [64] ob- tained but differ from one another and from all
"
served a high-temperature e form which crystallizes other polymorphs of Nb 2 0 5 Detailed structural in- .

without supercooling from the molten NboOs at 1708 formation is lacking at present and it is not known
K. The e form transforms on cooling irreversibly whether they can be classified as the true polymorphs
(without evolution of much heat) to the H-form at of Nb 2 0 5 Ox i to Ox vi change to H-Nb 2 0 5 above
.

1670 to 1470 K; e-Nb 2 0 5 melts at 1708 K whereas 1370 K.

the equilibrium melting point of H-Nb 05 is 1764 K. Electrical properties of Nb 2 Os have been examined
2

X-ray and DTA studies by Shafer and Roy h >' Greener and co-workers [66, 67], The stoichio
[47]
metric Nb2 ° 5 is a semiconductor and the defect
indicated the existence of a metastable H' form of
tvt, ^ ,
JSboOs obtained on heating the H-JNboOs above 1560
. , tt tvti /-x i
structure is interpreted
r
.
to be due to the oxyger
. . . , .
,
T_ vacancies; highly reduced material appears to bti,,
T_
K; H —>11 T / .

is
i , .

an endothermic and reversible transi-

.

•,
^ t-.. ,
degenerate. Dielectric properties have been reported
. , , J ®

tion. Recently, Jonejan and Wilkins [65] reported a

by a few workers in the i iterature [68> 69] .
Nb 20
;

high-temperature phase transition in 5 taking Systems Nb 0 5 -PbO -B O -Ln 0

2 [70], 2 s [71], 2 :

place at 1756 K; the true melting point of Nb 0

2 5 (Ln=Rare earth) [72], -Ge0 [73], -Ti0 [65],2 2

obtained is 1780 K as evidenced by DTA and hot- —P 0 2 5 [74], —V 0 2 5 [75], — Ta 0 [76, 77], — WO,
2 5

stage microscopic data. [78] have been examined in the literature.

Niobium oxides

Oxide and description Data Remarks and inferences References

of the study

Suboxides

Crystal structures. NbOx (Nb 6 0): forms at 570-620 K; These suboxides form only by oxi- [11, 12].
tetragonal; a = 3.387
A; c = 3.27 dation of metal or by ageing of
A. NbOy (NluO): forms at 620- Nb that is supersaturated with
670 K; orthorhombic or tetra- oxygen in definite ranges of
gonal; details not known. NbOx temperature and oxygen pres-
(Nb 2 0): forms at 670-970 K; sures. They are metallic in
tetragonal; a =6.645 A; c = nature but the detailed structure
4.805 A. and properties are not known.
NbO
Crystal structure and Narrow homogeneity range; cubic; No crystal structure transforma- [15-19, 79,
physical properties. space group, Fm3m; Z = 4; a = tions are known in this material. 80].
4.2101 A. Contains 25% cation The low value of k and the mag-
and anion vacancies. TEC (°/K): nitude of 70 indicate that NbO is

4.8 Xl0-« at ~297 K; k (cm 2 / metallic in nature. Banus and

dyn): 4.2 ±0.06 X10~ 13 C v (erg/ ; Reed [18] suggest that NbO can i
1

mol, deg at 297 K): 41.06X10 7 ; be considered as a simple cubic 1

7 G = 1.26. Melting point = 2218 oxide (with Z=3 and Nb and O

K. Pressure and temperature do in four-fold coordination and not
not produce any change in the octahedral type) with no vacan-
concentration of vacancies indi- cies in the structure which would
eating that these are either explain the results of pressure
greatly ordered or form an in- experiments.
herent part of the structure and
are not true lattice defects in
NbO.

94
 Niobium oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

Electrical and optical Metallic behavior in the range Detailed band picture and vacancy [14-16, 20-
properties. 2-900 K with low resistivity; ordering effects not known. 22, 81].
p (77 K)~10-« ficm; p (300 K)~ Available superconductivity data
-8
10 ficm. Seebeck coefficient and are qualitative and need rein-
Hall data not available. Exhibits vestigation.
superconductivity below 1.5 K.
Plasma edge from reflectance
data = 4.3 eV; IR frequency =
1080 ±10 cm -1 .

Nb0 2

Crystal structure, x-ray Rutile structure; space group, The first order nature of the [15, 24-29].
and DTA studies. I4i/a; Z = 32; a = 13.690 ±0.001 transition is established. Super-
A; c = 5.9871 ±0.0003 A. Super- structure lines of the a sublattice
structure and metal-metal bond- of rutile structure and metal-
ing below T T »1070 K; t. t metal bonding disappears above
thermal hysteresis ~10°; A = H T t.

600 cal/mol. The T obtained by t

x-ray data is higher (~50°) than

the DTA value. Melting point =
2190 K.

Magnetic and electrical Paramagnetic in the range 100- Paramagnetic semiconducting [21, 27, 28,
properties. 1300 K; xm s»20X10 -8 emu/mol; characteristics are confirmed below 30, 31, 37].
XM exhibits jump at T t. T and above T tNb0 2 appears
Semiconductor behavior below 7\; to be metallic. There is also
P'-’-'lO
5
ficm (300 K; polycrystal- discrepancy in the absolute
line material); p~14 12cm (300 K, magnitude of p for polycrystalline
single crystal). Ea «0.26 eV (both and single crystal samples of
samples). Drop in p by a factor of Nb0 2.

10 at T
Temperature inde-
f.

pendent p observed by Janninck

and Whitmore [31] above Tt
while Sakata [27] noted semi-
conductor behavior with Ea ~
0.15 eV in the range 1100-
1270 K.

Infrared studies. Bands at 715 and 1080 cm -1 are — [81].

noted and are correlated with the
metal-oxygen vibrations.

Homologous series,
Nbsn+lOgn-l

Crystal structure.
All phases are monoclinic; n =5; These homologous series have [11].
Nb 0 2 o = 21.2 A; 6 = 3.82 A;
> 37 ; structures somewhat to the
c = 12.0 A; 0 = 132.2°. n=6; high -temperature structure of
Nb0 2 ,«; o=20.73 A; 6=3.835 A; Nb 2 Os even though n =9 actually
c- 15.67 A; 0 - 112.93°. n= 7; corresponds to this oxide.
Nb0 8 ,4«; 0=21.19 A; 6-3.822 A;
c- 15.75 A; 0-124.51°. n -8;
NhOj.u; o -21.20 A; 6-3.824 A;
c -29.97 A; 0-95.07°.

95
 .

Niobium oxides — Continued

Oxide and description Remarks and inferences References

of the study

NbOj^nCNbuOig)

Crystal structure. Appears to exist in orthorhombic [40].

and monoclinic forms. Ortho-
rhombic form: space group.
Amma; Z = 4; a =28.99 A; 6 =
3.825 A; c = 20.72 A. Physical
properties not known.

NbO* .464 (NR47O116 )

Crystal structure. Monoclinic: a = 57.74 A; 6 = 3.823 [41].

A; c =21.18 A; 0 = 105.32°. The
oxide has been prepared using
NbCla/NbOCl 3 at 1520 and the K
structure is probably a combina-
tion ofNb 22 0a4 and Nb 2aOe 2 of
the homologous series. Physical
properties are not known.

Nl^Os

Crystal structures and Eight modifications known. The polymorphic behavior of [39, 42,
transformations TT-Nb 2 Oa: best prepared by the Nb 2 C>6 is complicated. Wadsley 44-49, 54-
oxidation of Nb0 2 in air at 590 K and Andersson [42] have been 57, 59-63].
for 24 h; pseudohexagonal; Z= able to explain the stability and
0.5;a =3.607 A; c = 3.925 A: structure of the stable poly-
Transforms continuously to morphs using the principle of
T-Nb 2 Oa on heating at 870-1073 crystallographic shear and even
K [50]; annealing at 1670 K re- predicted the existence of
sults in H-Nb 2 06 [49]. T-Nb 2 06: hitherto unknown forms: How-
best prepared by heating the ever, various metastable and
amorphous oxide at 870-1073 K nonequilibrium phases need ex-
[46, 47] or oxidation of Nb0 2 at planation. Hydrothermal be-
670 K for 4 to forms 5 h. Two havior, various impurity effects
are reported. Orthorhombic: a = and 'memory’ of Nb 2 Os warrant
6.19 A; 6 = 3.65 A; c = 3.94 A; careful and comprehensive
Z = 12. Monoclinic: a = 7.13 A; investigation.
6 = 15.72 A; c = 10.75 A; 0 =
120.7°; Z = 12. Changes to
B-Nb 206; T = 1090 K; exo-t

thermic and irreversible; heating

to higher temperatures produces
H-Nb 2 06. TT and T modifications
appear to be structurally related.
B-Nb 2 Os: Best prepared by the
oxidation of Nb0 2 in air (24 h at
590 and at 1120 K) or by vapor
transport. Monoclinic; space
group, C2/c; Z = 4; a = 12.73 A;
6=4.88 A; c = 5.56 A; 0 = 105.1°;
density = 5.29 g/cm 3 Densest .

of all the modifications; depicted

as the high-pressure form;
thermal studies indicate it to be

96
 Niobium oxide8=Gontinued

Oxid© and description Data Bemarke end inferences

©I the study

tb© thermodynamically stable

form at low temperatures, DTA
studies show endothermic B—»H
transition at 1230 K; however,
isothermal experiments in
NbOCb and Cl a atmospheres .

indicate the transition to be re-

versible and lower T< with ^//~2
keal/mel.
M-NbiOi: Pure phase is diffi-
cult to obtain and partial trans-
formation to H-form always oc-
curs; prepared by heating oxide
gels or amorphous form to 1170=
1220 K or by vapor transport of
NbgOg with NbOGls or NbQBr®
(7\ = 1120=1170 K and 7V>7\ =
100 K). Tetragonal; space group,
14/mmm; a =20,01 A; c = 3.84 A.
Transforms to H-Nb O s on heat- a

ing at 1170 K; no thermal effects

noticeable,
N-NbaQs: Best prepared by
heating NbQaF at 1270 K in
vacuum for some hours; F- ion
appears to stabilize the structure.
Monoclinic; space group, C2/m;
a = 28.51 A; 6 = 3.83 A; c = 17.48
A; /3 = 120.8°. Structures of M
and N forms appear to be
basically related [42]. N-NbaOe
transforms to H-NbaCb slowly
on heating at 1170-1270 K.
P-NbgOs: Prepared by vapor
transport (Cl a Ti = 1020 K;
;

7V-7W00 K). Cl= ions and

water vapor appear to have
stabilizing effect. Tetragonal:
space group, 14i/22; Z= 4; a =
3.896 A; 6=23.43 A. P=>H &
1120 K; endothermic and
irreversible.
B-NbiOiS Prepared by vapor trans-
port but usually associated with
other polymorphs, MonoeUnie;
space group, G2/m; a = 12.79 A;
6 = 3,826 A; e = 3.983 A;| =
§
90,75 . Thermal behavior not
known.
H-NbgOii Easy to obtain; any other
form heated in air at 1370 K
produces this form; also under
hydrothermal conditions. Mono-
clinic; space group, P2; Z-14;
a-21.16 A; 6-3.822 A; c-19.35

97
 Niobium oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

A; /3 = 119.83°. Most stable form;

structure based on the crystallo-
graphic shear has been worked
out by Gatehouse and Wadsley
[39, 42]. The melting points of
Nb 206 reported are inconclusive
and the values quoted are 1758,
1764, and 1780 K [46, 65, 78].

Electrical properties. Semiconductor; <r~10“4 ftcm at [66, 67].

^1000 K; E0 “1.65 eV. Reduced
NbjOj tends to behave as a de-
generate semiconductor. Defect
structure is interpreted to be due
to anion vacancies.

IR studies. Bands are noted at 790 and 1010 [81].

cm -1 for H-NbjOj and are inter-
preted in terms of metal-oxygen
vibrations.

References [
20 ]
Meissner, W., Franz, H., and Westerhoff, H., Ann
Phys. (Leipzig) 17, 593 (1933).
[
21 ] Roberson, J. A., and Rapp, R. A., J. Phys. Chem. Solids
[1] Brauer, G., Naturwiss. 28, 30 (1940); Z. Elektrochem. 30, 1119 (1969).
46, 397 (1940); Z. anorg. allgem. Chem. 248, 1 (1941). [
22 ] Chandrashekar, G. V., Moyo, J., and Honig, J. M.,
2] Elliot, R. P., Trans. ASM. 52, 990 (1960). J. Solid State Chem. 2, 528 (1970).
3] Brauer, G., Mueller, H., and Kuehner, G., J. Less- [23] Gel’d, P. V., Shveikin, G. P., Alyamovskii, S. I., and
Comm. Metals 4, 533 (1962). Tskhai, V. A., Russ. J. Inorg. Chem. 12, 1053 (1967).
"
4 Norman, N., J. Less-Comm. Metals 4, 52 (1962). [24] Marinder, B.-O., Arkiv Kemi 19, 435 (1962).
5 Blackburn, P. E., J. Electrochem. Soc. 109, 1142 (1962). [25] Rogers, D. B., Shannon, R. D., Sleight, A. W., and
6 Kofstad, P., and Espevik, S., J. Electrochem. Soc. 112, Gillson, J. L., Inorg. Chem. 8, 841 (1969).
153 (1965). [26] Sakata, T., Sakata, K., and Nishida, I., Phys. Stat.
[7] Taylor, A., and Doyle, N. J., J. Less-Comm. Metals 13, Solidi 20, K155 (1967).
313 (1967). [27] Sakata, K., Phys. Soc. Japan 26, 582 (1969); 26, 867
J.
[8] Fromm, E., and Jehn, H., J. Less-Comm. Metals 15, 242 (1969); 26, 1067 (1969).
(1968) [28] Rao, C. N. R., Rama Rao, G., and Subba Rao, G. V.,
[9] Schafer, H., Bergner, D., and Gruehen, R., Z. anorg. J. Solid State Chem. 6, 340 (1973).
allgem. Chem. 365, 31 (1969). [29] Rao, C. N. R., Natarajan, M., Subba Rao, G. V., and
10 Terao, N., Japan J. Appl. Phys. 2, 156 (1963). Loehman, R. E., J. Phys. Chem. Solids 32, 1147
11 Niebuhr, J., J. Less Comm. Metals 11, 191 (1966). (1971).
12 Chang, L. L. Y., and Phillips, B., J. Am. Ceram. Soc. [30] Sakata, K., Nishida, I., Matsushima, M., and Sakgta, T.,
52, 527 (1969). J. Phys. Soc. Japan 27, 506 (1969).
[13] Nakayama, T., Osaka, T., and Kitada, A., J. Less- [31] Janninck, R. F., and Whitmore, D. H., J. Phys. Chem.
Comm. Metals 19, 291 (1969). Solids 27, 1183 (1966).
[14] Pollard, E. R., Ph.D. Thesis, MIT, USA (1968). [32] Adler, D., Solid State Phys. 21, 1 (1968).
[15] Subbarao, G. V., Ph.D. Thesis, Indian Institute of Tech- [33] Rao, C. N. R., and Subba Rao, G. V., Phys. Stat.
nology, Kanpur, India, 1969. Solidi (a), 1, 597 (1970).
[16] Rao, C. N. R., Wahnsiedler, W. E., and Honig, J. M., [34] Marinder, B.-O., Dorm, E., and Seleborg, M., Acta
J. Solid State Chem. 2, 315 (1970). Chem. Scand. 16, 293 (1962).
[17] Taylor, A., and Doyle, N. J., J. Appl. Cryst. 4, 103 [35] Riidorff, W., and Luginsland, H. H., Z. anorg. allgem.
(1971). Chem. 334, 125 (1964).
[18] Banus, M. D., and Reed, T. B., in The Chemistry of [36] :
Kristensen, I. K., J. Appl. Phys. 40, 4992 (1969).
Extended Defects in Non-metallic Solids, Eds. L. [37 Rao, C. N. R., unpublished results (1971).
Eyring and M. O’Keeffe (North Holland Publ. Co., [38] Norin, R., and Magneli, A., Naturwiss. 47, 354 (1960).
Amsterdam, 1970), p. 488. [39] Gatehouse, B. M., and WadsleV, A. D., Acta Cryst. 17,
[19] Taylor, A., and Doyle, N. J., in The Chemistry of 1545 (1964).
Extended Defects in Non-metallic Solids, Eds. L. [40] Norin, R., Acta Chem. Scand. 17, 1391 (1963).
Eyring and M. O’Keeffe (North Holland Publ. Co., [41] Gruehn, R., and Norin, R., Z. anorg. allgem. Che
Amsterdam, 1970), p. 523. 367, 209 (1967).

98
 [42] Wadsley, A. D., and Andersson, S., in Perspectives in II. 4. Molybdenum Oxides
Structural Chemistry, Vol. Ill, Eds. J. D. Dunitz
and J. A. Ibers (John Wiley & Sons, New York, 1970),
Phase studies on the Mo-0 system have been
pp. 1-58.
[43] Blumenthal, R. N., Moser, J. B., and Whitmore, D. H., carried out by various workers [1-6]. In addition to
J. Am. Ceram. Soc. 48, 617 (1965).
Schafer, H., Gruehn, R., and Schulte, F., Angew. Chem.
the well-known dioxide and trioxide, many mixed
[44]
Intemat. Edit. 5, 40 (1966).
Frevel, L. K., and Rinn, H. W., Anal. Chem. 27, 1329
valence phases (between Mo0 2 and 0 O 3 ) have been M
[45]
reported [3-7]; of these, Mo 4 On and Mo 9 0 26 seem
(1955).
i [46] Holtzberg, F., Reisman, A., Berry, M., and Berkenblit,
M., Am. Chem. Soc. 79, 2039 (1957).
to be stable [1, 5, 6] whereas 017O 47 05 O 14 and M , M
[47] Shafer,
J.
M. W., and Roy, R., Z. Krist. 110, 241 (1958).
Mo 802 3 seem to be metastable and can be stabilized
[48] Schafer, H., Schulte, F., and Gruehn, R., Angew. Chem. by incorporation of other elements like Ti, V, and
[49]
Internat. Edit. 3, 511 (1964).
Sarjeant, P. T., and Roy, R., J. Am. Ceram. Soc. 50, 500
W [8]. These mixed valence oxides can not be con-

(1967). sidered to be truly nonstoichiometric, since they

[50] Brendel, C., quoted in ref. [44].
Nowotny, H., Benesovsky, F., Rudy, E., and Wittmann, have narrow ranges of homogeneity; some of them
! [51]
A., Mh. Chem. 91, 975 (1960). have tunnel and layer structures. No oxide of molyb-
[52] Mertin, W., and Jagusch, W., quoted in ref. [44].
[

[53] Goldschmidt, H. J., J. Inst. Metals 87, 235 (1958/59). denum in the range Mo-Mo0 2 is known and the
[54] Jahnberg, L., and Andersson, S., Acta Chem. Scand. reported existence of Mo 3 0 [2] is in doubt [1, 5, 6, 9].
21, 615 (1967).
[55] Laves, F., Moser, R., and Petter, W., Naturwiss. 51,
356 (1964).
M 0O 2 : Molybdenum dioxide, Mo0 2, has a mono-
[56] Laves, F., Petter, W., and Wulf, H., Naturwiss. 51, 633 clinic structure [1, 7, 10-12] and exhibits metallic

[57]
(1964).
Terao, N., Japan
J. Appl. Phys. 4, 8 (1965).
behavior in the range 4 to 300 K [12, 13]. No phase
[58] Schulte, F., Gruehn, K., and Gorbing, M., quoted in transitions are known in this material. Other proper-
ref. [44].
ties are not known.
[59] Mertin, W., Andersson, S., and Gruehn, R., J. Solid
State Chem. 1, 419 (1970). Mo0 2 forms solid solutions with Ti0 2 [14], Nb0 2
[60] Andersson, S., and Astrom, A., Acta Chem. Scand. 19, and V0 2 [15-17] which have rutile structures.
[14]
2136 (1965).
Lundberg, M., and Andersson, S., Acta Chem. Scand.
[61]
21, 615 (1967).
Mixed Valence Phases: M 04O 11 has a monoclinic
[62] Andersson, S., Z. anorg. allgem. Chem. 351, 106 (1967). structure (stable below 890 K) and assumes an
[63] Gruehn, R., J. Less-Comm. Metals 11, 119 (1966).
orthorhombic symmetry when synthesized in the
[64] Reisman, A., and Holtzberg, F., J. Am. Chem. Soc. 81,
3182 (1959). range 890 to 950 K; both the forms are closely re-
[65] Jonejan, A., and Wilkins, A. L., J. Less-Comm. Metals lated [3, 7, 18] in structure and T appears to be t
19, 185 (1969).
1

[66] Greener, E., Whitmore, D., and Fine, M., J. Chem. M

^900 K. 04 O 11 appears to be metallic [3] with no
'
Phys. 34, 1017 (1961). significant change in p at T t 017 O 47 has an or- . M
Greener, E. H., and Hirthe, W. M., J. Electrochem. Soc.
i [67]
109, 600 (1962).
thorhombic symmetry [3, 18] whereas 06 O 14 is M
[68] Robinson, M. L. A., and Roetschi, H., J. Phys. Chem. tetragonal [8]; Mo 0 8 23 is monoclinic [3, 7, 18-20],
1

[69]
Solids 29, 1503 (1968).
Emmenegger, F. P., and Robinson, M. L. A., J. Phys.
M 09O 26 is dimorphic and can assume a triclinic or

,
Chem. Solids 29, 1673 (1968). monoclinic structure depending on the method of
[70] Roth, R. S., J. Res. Nat. Bur. Stand. (U.S.), 62, 27 preparation [5, 9, 18, 19]. Phillips and Chang [5]
(1959).
I

[71] Levin, E. M., J. Res. Nat. Bur. Stand. (U.S.), 70A

report a phase transformation in Mo 0 9 2e at 1040 K;
i (Phys. and Chem.), No. 1, 11-16 (Jan.-Feb. 1966). the low-temperature form is monoclinic, but the
[72] Godina, N. A., Savchenko, E. P., and Keler, E. K., structure of the high-temperature form is not ex-
Russ. J. Inorg. Chem. 14, 1162 (1969).
'

[73] Levin, E. M., J. Res. Nat. Bur. Stand. (U.S.) 70A (Phys. actly known. M 017 O 47 exhibits low resistivity and
1
and Chem.), No. 1, 5-10 (Jan.-Feb. 1966).
Levin, E. M., and Roth, R. S., J. Solid State Chem. 2,
appears to be metallic [3]. M
04 O 11 and Mo 9 0 2 6 melt
[74]
250 (1970). at high temperature (>1000 K) and decompose to
[75] Waring, J. L., and Roth, R. S., J. Res. Nat. Bur. Stand. lower oxides [5]. Detailed physical properties are
(U.S.), 69A (Phys. and Chem.), No. 2, 119-129 (Mar.-
Apr. 1965).
not known for these mixed valence phases.

,
[76] Holtzberg, F., and Reisman, A., J. Phys. Chem. 65,
1192 (1961). M 0O 3 : Molybdenum trioxide, M 0O 3, has an or-
[77] Mohanty, G. P., Fiegel, L. P., and Healy, J. H., J. Phys. thorhombic symmetry and consists of a layered
Chem. 68, 208 (1964).
i
(or chain) structure [1, 5, 7, 21]. Detailed studies [5]
[78] Roth, R. S., and Waring, J. L., J. Res. Nat. Bur. Stand.
(U.S.), 70A (Phys. and Chem.), No. 4, 281-303 (July- indicate no phase transitions in this material up to
Aug. 1966). the melting point (^1055 K). MoOs is a semicon-
[79] Taylor, A., and Doyle, W. J., J. Appl. Cryst. 4, 109
. (1971). ductor 22 ]. [

[80] Gel’d, P. V., and Kusenko, F., Izv. Akad. Nauk SSSR, Molybdenum bronzes are formed from M 0O 3 and
Otdel. Tekhn. Nauk Met. i Toplivo 2, 79 (1960).
1 other metallic oxides; these interesting materials
[81] Alyamovskii, S. I., Shveikin, G. P., and Gel’d, P. V.,
Russ. J. Inorg. Chem. 12, 915 (1967). have been discussed in detail in the literature [23]

99
 Molybdenum oxides

Oxide and description Remarks and inferences References

of the study

Mo0 2

Crystal structure and
electrical properties.
Monoclinic; space group, P2i/c; The structure is closely related to [1, 7, 10-
Z = 4; a = 5.6109 ±0.0008 A; 6 = that of rutile; the metallic 13].
4.8562 ±0.0006 A; c = 5.6285 ± properties have been interpreted
0.0007 A; 0 = 120.95°. No phase in terms of a modified Good-
transitions are known. Metallic enough’s model.
behavior; p (4.2 K)»5.4X10~7
(2cm; p (300 K) *8.8X10" 8 12cm.

Mixed Valence Phases

M04O11

Crystal structure and
electrical properties.
Monoclinic (<900 K); a =24.54 A;
6 = 5.439 A; c = 6.701 A; 0 =
94.28°. Orthorhombic (>900 K);
a =24.49 A; 6 = 5.459 A; c =
6.752 A. T » 900
t K. Monoclinic
and orthorhombic forms can be
obtained at ordinary tempera-
tures depending on the method of
preparation. Both forms show
metallic behavior; p (300 K)~0.2
12cm; p does not show much
change at <.T
Both the modifications are closely [3, 7, 18].
related structurally and are
built up of M
0O 4 tetrahedra and
distorted MoO e octahedra; the
difference lies in the relative
orientation of the substructures
in nieghboring slabs, being
parallel in the monoclinic and
alternating in the orthorhombic
form. Detailed data on the
physical properties are lacking.

M017O47

Crystal structure and
electrical properties.
MosOu
Orthorhombic; space group, Pba2; This has a tunnel structure which [3, 18].
Z-2; 0-21.61 A; 6-19.63 A; may be considered as built up
c- 3.951 A. Metallic behavior; from MoO« octahedra and 0O7 M
p (300 K)~5X10“* (2cm. Detailed pentagonal bipyramids. Metal-
data are lacking. metal bonding is noted and
probably accounts for the low
measured resistivity.

Crystal structure. Tetragonal; a = 11.50 A; c = 3.937 The structure is related to that of [ 8 ].

A. Metastable form and de- M 017O 47 . Detailed data are
composes on prolonged heat lacking.
treatment; Ti, V, and W
seem to
stabilize the phase.

Mo»02j

Crystal structure. Monoclinic; a = 16.88 A; 6 > = 4.052 The structure is that of distorted [3, 7, 18-

A; c = 13.39 A; 0 = 106.19°. ReOs-type which recurrent

in 20 ].
Properties not known. dislocations of atoms occur along
the shear planes.
MogOw (M018O62)

Crystal structure and Dimorphic: Triclinic phase; a — The triclinic phase has a basic [5, 9, 18,
x-ray studies. 8.145 A; 6 = 11.89 A; c = 21.23 A; M 0O 3 structure. According to 19].
a = 102.67°; 0=67.82°; 7 = Kihlborg [24], MoigOs 2 is the

100
 Molybdenum oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

109.97°. Monoclinic phase; a = first member (m = 1 ) of a

16.74 A; b =4.019 A; c = 14.53 A; homologous series, Mo n 03 n -m+i*
0 =95.45°. Both forms can be The existence of oxides M 012O 33

prepared
5
at room temperature. and M 026 O 76 is suggested.
Monoclinic phase shows a transi-
tion at 1040 K; the structure of
the high -temperature phase is not
known in detail. Physical prop-
erties are not known.

M0 O 3

Crystal structure and Orthorhombic; space group, Pbnm; It has a chain structure. The break [1, 5, 7, 21,
properties. Z = 4; a =3.966 A; 6 = 13.88 A; in lnp — 1/T plot at 650 K may 22].
c = 3.703 A. No phase transforma- correspond to a change in the
tions exist up to the melting mechanism of conduction.
point (1055 K). Semiconductor;
p (450 K)~10 10 Stem; p (900 K)
~10 — 1/T plot shows
Stem; lnp a
break at ~650 K; Eo (<650 K)
«0.56 eV; Ea (>650 K)«1.83
eV.

References [12] Rogers, D. B., Shannon, R. D., Sleight, A. W., and

Gillson, J. L., Inorg. Chem. 8, 841 (1969).
[13] Perloff, D. S., and Wold, A., Crystal Growth, Proc. Int.
Conf. on Cryst. Growth, Ed. H. S. Peiser (Pergamon,
[1] Hagg, G., and Magneli, A., Arkiv Kemi, Mineral Geol. London, 1967).
19A, 1 (1945). [14] Marinder, B.-O., Dorm, E., and Seleborg, M., Acta
[2] Schonberg, N., Acta Chem. Scand. 8, 221 (1954); 8, 617 Chem. Scand. 16, 293 (1962).
(1954). [15] Marinder, B.-O., and Magneli, A., Acta Chem. Scand.
[3] Kihlborg, L., Acta Chem. Scand. 13, 954 (1959); Adv. 11, 1635 (1957); 12, 1345 (1958).
Chem. Ser. 39, 3745 (1963). [16] Israelson, M., and Kihlborg, L., Mat. Res. Bull. 5, 19
[4] Rode, E. Ya., and Lysanova, G. V., Dokl. Akad. Nauk (1970).
SSSR 145, 351 (1962). [17] Rao, C. N. R., Natarajan, M., Subba Rao, G. V., and
[5] Phillips, B., and Chang, L. L. Y., Trans. AIME 233, Loehman, R. E., J. Phys. Chem. Solids 32, 1147
1433 (1965). (1971).
[6] Chang, L. L. Y., and Phillips, B., J. Am. Ceram. Soc. [18] Kihlborg, L., Arkiv Kemi 21, 471 (1963).
52, 527 (1969). [19] Magneli, A., Acta Chem. Scand. 2, 501 (1948).
[7] Magneli, A., Andersson, G., Holmberg, B., and Kihlborg, [20] Kihlborg, L., Arkiv Kemi 21, 461 (1963).
L., Anal. Chem. 24, 1998 (1952). [21] Kihlborg, L., Arkiv Kemi 21, 357 (1963).
[8] Kihlborg, L., Acta Chem. Scand. 23, 1834 (1969). [22] Deb, S. K., and Chopoorian, J. A., J. Appl. Phys. 37,
[9] Kihlborg, L., Acta Chem. Scand. 16, 2458 (1962). 4818 (1966).
[10] Magneli, A., Arkiv Kemi, Mineral Geol. 24A, 11 (1946). [23] Rao, C. N. R., and Subba Rao, G. V., Phys. Stat. Solidi
[11] Brandt, B. G., and Skapski, A. C., Acta Chem. Scand. (a) 1, 597 (1970).
21, 661 (1967). [24] Kihlborg, L., Arkiv Kemi 21, 443 (1963).

101
 II. 5. Technitium Oxides ent monoclinic cell was suggested by Zachariasen
[6]; it has been pointed out [3] that Tc0 2 may exhibit
polymorphism like Re0 2 .

Studies by various workers [1-3] have shown that Tc 2 0 7

orthorhombic and the structure consists
is

in the system Tc-O, Tc0 2 is the only stable oxide at of an arrangement of isolated Tc 2 0 7 molecules with
high temperatures. A covalent heptoxide, Tc 2 0 7 , is tetrahedral coordination of Tc atoms; the structure
also known. Tc0 2 has a monoclinic, Mo0 2 -type struc- of Tc 2 0 7 is more closely related to Cr0 3, Ru0 4 and
ture [1, 3] and according to Marinder and Magneli 0s0 4 than to Re 2 0 7 . Physical properties are not
[5], metal-metal bonds exist in this material. A differ- known at present.

Technitium oxides

Oxide and description Data Remarks and inferences References

of the study

Tc0 2

Crystal structure. Monoclinic; space group, P2 i/C; Rutile based structure with metal- [1, 3, 5].
Z = 4; = 5.55±0.01 A; 6 =
a metal bonds.
4.85 ± 0.01 A; c = 5.62 ± 0.01 A;
/3= 121.9±0.1°.

TC 2 O 7

Crystal structure. Orthorhombic; space group,- Pbca; The structure consists of isolated [4].

Z = 4; a = 13.756 A; 6 = 7.439 A; TC 2O molecules.

7

c = 5.617 A.

Rogers, D. B., Shannon, R. D., Sleight, A. W., and

References [3]
Gillson, J. L., Inorg. Chem. 8 , 841 (1969).
[4] Krebs, B., Angew. Chem. Int. Ed. (Engl.) 8 , 381 (1969);
Z. anorg. allgem. Chem. 380, 146 (1971).
[1] Muller, O., White, W. B., and Roy, R., J. Inorg. Nucl. [5] Marinder, B.-O., and Magneli, A., Acta Chem. Scand.
Chem.
26, 2075 (1964). 11, 1635 (1957).
[2] Rulfs, C. L., Pacer, R. A., and Hirsch, R. F., J. Inorg. [
6 ]
Zachariasen, W. H., ACA Program and Abstr. of Winter
Nucl. Chem. 29, 681 (1967). Meeting, F-4 (1951).
 II. 6. Ruthenium Oxides sistivity is very low and exhibits metallic behavior
[3, 5-7, 11-14].
Phase relations in the Ru-0 system have been Fletcher and co-workers [13] have shown that the
reported in the literature [1,2]. In the temperature oxidation state of Ru in Ru0 2 is more than 4. The

range 1070 to 1770 K, Ru02 is the only stable oxide de Hass-van Alphen effect [15], magnetoresistance
(in air); Ru0 3 and Ru0 4 exist as vapor species. [16] and Azbel-Kaner cyclotron resonance [17] stud-
Attempts to prepare the stable nonstoichiometric ies on Ru0 2 suggest that the simple band picture

oxide, Ru 0 2 ± x have not been successful [2]. Ru0 2

, proposed by Rogers and co-workers [7] is inadequate
dissociates in air at ^1680 K to the metal. to explain the observed properties. Ryden et al. [12]
Several workers have studied the crystal growth have found that electron-phonon and electron -elec-
of Ru0 by 2 chemical transport [3-5] and other tron interband scattering mechanism accounts
methods [6, 7]. Ru0 2 has a tetragonal rutile structure quantitatively for the observed resistivity behavior
[2, 3, 5-9] at room temperature and no phase transi- of Ru0 2 in the range 10 to 1000 K.
tions are known in the temperature range 4.2-1270 K McDaniel and Schneider [2] report that Ru0 2 and
[5, 8, 10-12]. It has a low and almost temperature Ir0 2 can form complete solid solutions of rutile
independent magnetic susceptibility [6, 13]; the re- structure in the entire composition range.

Ruthenium oxides

Oxide and description Data Remarks and inferences References

of the study

Ru0 2

Crystal structure and TEC. T = 298 K: Tetragonal; space The c lattice parameter decreases [5, 10].

group, P4 2 /mnm; Z = 2; a = with rise in T; slight anisotropy

4.4910 ±0.0003 A; c = 3.1064± is evident.
0.0002 A. TEC (XlO -6 /°C:
||
c = —1.4; ||- = +7.0.

Magnetic and electrical Xm=2.03X10 -4 cgs units at 298 K. The metallic behavior of Ru0 2 is [3, 6, 7, 11,

properties. K)~l .0X10-

p (4.2
8
ftcm; p (100 evident; the Lorentz number is 12, 18].
K)~1X10 -6 ftcm; p (298 K)~
[9] close to the theoretical value for
4.0X10 -5 ftcm. At 77 K, Rh = typical metals.
—0.79, mh=61 cm 2 /V s; at
300 K, Rn = —1.10, Mh=3.1
cm 2 /V s. 0d (calc.) =900±5 K.
l/x = d/T+aT" (for T <1.5 Tm )
where /3 = 18.1 cm K 2 /W, a =
8.42X10' 4 cm K^/W, n =1.66
and Tn is the temperature at
which K is a maximum. Lorentz
ratio =2.6 X10
_8
ft/ 2
W .

Boman, C. E., Acta Chem. Scand. 24, 116 (1970).

References Hazony, Y., and Perkins, H. K., J. Appl. Phys. 41, 5130
[10]
[1] Bell, W. E., and Tagami, M., J. Phys. Chem. 67, 2432 (1970).
(1963). [11] Osburn, C. M., and Vest, R. W., Bull. Am. Ceram. Soc.
[2] McDaniel, C. L., and Schneider, S. J., J. Res. Nat. Bur. 47, 354 (1968).
Stand. (U.S.), 73A (Phys. and Chem.), No. 2, 213-219 [12] Ryden, W. D., Lawson, A. W., and Sartain, C. C.,
(Mar.-Apr. 1969). Phys. Rev. B 1, 1494 (1970).
Schafer, H., Schneidereit, G., and Gerhardt, W., Z. anorg.
[3]
[13] Fletcher, J. M., Gardner, W. E., Greenfield, B. F.,
allgem. Chem. 319, 327 (1963). and Rand, M. H., Chem. A
Holdoway, M. J., J. Soc.
[4] Schafer, H., Chemical Transport Reactions (Academic
653 (1968).
Press, New York, 1964), p. 48.
[14] Ryden, W. D., Lawson, A. W., and Sartain, C. C.,
[5] Butler, S. R., and Gillson, J. L., Mat. Res. Bull. 6, 81
Phys. Letters 26A, 209 (1968).
U97D. Marcus, S. M., and Butler, S. R., Phys. Letters 26A, 518
Cotton, F. A., and Mague, Inorg. Chem. 317 [15]
[6] J. T., 5,
(1.966).
(1968).
[7] Rogers, D. B., Shannon, R. D., Sleight, A. W., and [16] Marcus, S. M., Phys. Letters 28A, 191 (1968).
Gillson, J. L., Inorg. Chem. 8, 841 (1969). [17] Slivka, R. T., and Langenberg, D. N., Phys. Letters
[8] Krishna Rao, K. V., and Iyenger, L., Acta Cryst. 25A, 28 A, 169 (1968).
302 (1969). [18] Millstein, J., J. Phys. Chem. Solids 31, 886 (1970).

103
 II. 7. Rhodium Oxides temperature low-pressure form can be prepared
from Rh metal at 1270 K [1], Shannon and Prewitt
In the Rh-0 system, the only well-established [6] have prepared a high-temperature high-pressure

oxides are Rh 2 Os and RI1 O 2 even though there are

, form of Rh 2 Og (at 65 kbar pressure and 1470 K)
numerous claims and counter claims regarding the which has an orthorhombic symmetry but closely
existence of oxides such as Rh 2 0 and RhO [1-5]. related to the corundum structure. The high-temper-
Rh 2 Os exhibits polymorphism; the low-temperature ature form of Wold et al., and the high-pressure
low-pressure form belongs to the corundum struc- form of Shannon and Prewitt appear to be closely
ture and the high-temperature low-pressure form has related [6]. The latter material appears to be semi-
the orthorhombic perovskite structure [1, 5], Ac- conducting at room temperature [6].
cording to Wold and co-workers [1], the transition Rh0 2 has the rutile structure [2-4]; it has a low
temperature is '"-'1020 K and is sluggish; T t also de- and exhibits metallic behavior
resistivity [3, 4], Other
pends on the starting materials used. The high- Physical properties are not known.

Rhodium oxides

Oxide and description Data Remarks and inferences References

of the study

RI12O3

Crystal structures and Low-temperature low-pressure The low-temperature—^high-temper- [1, la, 6, 7].
electrical properties. form: Hexagonal (Corundum ature transformation is sluggish
structure); space group, R3C; and depends on the starting ma-
Z = 6 a =5.108 A; c = 13.810 A.
; terialsemployed; the high tem-
T is ~1020 K. High tempera-
t perature form can be prepared
ture form: Orthorhombic; space directly from Rh metal at 1270 K.
group, Pbca; a = 5.1477 A; 6 = The orthorhombic structures are
5.4425 A; c = 14.6977 A. High- related to the corundum structure [ 6 ].
temperature high-pressure form: and may be described as contain-
Orthorhombic; space group, ing layers of the corundum struc-
Pbna; Z = 4; 0 = 5.1686 ±0.0003 ture cut parallel to (lOll) and
A; b = 5.3814±0.0004 A; c = stacked together.
7.2486 ±0.0004 A. p (300 K)~
130 Ocm; Ea “0.16 eV.

RhOj

Crystal structure and Rutile structure; space group Rutile structure characteristic of [2-4].
electrical properties. P4 2 /mnm; Z = 2 a=4.4862± ; many transition metal dioxides.
0.0005 A; c = 3.0884 ±0.0005 A. Typical metallic behavior.
K)~2X10 -6 ftcm; p (300
p (4.2
K)~lXlO -4 ficm. RI O de- 1 3

composes to RhOs at ~1120 K

followed by decomposition to the
metal and oxygen at ~1320 K.

References [3] Shannon, R. D., Solid State Commun. 6, 139 (1968).

[4] Rogers, D. B., Shannon, R. D., Sleight, A. W., and
[1] Wold, A., Arnott, R. J., and Croft, W. J., Inorg. Chem. Gillaon, J. L., Inorg. Chem. 8, 841 (1969).
2, 972 (1963). [5] Prewitt, C. T., Shannon, R. D., Rogera, D. B., and
[la] Bieaterboa, J. W. M., and Horuatia, J., J. Le»>. Common Sleight, A. W., Inorg. Chem. 8, 1985 (1969).
Metalt, 30, 121 (1973). [6] Shannon, R. D., and Prewitt, C. T., J. Solid State Chem.
[2] Muller, O., and Roy, R., J. Leaa-Common Metala 16, 129 2, 134 (1970).
[7] Coey, J. M. D., Aota Cryat. 26B, 1876 (1970).

104
 1 1. 8. Palladium Oxide single crystals indicate that the material is a p-type
semiconductor. No phase transformations are known
in this material; it decomposes in air at ~1070 K
Palladium monoxide is the only stable oxide known [5].

in the Pd-0 system. Attempts to prepare PdsCX PdO forms solid solutions with CuO [6, 7], PbO
have not been successful [1]. PdO has a tetragonal [8] and rare-earth sesquioxides [5] and the phase
structure [2-4], Studies by Rogers et al. [4] on PdO relations have been described in detail.

Palladium oxide

Oxide and description Data Remarks and inferences References

of the study

PdO

Crystal structure and Tetragonal; space group, P42/ The material is a p- type extrinsic [2-5].
properties. mmc; Z = 2; a = 3.0434 ±0.0002 semiconductor.
A; c = 5.3363 ±0.0004 A. Semi-
conductor (p-type); p (300 K)~
10-1000 ficm; Ea =0.04-0.10 eV.
Decomposes to the metal and
oxygen in air at ~1070 K; the
process of decomposition is re-

versible. No phase transitions are

known.

References [5] McDaniel, C. L., and Schneider, S. J., J. Res. Nat. Bur.
Stand. (U.S.), 72A (Phys. and Chem.), No. 1, 27-37
[1] Muller, 0., and Roy, R., J. Less-Comm. Metals 16, 129 (Jan.-Feb. 1968).
(1968).
[6] Schmahl, N. G., and Minzyl, E., Z. Phys. Chem. (N.F.)
[2] Moore, W. J., Jr. and Pauling, L., J. Am. Chem. Soc. 63,
1392 (1941). 47, 142 (1965).
[3] Wasor, J., Levy, H. A., and Peterson, S. W., Acta Cryst. [7] Schmahl, N. G., and Eikerling, G. F., Z. Phys. Chem.
6, 661 (1953). (N.F.) 62, 268 (1968).
[4] Rogers, D. B., Shannon, R. D., and Gillson, J. L., J. [8] Shaplygin, I. S., Bromberg, A. V., and Sokol, V. A.,
solid State Chem. 3, 314 (1971). Russ. J. Inorg. Chem. (English Transl.) 15, 1195 (1970).

105
 II. 9. Silver Oxides modification of Ag 0
2 has been described by Kabal-
kina et al. [16]; have a layered Cdl 2
this appears to
structure possesing metal-metal bonds. These au-
Even though the literature contains many refer-
thors report that it may be a degenerate semiconduc-
ences [1-8] where silver oxides have been studied, it
tor or a semiconductor with a low energy gap.
appears that only Ag 0 and AgO (and probably
2

Ag 0
2 3) are the only well-characterized oxides of
AgO: Silver monoxide, AgO, has a monoclinic struc-
silver. Silver sesquioxide, Ag 0
2 3, is prepared at low
ture [3, 17, 18]; theoxygen content seems to vary
temperature in aqueous solutions [8]; it appears to
depending on the method of preparation [3], but
have cubic structure [9] and decomposes to AgO at
no other crystalline modifications of AgO are known.
higher temperatures.
The material is diamagnetic and has a very low room
temperature resistivity (^TOficm), but p shows nega-
Ag 0: The
2 stability range of Ag 0 2 is limited [8, tive temperature coefficient in the range 230 to 290 K
10-13] and decomposes to the metal above ~500 K. [1, 18]; these properties are explained as due to the

Ag 0
2 has a cubic structure [11] and exhibits semi- existance of monovalent and trivalent Ag ions in
conducting behavior [14, 15], A new high pressure AgO and confirmed by x-ray structure analysis [17].

Silver oxides

Oxide and description Data Remarks and inferences References

of the study

AgjO

Crystal structure and Cubic; space group, Pn3m; Z — 2; Ag 2 0 has the same structure as [11, 16].
x-ray studies. a *4.720 ±0.004 A. TEC~2X Cu 2 0 with considerable coval-
10“«/°C (not very accurate ency; the high-pressure modifica-
value). Decomposes above <~500 tion has a layer -structure prob-
K at atmospheric pressure. High- ably with metal-metal bonding.
pressure form (prepared at 115-
125 kbar and 1670±200 K):
Hexagonal; a =3.072 ±0.003 A;
c = 4.941 ±0.004 A. The high
pressure phase is denser by
~30%.

Thermal properties Heat capacity data have been re- Anomalies have been noted in the [19-21].
(10-470 K). ported in the 10-500 K range. heat capacity curves around 30
DTA studies have been carried and 420 K. The low temperature
out in the 300-470 K range. anomaly is difficult to under-
stand in terms of particle size of
surface area effects alone. The
high temperature anomaly is

probably associated with an-

nealing of crystal defects or
crystalization.

Electrical properties Semiconductor; p- type behavior a data lacking; the conduction [14, 15].
measured in oxygen with p «po* -1/4 p (500 K)~10* —
. mechanism is interpreted as due
atmospheres (300 and 450 bar) 10< Qcm; p (620 K)~10 -10 l a
to positive holes excited from
ficm; E„ *0.64 eV. traps (cation vacancies).

106
 Silver oxides —Continued

Oxide and description Data Remarks and inferences References

of the study

AgO

Crystal structure, magnetic Monoclinic; space group, P2i/c; AgO and CuO are isomorphous; the [1, 3, 17,
and electrical properties. Z = 4; a=5.85±0.02 A; 6 = 3.47 ± unusual physical properties of 18].
0.08 A; c = 5.49 ±0.05 A; 0 = AgO compared to CuO are ex-
107.5°. Structure analysis indi* plained as due to the coexistence
cates that Ag + and Ag 8+ ions of mono- and trivalent Ag. p-T
exist; two Ag-0 dis-
different behavior indicates either near
tances are encountered. Diamag- degeneracy or a semiconductor
netic in the range 90-370 K; with a low energy gap. Detailed
Xm = — 19.1X10 -6 emu; Unusually studies on AgO are urgently
low room temperature resistivity needed.
(p~10 flem); p decreases with
rise in T in the range 230-290 K.

References II. 10. Cadmium Oxides

f
l] Neiding, A. B., and Kazarnovskii, I. A., Dokl. Akad.
Nauk SSSR 78, 713 (1951).
Jones, P., and Thirsk, H. R., Trans. Faraday Soc. 50,
[2]
732 (1954).
Cadmium monoxide, CdO, is the well known oxide
[3] Graff, W. S., and Stadelmair, H. H., J. Electrochem. Soc. in the Cd-0 system [1-4]. Hoffman et al. [5] re-
105, 446 (1958). ported the preparation and structure of the peroxide
[4] Ylach, J., and Stehlik, B., Collec. Czech. Chem. Commun.
25, 676 (1960). Cd0 2, but detailed properties are not known.
[5] Amlie, R. F., and Riietschi, P., J. Electrochem. Soc. 108,
813 (1961).
[6] Karpov, A. A., Borisova, T. I., and Veselovskii, V. I., CdO: CdO has the cubic rock salt structure and is
Zh. Fiz. Khim. 36, 1426 (1962).
diamagnetic [6]. No phase transitions are known in
[7] Allen, J. A., Proc. Australian Conf. Electrochem., Sydney,
Hobart, Australia, 72, (1963) Publ. 1965. this oxide. The substance is usually nonstoichiome-
[8] Nagy, G. D., Moroz, W. J., and Casey, E. J., Proc. Am. pronounced cation
Power Sources Conf. 19, 80 (1965).
trie (Cd excess) with interstitials

[9] Stehlik, B., Weidenthaler, P., and Vlach, J., Chem. Listy or anion vacancies [2, 7-9], resulting in a free electron

[10]
52, 2230 (1958).
Garner, W. E., and Reeves, L. W., Trans. Faraday Soc.
concentration of ^10 19 -10 21
cm -3 . Such high elec-
50, 254 (1954). tron concentration induces degenerate behavior; at
Suzuki, T., J. Phys. Soc. Japan 15, 2018 (1960).
[11]
[12] Weidenthaler, P., Collec. Czech. Chem. Co mmun 28, .
high temperatures, CdO is either nondegenerate or
137 (1963). degenerate n-type semiconductor depending on the
[13] Otto, E. M., J. Electrochem. Soc. 113, 643 (1966).
history of the sample, i.e., sintering time and tem-
[14] Cahan, B. D., Ockerman, J. B., Amlie, R. F., and
Riietschi, P., J. Electrochem. Soc. 107, 725 (1960). perature, carrier concentration and oxygen pressure
[15] Talukdar, M. I., and Baker, E. H., Solid State Commun.
[1]. Donor impurities which contribute conduction
7, 309 (1969).
[16] Kabalkina, S. S., Popova, S. V., Serebryanaya, N. R., electrons give rise to an impurity level a few tenths
and Vereshchagin, L. F., Dokl. Akaa. Nauk SSSR band
of an electron volt below the conduction [10].
152, 853 (1963).
[17] Scatturin, V., Bellon, P. L., and Zannetti, R., J. Inorg. Detailed resistivity, Seebeck coefficient and Hall
Nucl. Chem. 8, 462 (1958).
coefficient measurements [1, 2, 9-14] as well as opti-
[18] Scatturin, V., Bellon, P. L., and Salkind, A. J., J. Electro-
chem. Soc. 108, 819 (1961). cal [15, 16], NMR [17, 18] and Faraday rotation
[19] Pitzer, K. S., and Smith, W. V., J. Am. Chem. Soc. 59,
[19] studies indicate that depending on the carrier
2633 (1937).
[20] Kobayashi, K., Sci. Rep. Tohoku Univ. 35, 173 (1951). concentration, the impurity band may overlap with
[21] Pitzer, K. S., Gerkin, JR. E., Gregor, L. V., and Rao,
C. N. R., Pure and Applied Chem. (J.IUPAC) 2, 211
the conduction band in CdO giving rise to quasi-
(1961). metallic or metallic properties.

107
 Cadmium oxides

Oxide and description Data Remarks and inferences References

of the study

CdO

Crystal structure and Cubic; space group,

2 Fm3m; Z = 4; CdO exhibits pronounced non- [3, 6, 7].
magnetic properties. a=4.6949 A. Slight variation of stoichiometry which is attributed
a with the stoichiometry. Dia- to either Cd interstitials or oxy-
magnetic; x = —48.74 X 10 -8 gen vacancies.
emu/g.

Electrical properties. Degenerate semiconductor be- Nonstoichiometry gives rise to [1, 2, 9-

-2 -3
havior; p (300 K)~10 -10 large number of charge carriers; 14].
-3
flcm; n~10 18 -10 21
cm depend- n can be controlled by sample
ing on the sample history but treatment. The impurity level
independent of temperature; belonging to the ionized donors
a (300 K)~20 mV/°C; Mh (81 K) merges into the conduction band
^700-1100 cm /V s; m* = 0.15— giving rise to quasi -metallic
0.45 m. behavior in some samples. De-
tailed conduction mechanism
treated.

Optical properties. Band gap = 2.3 eV; a possible in- Free carrier absorption is noted in [15, 16, 19].
directgap noted at ~1.2 eV; m* the optical spectra due to quasi-
(optical) = 1.4 m. Plasma edge free electrons. The results are
is ~0.2-0.5 eV depending on n. interpreted in terms of the band
eo = 18.1; Coo = 5.6. structure of CdO [20].

113
Cd NMR studies Results indicate that the nuclei [17, 18].
(1.4-300 K). interact strongly with the de-
generate conduction electrons and
the electrons are in the host
lattice conduction band, r «
n~ il3 T~ i; k « n 113 .

cao 2

Crystal structure Cubic; space group, Pa3; Z = 4; [5].

a = 5.313 ±0.003 A. Decomposes

violently at ~450-470 K to CdO
and oxygen. Other properties not
known.

References [11] Bastin, J. A., and Wright, R. W., Proc. Phys. Soc.
[10]
(Lond.) 68 A, 312 (1955).
[12] Konak, C., Hoschl, P., Dillinger, J., and Prosser, V.,
Crystal Growth, Suppl. J. Phys. Chem. Solids 341
[1] Hogarth, C. A., Proc. Phys. Soc. (Lond.) 64B, 691 (1951). (1967).
[2] Wright, R. W., and Bastin, J. A., Proc. Phys. Soc. [13] Wada, M., Japan J. Appl. Phys. 9, 327 (1970).
(Lond.) 71, 109 (1958). [14] Koffeyberg, F. P., J. Solid State Chem. 2, 176 (1970);
[3] van Houten, S., Nature (Lond.) 195, 484 (1962). Canad. J. Phys. 49, 435 (1971).
[4] Hoschl, P., Konak, C., and Prosser, V., Mat. Res. Bull. [15] Finkenrath, H., and von Ortenberg, M., Z. angew. Phys.
4, 87 (1969). 23, 323 (1967).
[5] Hoffman, C. W. W., Ropp, R. C., and Mooney, R. W., [16] Altwein, M., Finkenrath, H., Konak, C., Stuke, J., and
J. Am. Chem. Soc. 81, 3830 (1959). Zimmerer, G., Phys. Stat. Solidi 29, 203 (1968).
[6] Mookherji, T., J. Electrochem. Soc. 117, 1201 (1970). [17] Look, D. C., Phys. Rev. 184, 705 (1969).
[7] Cimino, A., and Merezio, M., J. Phys. Chem. Solids 17, [18] Benedict, R. P., and Look, D. C., Phys. Rev. B 2, 4949
57 (1960). (1970).
[8] Haul, R., and Just, D., J. Appl. Phys. 33, 487 (1962). [19] Zvara, M., Kocka, J.,Konak, C., and Hoschl, P., Phys.
[9 Koffyberg, F. P., Phys. Letters 30A, 37 (1969). Stat. Solidi 42, K5 (1970).
Lamb, E. F., and Tompkins, F. C., Trans. Faraday Soc. [20] Maschke, K., and Rossler, U., Phys. Stat. Solidi 28, 577
58, 1424 (1962). (1968).

108
 III. Oxides of 5 d Transition Elements

III.l. Lanthanum Oxides The C-form La 2 0 3 can be prepared by decom-

of
posing the precipitated hydroxide under vacuum
The common oxide of lanthanum is the sesqui-
and slow heating to 670 K [9]. DTA and resistivity
oxide, La 2 03 [1]. Warf and Korst [2] have reported
the monoxide, LaO, (probably a surface film), but
studies indicate the C—»A transition at ~870 K
which is irreversible and apparently sluggish; mois-
the material has not been prepared in bulk form.
ture seems to affect the T considerably. According
t
Rare-earth sesquioxides (of which La 2 03 is the
to Foex et al. [5, 6, 10], the A«=±H transition (marked
first member) generally exist in the cubic (C), hex-
by small thermal effects and lack of hysteresis) is of
agonal (A) or the monoclinic [1, 3] modifications;
the displacive type [11] whereas the H«=*X transition
the C-form is a defect structure of fluorite type
(marked by strong thermal effects) belongs to the
where the metal ion has the MO
0V2 coordination,
reconstructive type. During the course of the latter
where V stands for a vacancy along the body diag-
transition, the two corresponding modifications are
onal. The A- and B -forms are essentially close -packed
usually observed to coexist over a remarkably ex-
structures with MO7 coordination. All the oxides
tended range of temperatures; the energy barrier
have the C-type structure at low temperature. The
between the corresponding modifications is relatively
sesquioxides of heavier rare earths (Dy to Lu) as
high. No high pressure transitions are known in
well as Sc2 0 3 and Y 2 0 3 retain the C structure even
La 2 0 3 Daire and
. Wilier have recently reported the
up to very high temperatures (^2300 K); however,
existence of the B -modification of La 2 0 3 [12, 13];
sesquioxides from La to Nd revert to the A-type
thus, in this oxide it is possible to realize all the
structure depending on the temperature and method
different modifications that are generally exhibited
of preparation of the sample etc. High-temperature,
by the rare-earth oxides.
high-pressure transitions are exhibited by almost all
The magnetic behavior of La 2 0 3 has been examined
the rare-earth sesquioxides and these have been dis-
in the range 290 to 1070 K by Smol’kov and
cussed in detail in the literature [1, 3].
Dobrovol’skaya [14] who found that the substance is

La 2 0 3 : The usual form of La 2 0 3 that is encountered diamagnetic. Electrical properties have been ex-
is the hexagonal (A) modification [1, 4]. Detailed amined in detail by various workers in the literature
studies by Foex and co-workers [5, 6] indicate that [9, 15-21]. La 2 0 3 is a p-type semiconductor and
the A-form transforms on heating to another hex- shows considerable ionic conductivity at relatively
agonal form (H) at 2310 K which is followed by an low temperatures (<800 K). Impurities seem to
additional transformation at 2380 K to an unidenti- play a significant role in determining the contribution
fied structure (X) before melting (at 2573 K); A—>H to ionic conductivity [22]; pure electronic conduction
and H—>X transformations are reversible. The A<p*H exists at high temperatures.
transition does not involve a change in the crystal La 2 0 3 forms solid solutions with oxides of the type
symmetry, but discontinuities are noted in the a MO (M = Be [23], Mg [24], Ca [20, 25], Pb [26], and
and c parameters as well as in the c/a ratio at T t. M
Pd [27]); 2 0 3 (M = B [28], Al [29, 30], Cr [29], Fe
The presence of the X -modification is indicated by [29], Ga [29], Pr [31], and Y [29]); M0 2 (M = Ti
the appearance of one or two characteristic fines in [29, 32], Zr [29, 32-35], Hf [36], Ce [18, 29], and Sn
the x-ray diffraction patterns. The X-form appears [29]); M0
2 6 (M = Pa [37]) and M0 3 (M = W [38],
to be denser than the H-form, but the detailed and U [39]). The crystal structures and electrical
structure has not yet been established; preliminary properties of these solid solutions have been ex-
data seem to indicate [7, 8] a cubic structure differ- amined in detail in the literature with particular
ent from the C modification. reference to ionic conduction.

109
 Lanthanum oxides

Oxide and description Remarks and inferences References

of the study

La20 3

Crystal structure and C-type Cubic; space group, Ia3;

: Depending on the method of [1, 4-9, 12,
high temperature x-ray Z = 16; = 11.39±0.03 A. C-form
o preparation of the sample, differ- 13].
studies. is metastable; C—*A transition at ent types of polymorphs of La 20 3
~870 K; energy of activation can be realized. C—+A transition
~20 Kcal/mol. is irreversible; A—*H and H—*X
transitions are reversible but
A -type: Hexagonal; space group, differ in the mechanism of the
P3ml; Z = 1; at T = 293 K, a = process.
3.937 A; c = 6.13 A; at T = 2213
K, o=4.028 A; c = 6.385 A.
A-+H transition at 2310 K.

H-type: Hexagonal; at 2393 K, a =

4.063 A; c = 6.43 A. if-*X transi-
tion at (or above) 2380 K.

X-type Most probably cubic; de-

:

tailed structure not known.

Melting point ~2570 K.

B-type: Monoclinic; space group,

C2/m; Z = 6; a = 14.60 A; b =
3.717 A; c = 9.275 A; 0=99.77°.

Magnetic and electrical Diamagnetic (range 290-1070 K);
properties. X= — 0.23 X10 -6 emu/g.
Semiconductor; p (700 K)~10 6-
10® Ocm; Ea (C-form) ~1.1 eV; Ea
(A-form)~1.2 eV. C—*A transi-
tion is shown as a change in the
slope of lnp — 1/T plot; moisture
seems to affect T considerably,
t ductivity behavior of highly pure
p-type behavior; p oc po 2 _1/4
The magnetic behavior is under- [9, 14-21].
standable because there are no 4f
electrons to contribute to para-
magnetism. Electrical data are
lacking especially at high tem-
peratures where crystal structure
transitions occur. The con-
; and single crystalline material is

seems to show p- to n -transition urgently needed to elucidate the

at low po 2 and high temperature.
Considerable ionic conductivity
at low enough temperatures and
probably controlled mostly by
impurities.
detailedmechanism of conduction
and the contribution of the ionic
conductivity.

Infrared studies. Bands are noted in the range 280- [40].

430 cm -1 and are ascribed to the
metal-oxygen vibrations.

Heat capacity studies C„ (300 K) =25.92 ±0.08 cal/mol, [41].

(5-1800 K). K. There are no anomalies in the
measured temperature range.

References [2] Warf, J., and Korst, W., U.S. At. Energy Comm. NP-
6078, 1956.
[3] Eyring, L., and Holmberg, B., in Non-stoichiometric
[1] Brauer, G., Progr. in the Science and Technology of Rare Compounds (Adv. in Chem. Series) 39, 46 (1963).
Earths Ed. L. Eyring (Pergamon, Oxford) 1, 152 [4] Brauer, G., and Siegert, A., Z. anorg. allgem. Chem.
(1964); 2, 312 (19 66); 3, 434 (1968). 371, 263 (1969).

110
 [5] Foex, M., Z. anorg. allgem. Chem. 337, 313 (1965). III. 2. Hafnium Oxides
[6] Foex, M., and Traverse, J.-P., Bull. Soc. Franc. Mineral
Crist. 89, 184 (1966); Compt. Rend. (Paris) 262C,
743 (1966). Phase studies on the Hf-0 system [1-3] have shown
[7] Foex, M., and Pierre, J., Rev. Inst. Hautes Temp.
Refract. 3, 429 (1966). that the dioxide, Hf0 2, is the only stable oxide. Hf0 2
[8] Foex, M., Sci. Ceram. 4, 217 (1967), Publ. 1968; Chem. exhibits polymorphism and has been investigated in
Abstr. 70, 60406s (1969).
[9] Mehrotra, P. N., Chandrashekar, G. V., Rao, C. N. R., detail by many workers.
Subbarao, E. C., Trans. Faraday Soc. 62, 3586 (1966). The stable room temperature modification of Hf0 2
[10] Foex, M., and Traverse, J.-P., Compt. Rend. (Paris)
262C, 636 (1966). is monoclinic [4, 5] which transforms to the tetragonal
[11] Buerger, M. J., in Phase Transformations in Solids Ed. structure reversibly at ~1890 K [6, 7] with appreci-
R. Smoluchowski (John Wiley, New York, 1951).
[12] Daire, M., and Wilier, B., Compt. Rend. (Paris) 266C, able thermal hysteresis [8]. A reversible tetragonal-
548 (1968). cubic inversion in Hf0 2 has been reported at ~2970
[13] Wilier, B., and Daire, M., Bull. Soc. Franc. Mineral
Crist. 92, 33 (1969).
K, which is close to the melting point [7]. Even
[14] Smol’kov, N. A., and Dobrovol’skaya, N. V., Izv. Akad. though the detailed mechanism of the monoclinic-
Nauk SSSR, Neorg. Mater. 1, 1564 (1965).
Foex, M., Compt. Rend. (Paris) 220, 359 (1945). tetragonal transition in Hf0 2 is not known, compari-
[15]
[16] Rudolph, J., Z. Naturforsch. 14a, 727 (1959). son with the analogous transition in Zr0 2 suggests
[17] Noddack, W., and Walch, H., Z. Elektrochem. 63, 269 the first order, diffusionless and athermal nature of
(1959); Z. Phys., Chem. (Leipzig) 211, 194 (1959).
[18] Neuimin, A. D., and Pal’guev, S. F., Tr. Inst. Elektro- the transformation in this oxide [5, 6, 8, 9].
khim., Akad. Nauk SSSR Ural’sk. Filial 133 (1963). A high pressure orthorhombic modification of Hf0 2
[19] Pal’guev, S. F., and Yol’chenkova, Z. S., in Electro-
chemistry of Molten and Solid Electrolytes Ed. A. N. has been described by Bocquillon et al. [10]; this is
Baraloshkin (Consultants Bureau, New York, 1968), obtained by heating the monoclinic Hf0 2 at ^1870
Yol. 6.
[20] Etsell, T. H., and Flengas, S. N., J. Electrochem. Soc.
K under a minimum pressure of ~15 kbar; this
116, 771 (1969). metastable phase reverts to the monoclinic form on
[21] Subba Rao, G. V., Ramdas, S., Mehrotra, P. N., and prolonged heating at ~570 K.
Rao, C. N. R., J. Solid State Chem. 2, 377 (1970).
[22] Etsell, T. H., and Flengas, S. N., Chem. Rev. 70, 339 The tetragonal or cubic modification of Hf0 2 can-
(1970). not be quenched nor can it be stabilized at room
[23] Kuo, C.-K., and Yen, T.-S., Chem. Abstr. 63, 10743e
(1965).
temperature [7, 10] and efforts to obtain these forms
[24] Tresvyatskii, S. G., and Lopato, L. M., Vpor. Teorii i by precipitating Hf0 2 in finely divided form have
Prim. Redkozem. Metal. Akad. Nauk SSSR 155 (1964).
been unsuccessful [9]. Submicron Hf0 2 prepared by
[25] Barry, T. L., Nucl. Sci. Abstr. 20, 36784 (1966).
[26] Cassedanne, J., Anais Acad. Brasil. Cienc. 36, 413 (1964). the hydrolytic decomposition of alkoxides [9] is amor-
[27] McDaniel, C. L., and Schneider, S. J., J. Res. Nat. Bur. phous and transforms directly to the monoclinic
Stand. (U.S.), 72A (Phys. and Chem.), No. 1, 27-37
(Jan.-Feb. 1968). form at ~600 K. However, the cubic form (and not
[28] Levin, E. M., Phys. Chem. Glasses 7, 90 (1966). the tetragonal form) seems to be stabilized in thin
Andreeva, A. B., and Keler, E. K., Zh. Prikl. Khim. 39,
[29]
films of Hf0 2 and recently El-Shanshoury et al. [11]
489 (1966).
[30] Bonder, I. A., and Toropov, N. A., Izv. Akad. Nauk have discussed their polymorphic behavior.
SSSR, Ser. Khim. 212 (1966). Electrical properties of Hf0 2 have been examined
[31] Brauer, G., and Pfeiffer, B., Paper presented in Fifth
Rare Earth Conference’, Chem. Session C, 1965. in detail by Tallan, Tripp, and Vest [12]. The ma-
[32] Collongues, M. R., Queyroux, F., Perez, M., Zorba, Y., terial is a p-type semiconductor and a is essentially
and Gilles, J.-C., Bull. Soc. Chim. France 4, 1141
electronic in the range 1300-1800 K (po 2 from 10
-18
(1965).
[33] Lin, T.-H., and Yu, H.-C., Kuei Suan Yen Hsueh Pao to 1 atm). At low oxygen partial pressures, a small
3, 159 (1964).
contribution due to the ionic conductivity has been
[34] Fehrenbacher, L. L., Jacobson, L. A., and Lynch, C. T.,
Proc. Conf. Rare Earth Res., 4th, Phoenix, Arizona, noticed [12-14]. Measurements on polycrystalline
1964, p. 687 (Publ. 1965). Hf0 2 by Tallan et al. [12] did not show a discon-
Strickler, D. W., and Carlson, W. G., J. Am. Ceram. Soc.
[35]
48, 286 (1965).
tinuity in the ln<r — 1/T plot at the monoclinic-
[36] Komissarova, L. N., Wang, K. S., Spitsyn, V. I., and tetragonal phase transition.
Simanov, Yu. P., Russ. J. Inorg. Chem. (English
Transl.) 9, 385 (1964).
Hf0 2 forms a complete series of solid solutions with
[37] Keller, C., J. Inorg. Nucl. Chem. 27, 797 (1965). Zr0 2 (8, 15-17] and generally, the monoclinic-
[38] Tyushevskaya, G. I., Afonskii, N. S., and Spitsyn, V. I., tetragonal transition temperature is decreased with
Dokl. Akad. Nauk. SSSR 170, 859 (1966).
[39] Koshcheev, G. G., and Kovba, L. M., Izv. Akad. Nauk increasing concentration of Zr0 2. A decrease in T t

SSSR, Neorg. Mater. 2, 1254 (1966). is also observed in the solid solutions of Hf0 2 with
[40] Subba Rao, G. V., Rao, C. N. R., and Ferraro, J. R.,
Appl. Spec. 24, 436 (1970) and references therein.
rare-earth sesquioxides [18]. Hf0 2 -MO (M =
Systems
[41] Holley, C. E., Jr., Huber, E. J., Jr. and Baker, F. B.» Mg [19], Ca [19-22]), and Hf0 2 -M 0 (M = Sc [23, 2 3

Progr. in the Science and Technology of Rare Earths,

24], Y [20, 25-27], La [25, 28], Nd [25, 29], Sm [30],
Ed. L. Eyring, (Pergamon, Oxford) 3, 343 (1968) and
references therein. and Gd [31]) have been investigated in the literature.

Ill
 Hafnium oxides

Oxide and description Data Remarks and inferences References

of the study

HfOg

Crystal structure and fe 298 K: Monoellnie; space In many respects, HfOg resembles [4-8, 10,
x-ray studies. group, P2i/c; Z = 4; a=»5.1156± Zr0 2 even though there are subtle 32],
0.0005 A; b = 5.1722 ±0.0005 A; differences in behavior. The se-
c = 5.2948 ±0.0005 A; 0= 99.02 ± quence (and the mechanism )of
0.08 A. TEC (470-670 K): [100], the transformations from the low
5.9X10-®; X10-®.
[001], 11.9 symmetry to the high symmetry
TEC slightly increases with tem- in the crystal structure are the
perature up to 1470 K. Mono- same in Hf0 and Zr0 2 except
2

clinic—tetragonal transition at that the T for Hf0 are higher

< 2

1890 K; thermal hysteresis, 30 K. and the thermal hysteresis values

The transition appears to be are lower. The high temperature
endothermic associated with a modifications of HfOg cannot be
volume contraction, but detailed quenched nor can they be
data are not available. Boganov stabilized at room temperature by
et al. [7] report the T to be j solid solution formation.
~2170-2270 K for this transition.
At 2770 K, a = 5.21 A, c = 5.35 A;
this tetragonal phase is stable up
to ~2970 K and then transforms
to cubic fee modification with
a = 5.300 A. The tetragonal-
cubic inversion is reversible; how-
ever detailed data are lacking.
High-pressure form: obtained by
heating at 1870 K under 60 kbar
pressure and quenching; ortho-
rhombic; a =5.008 ±0.006 A; b =
5.062 ±0.006 A; c = 5.223 ±0.006
A. This metastable phase reverts
to the monoclinic form on pro-
longed heating at 570 K.
Amorphous Hf0 2 obtained by the
thermal decomposition of the
metal alkoxide goes to the mono-
clinic variety on heating at ~600
K; the intermediate cubic and
tetragonal forms are not realiz-
able, neither they can be
quenched to room temperature
from the respective temperature
ranges of existence. Melting
point of HfOj is 3070 K.

Electrical properties. p-type semiconductor in the range The electrical behavior is as ex- [12].

1270-1770 K; <r (1570 K)~10-» pected and similar to Zr0 2 which

B" cm" E. is 0.7 eV ( <1570 K)
1 1
; also behaves as an extrinsic p-
and 0.2 eV ( >1570 K); a « poj 1/# type semiconductor. Apparently,
(poi>10“® atm); md = 0.3-1.6X no discontinuity in the ln<r — 1/T
10“® cm 2 /V s. At low po*(<10 -1 plot has been noticed at the
atm) small contribution due to monoclinic -tetragonal transition
ionic conductivity seems to be in Hf0 2.

present. The defect structure is

interpreted in terms of holes and

fully ionized cation vacancies.

112
 References and Chang and Phillips [10]. In addition to the sub-
oxides, TaO* (Ta@0), TaO y (Ta 4 0) and TaO* (Ta 2 0),
[1] Rud^, E., and Steeher, P., J. Lesa-Comm. Metals 5, 78 the monoxide TaO (whose existence is not proved
[2] Bomagala, R. F., and Ruh, R., Trans. Am. Soe. Met. 58,
beyond doubt), dioxide, TaG 2 and the pentoxide,
164 (1965). Ta 2 0 6 are known; however, Ta 2 0 6 is the only oxide
[3] Karnilov, I. L, Glazova, V. V., and Ruda, I. G., Izv.
Akad. Nauk SSSR, Neorg. Mater. 4, 2106 (1968). which is well-characterized and extensively investi-
[4] Adam, J., and Rogers, M. D., Acta Cryst. 12, 951 (1959). gated in recent years.
[5] Ruh, R., and Corfield, P. W. R., J. Am. Ceram. Soc. 53,
126 (1970).
[6] Wolten, G. M., J. Am. Ceram. Soc. 46, 418 (1963).
Boganov, A. G., Rudenko, V. S., and Makarov, L. P., Suboxides: The suboxides form only by the oxida-
[7]
Dokl. Akad. Nauk SSSR 160, 1065 (1965). tion of tantalum metal or tantalum compounds.
[8] Ruh, R., Garret, H. J., Domagala, R. F., and Tallan,
N. M., J. Am. Ceram. Soc. 51, 23 (1968).
Ta 6 0 (tetragonal) forms at ~570 K; Ta 4 0 (orthor-
[9] Mazdiyasni, K. S., and Brown, L. M., J. Am. Ceram. hombic) forms below 770 K and Ta 2 0 (tetragonal)
Soc. 53, 43 (1970).
Bocquillon, G., Susse, C., and Vodar, B., Rev. Int.
forms between 620 to 1470 K. A complex suboxide
[10]
Hautes, Temp. Refract. 5, 247 (1968). of unknown structure is formed above 1770 K. Elec-
[11] El-Shanshoury, I. A., Rudenko, V. A., and Ibrahim, I. A.,
tron diffraction studies of monocrystalline samples
J. Am. Ceram. Soc. 53, 264 (1970).
[12] Tallan, N. M., Tripp, W. C., and Vest, R. W., J. Am. above 1770 K. Electron diffraction studies of mono-
Ceram. Soc. 50, 279 (1967).
Robert, G., Deportee, C., and Besson, J., J. Chim. Phys. crystalline samples reveal superlattices
[8, 9]. These
[13]
64, 1275 (1967). suboxides appear to be metallic, but detailed data
[14] Etsell, T. H., and Flengas, S. N., Chern. Rev. 70, 339
(1970).
are lacking.
[15] Mazdiyasni, K. Lynch, C. T., and Smith, J. S.,
S.,
J. Am. Ceram. Soc. 48, 372 (1965).
[16] Stansfield, O. M., J. Am. Ceram. Soc. 48, 436 (1965). Monoxide, TaO: Lagergren and Magn61i [1] and
[17] Gavrish, A. M., Sukharevskii, B. Ya., Krivornchko, P. P.,
Schonberg [3] reported the existence of tantalum
and Zoz, E. I., Ivz. Akad. Nauk SSSR, Neorg. Mater.
5, 547 (1969). monoxide with a narrow homogeneity range; it has
[18] Koehler, E. K., and Glushkova, V. B., Sci. Ceramics 4,
a cubic rock salt structure with a variable lattice
233 (1967, publ. 1968).
[19] Strekalovskii, V. N., Volchenkova, Z. S., and Pal’guev, parameter. Physical properties are not known. The
S. F., Izv. Akad. Nauk SSSR, Neorg. Mater. 2, 1230
existence of this monoxide has not been proved be-
(1966).
[20] Volchenkova, Z. S., and Pal’guev, S. F., Trans. Inst. yond doubt and systematic investigations are called
Elektrokhim Akad. Nauk SSSR, Ural. Filial 5, 133
for.
(1964).
[21] Johansen, H. A., and Cleary, J. G., J. Electrochem. Soc.
Ill, 100 (1964).
[22] Delamarre, C., Silicates Ind. 32, 345 (1967). Ta0 2 : Rutile type Ta0 2 is known to be a stable
[23] Komissarova, L. N., and Spiridinov, F. M., Dokl. Akad. oxide but detailed data on the physical
[1, 3, 11],
Nauk SSSR 182, 834 (1968).
[24] Kalinovskaya, C. A., Spiridinov, F. M., and Komissarova, properties are lacking. Ta0 2 appears to form solid
L. N., J. Less-Comm. Metals 17, 151 (1969). solutions with Ti0 2 [3, 12], although there are
[25] Komissarova, L. N., Wang, C. S., and Spitsyn, V. I.,
Izv. Akad. Nauk SSSR, Ser. Khim. 1, 3 (1965). changes in the cation valencies.
[26] Besson, J., Deportee, C., and Robert, G., Compt. Rend.
(Paris) 262,327 (1966).
[27] Duclot, M., Vicat, J., and Deportee, C., J. Solid State Ta 0 Tantalum
2 6 : pentoxide, Ta 2 0 6 , is a stable oxide
Chem. 2, 236 (1970).
with a very narrow homogeneity range [13] and has
[28] Komissarova, L. N., Wang, C. S., Spitsyn, V. I., and
Simanov, Yu. P., Russ. J. Inorg. Chem. 9, 385 (1964). been well-investigated by various workers. The exact
[29] Komissarova, L. N., Spitsyn, V. I., and Wang, C. S.,
relationships of the various polymorphs of Ta 2 Oa are
Dokl. Akad. Nauk SSSR 150, 816 (1963).
[30] Isupova, E. N., Glushkova, V. B., and Keler, E. V., not clearly understood because of the complexity of
Izv. Akad. Nauk SSSR, Neorg. Mater. 4, 399 (1968).
the structures of the phases, sluggish nature of the
[31] Spiridinov, F. M., Stepanov, J. A., Komissarova, L. N.,
and Spitsyn, V. I., J. Less-Comm. Metals 14, 435 transitions and the existence of various metastable
(1968).
phases that can be stabilized by impurities.
[32] Filatov, S. K., and Frank-Kamenetskii, V. A., Sov.
Phys. -Cry stallogr. (English Transl.) 14, 696 (1970). It is fairly well established that Ta 2 C>6 exists in
two polymorphic forms, /3 and a, with a reversible
phase transition at ~1630 K [1, 14]; the transition
III. 3. Tantalum Oxides between them is sluggish and the low temperature /3
form can persist as a metastable phase in the stabil-
The Ta-0 system has been investigated by many ity field of the a form and can be melted at ~2060
workers [1-7] and the stability and phase relation- K. The high temperature (a) form melts at ^2160 K
ships of the various oxides have been reviewed and [14, 15].
discussed by Steeb and Renner [8], Niebuhr [9], The proper method of indexing the powder pattern

113
of the /3 form has puzzled crystallographers for a studies have, however, indicated [15, 29] that the
long time; the more intense diffraction lines can be a form actually undergoes several unquenchable
indexed on the basis of a simple orthorhombic sub- phase transitions upon cooling from high tempera-
cell with a = 6.20, 6 = 3.66, and c = 3.89 A. However, tures. The true high-temperature form is postulated
numerous weak lines which also appear in the pat- to be tetragonal in its field of stability and several
tern have not been interpreted unambiguously main- metastable phases occur in the stability field of the
ly because the position of these super-structure lines low-temperature polymorph. Ta 2 0 B when quenched
is upon both the nature of the
strongly dependent from above 1630 K (T\) is triclinic and transforms
heat treatment and the amount of impurities [16, to a monoclinic form on heating to ~590 K and this
17]. Consequently, different workers have suggested in turn reverts to the tetragonal form at ~1220 K.
different lattice parametersand symmetries to ex- Sarjeant and Roy [30] reported a metastable high-
plain the x-ray pattern of the /3 form of Ta 2 C>6 [7, temperature hexagonal form of Ta 2 0& obtainable by
18-25]. Systematic examination of the polymorphic rapid quenching techniques; this 5 form reverts to
behavior of Ta 2 06 by Roth and co-workers [15, 16, the /3 form on annealing at ~1470 K. Impurities
26-28] has contributed significantly to the under- like titanium lower the T t of the /3
—>a transition
standing of the structure of the low-temperature and Sc 8+ in low concentrations appears to stabilize
phase. These workers found that many metallic the high-temperature tetragonal phase [16, 28]; the
oxides, especially WOa, can stabilize the /3-form and crystal structure consists of a-UOa-type blocks in
that this pure phase exists in two slightly different which Ta atom is surrounded by a pentagonal bi-
modifications with 6-axis multiplicities of 11 and 14 pyramid of oxygen atoms. These blocks are infinite
at low temperatures and at ~1580 K respectively. in two directions and are separated from similar
At intermediate temperatures, an infinite number of blocks along a third direction by shear planes and in
at least partially ordered sequences of these two the vicinity of these shear planes, the Ta atoms are
modifications exist in equilibrium. The addition of surrounded by distorted octahedral coordination
WO 3 (or other impurities) causes the stabilization polyhedra.
of an infinite number of phases similar in structure Semiconducting behavior of Ta 2 0 B has been ex-
to the low-temperature form of Ta 2 0 6 . amined by Kofstad [13] who finds that the material
The structure of the high-temperature (a) form isp- or n-type depending on the po2 Differences in.

ofTa 2 0 6 has been a subject of intensive study and the dielectric behavior of the polymorphs of Ta 2 06
and tetragonal, hexagonal, orthorhombic, mono- have been reported by Pavlovic [31]. Systems K 2 0-
clinic, and triclinic symmetries have been suggested Ta 2 0 6 [32] and Nb 2 06-Ta 2 0 B [33, 34] have been in-
by various workers [1, 14, 20, 22, 29]. Detailed vestigated in the literature.

Tantalum oxides

Oxide and description Data Remarks and inferences References

of the study

Suboxidea

Crystal structure.
Ta#0: Tetragonal; a *=3.36 A; c =
3.25 A. Ta 4 0: Orthorhombic; o =
3.61 A; b “3.27 A; c = 3.20 A.
TajO: Tetragonal; a = 6.63 A;
c = 4.75 A. Detailed data on the
physical properties are lacking.
These oxides are formed from Ta by [It 2, 3, 5,
the oxidation at various tempera- 9, 10].
tures; some reveal superstructure
in electron diffraction patterns.

TaO

Crystal structure. Cubic; space group, Fm3m; 2 = 4; [1. 31.

0 = 4.422-4.429 A. Formed in the
range 870-1770 K; physical prop-
erties not known in detail.

114
 Tantalum oxides —Continued

Oxide and description Remarks and inferences References

of the study

TaOj

Crystal structure. Tetragonal; space group, P42/mnm; [1. 31-

Z = 2; 0 = 4.709A; c = 3.065 A.
Physical properties are not known
in detail.

TagOg

Crystal structures and
x-ray studies.
Low -temperature 03) form: Sub- Systematic examination of the de- [15, 16,
cell: orthorhombic; Z = 1; a — tailed phase relationships by 26-28].
6.20 A; 6 = 3.66 A; c = 3.89 A. Roth and coworkers has revealed
True-cell: orthorhombic; Z = ll; a proper understanding of the
o=6.198 A; 6=40.29 A; c = 3.888 structures of TagOg modifications
A; 6-axis multiplicity = 11. and cleared the ambiguities of
0-form at a given temperature the earlier workers.
consists of an infinite number of
partially ordered sequences of
two simple modifications with
multiplicities 11 and 14 and these
sequences are affected both by
heat treatments and by impuri-
ties thus explaining considerable
ambiguity encountered by various
workers in the interpretation of
the powder patterns. T <~1630 K;
sluggish but completely reversible
transition. High -temperature (a)
form: tetragonal; space group;
I4j/amd; Z = 6; a = 3.81 A; c*
36.09 A. This phase is un-
quenchable in pure TagOg; how-
ever, Sc ,+ appears to stabilize this
form. The structure consists of
a-UOj type blocks in two direc-
tions and separated in the third
direction by shear planes. Sc 8+
doping seems to introduce ran-
dom shear planes (Wadsley de-
fects) which stabilize the struc-
ture. TagOg quenched from
temperatures above T, is tri-
clinic: a =3.801 A; 6 = 3.785 A;
c = 35.74 A; <*=90.91®; /3 =90.19®;
6
yss*90 This triclinic phase
.

transforms to monoclinic phase

on heating to ~590 K; a mea o -
V2 6meao “ y/% bttlei Csnooo®*
Ot,i„;

cuio.Monoclinic phase reverts to

the tetragonal phase on heating
to '>-'1220 K. Rapid quenching of
TagOg from high temperatures
appears to produce a hexagonal
modification; a =3.874 A; c =

115
 Tantalum oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

3.62 A. This 6 form reverts to the

/3form on annealing at ~1470 K.
Melting pointcii2160±20 K.

Electrical properties.
Semiconductor in the range 1000- The defect structure is interpreted [13].
1670 K. cr (1000 K)~10" 5 0" 1
in terms of oxygen interstitials
cm" ; E0 = 1.79 eV; a (1300 K;
1
(p-type) and oxygen vacancies
P 02 ~l atm)~l mV/K. p- type (re-type). No change in the slope
behaviour at poj^l atm and re- of bnr-l/T plot noticed at T <; the
type at lower po*. p to re transi- reason is not clearly understood.
tion takes place at lower po* with
decreasing T.

Infrared spectra. Bands are noted at 720 and 860 [34],

•
cm -1 for a-Ta 2 06 and interpreted
in terms of the metal-oxygen
vibrations.

Simanov, Yu. P., Lapitskii, A. V., and Artamanova,

References [19]
E. P., Vetn. Mosk. Univ. 9, Ser. Fiz. Mat. i Estestven
[
1] Lagergren, S., and Magneli, A., Acta Chem. Scand. 6, Nauk (6), 109 (1954).
\\\ (1952). [
20 ]
Zaslavskii, A. I., Zvinshuk, R. A., and Tutov, A. G.,
[2 Wasilewski, R. J., J. Am. Chem. Soc. 75, 1001 (1953). Dokl. Akad. Nauk SSSR 104, 409 (1955).
3 Schonberg, N., Acta Chem. Scand. 8, 240 (1954). [
21 ]
Lapitskii, A. V., Simanov, Yu. P., Semenen, K. N., and
Pawel, R. E., Cathcart, J. V., and Campbell, J. J., Acta Yarembash, E. I., Vetn. Mosk. Univ. 9, Ser. Fiz. Mat.
Met. 10, 149 (1962). i Estestven Nauk, (2), 85 (1959).

Norman, N., J. Less-Comm. Metals 4, 52 (1962). [

22 ]
Harvey, J., and Wilman, H., Acta Cryst. 14, 1278 (1961).
B Kofstad, P„ J. Inst. Metals 90, 253 (1962); 91, 209
(1963).
23
24
Lehovec, K., J. Less-Comm. Metals 7, 397 (1964).
Turnock, A. C., J. Am. Ceram. Soc. 48, 258 (1965);
Terao, N., Japan J. Appl. Phys. 6, 21 (1967). 49, 382 (1966).
[si Steeb, S., ana Renner, J., J. Less-Comm. Metals 10, 246 [25] Wolten, G. M., and Chase, A. B., Z. Krist. 129, 365
(1966). (1969).
Niebuhr, J., J. Less-Comm. Metals 10, 312 (1966). [26] Roth, R. S., and Stephenson, N. C., in The Chemistry
(ioj Chang, L. L. Y., and Phillips, B., J. Am. Ceram. Soc. of Extended Defects in non-Metallic Solids, Eds. L.
52, 527 (1969). Eyring and M. O’Keeffe, (North Holland Publ. Co.,
[11] Rogers, D. B., Shannon, R. D., Sleight, A. W., and Amsterdam, 1970).
Gillson, J. L., Inorg. Chem. 8, 841 (1969). [27] Roth, R. Waring, J. L., and Parker, H. S., J. Solid
S.,
[
12 ] Riidorff, W., and Luginsland, H. H., Z. anorg. allgem. State Chem. 2, 445 (1970).
Chem. 334, 125 (1964). [28] Stephenson, N. C., and Roth, R. S., J. Solid State Chem.
13 Kofstad, P., J. Electrochem. Soc. 109, 776 (1962). 3, 145 (1971).
14 Reisman, A., Holtzberg, F., Berkenblit, M., and Berry, [29] Laves, F., and Petter, W., Helv. Phys. Acta 37, 617
M., J. Am. Chem. Soc. 78, 4514 (1956). (1964).
[15] Waring, J. L., and Roth, R. S., J. Res. Nat. Bur. Stand. [30] Sarjeant, P. T., and Roy, R., J. Am. Ceram. Soc. 50, 500
(U.S.), 72A (Phys. and Chem.) No. 2, 175-186 (Mar.- (1967).
Apr. 1968). [31 Pavlovic, A. S., J. Chem. Phys. 40, 951 (1964).
[16] Rotn, R. S., Waring, J. L., and Brower, W. S., Jr., [32 Holtzberg, F., and Reisman, A., J. Phys. Chem. 65, 1192
J. Res. Nat. Bur. Stand. (U.S.), 74A (Phys. and (1961).
Chem.), No. 4, 485-493 (July-Aug. 1970). [33] Mohanty, G. P., Fiegel, L. J., and Healy, J. H., J. Phys.
[17] Jahnberg, J., and Andersson, S., Acta Chem. Scand. 21, Chem. 68, 208 (1964).
615 (1967). [34] Alyamovskii, S. I., Shveikin, G. P., and Gel’d, P. V.,
[18] Frevel, L., and Rim, H., Anal. Chem. 27, 1329 (1955). Russ. J. Inorg. Chem. 12, 915 (1967).

116
 III.4. Tungsten Oxides elinie WO§ ean be partially transformed to th© tri-
elinie phas© by grinding. Th© latter phai© ii itabl©
Tungsten dioxide and trioxide are the well-known in th© rang© 233 to 290 K. On cooling to 233 K, th©
oxides in the W»0 system [1=3]. Two mixed valence phai© of pur© WO§ changes to a monoclinic
trielinie
phases, Wi§04§ (WOg,?g) and WggOig (WOg.go) also phas© with observable temperature hysteresis, TEC,
exist [1, 4=7] in the range WOg-WO§ and substoiehio- AH and AS changes, discontinuities in p, g, H#, and
metrie phases of WO§, viz., WOg,g§ (WioOiu) and Hu [18, 23=23, 27=29] and changes in the domain
WOg.ii (WioOiw) have been characterized in the structure [29]. This monoelinie form seems to be
literature 8 ]. Even though earlier workers [9, 10]
[ stable in the range 77 to 233 K and has been found
have claimed the existence of an oxide 3 O, recent W to be ferroelectric [28, 30, 31]. Roth and Waring [26]
studies [7, 11] indicate that the oxide is not a stable obtained this phase at room temperature by quench-
phase. ing a soid solution of 2 percent Nb205 in WO3 from
1500 to 1660 K; however, this solid solution does
WO2: The range of homogeneity of W0 2 appears to
not exhibit ferroelectricity whereas specimens of sin-
be small (1.94-2.025) [12] and the material is stable tered W0
8 containing 2-4 percent Ta 2 Os have been
up to 1800 K
after which it decomposes. It has a
reported to be ferroelectric at room temperature
monoclinic structure and exhibits metal-
[2, 5, 13, 14]
[32], Nonstoichiometry in W0 3, by way of removal
lic behavior [13]; no phase transitions are known in
of oxygen from the lattice, apparently decreases the
W0 2. .
T t of the two low -temperature transitions and brings
W0 forms solid solutions with Ti0 2 [15] and
2
about changes in the electrical properties [18].
V0 2 [14, 16] giving rise to rutile based structures The room -temperature monoclinic modification of
WO3 transforms to an orthorhombic structure re-
Wi 8 049: This oxide is monoclinic [4, 5] and is stable

above 860 K; below this temperature, it decomposes

versibly at '"‘-'580 K
DTA peak [31]
[24, 33-37];
and have been noted at this
resistivity discontinuity
to W0 2 and W 20 O 58 Wi
.
8 C>49 is the most refractory
temperature [24]. Roth and Waring [26] obtained the
oxide (stable up to 1970 K) of the W-0 system [7].
orthorhombic form at room temperature on heating
Physical properties of this oxide are not known.
the stabilized monoclinic W0 3 (containing 2%
W O { This monoclinic oxide seems to have a nar- Nb Oe) 2 to —'1170 K
-
and rapid cooling. The orthor-
20 68

row range of homogeneity [4, 5, 17, 18] and decom- hombic—^tetragonal transition in WO3 is well estab-

K W0 lished and investigated by many workers [26, 33, 34,

poses below 760 to 2 and WOa [7]. Measure-

ments of resistivity and Seebeck coefficient indicate 36, 38-41]; x-ray diffraction, DTA and resistivity
metallic behavior [18].
measurements indicate the T to be 1010 K (accom- t

panied by thermal hysteresis). The tetragonal phase

Substoichiometric phases B oOi48 and W40O119 : W is related to the ReOa structure and doping with

are monoclinic and according to Gebert and Acker- Nb lowers the T t considerably [26]; according to
man [8], a high-temperature polymorph of 6 oOi4 8 W Roth and Waring [26], the (Nb) stabilized mono-
exists. Detailed data are lacking. clinic phase of WOa transforms to the tetragonal
modification (without going through the triclinic,

W0 8 : Tungsten trioxide is a stable phase and is monoclinic and orthorhombic structures as in the
usually associated with slight nonstoichiometry [1, case of pure WO3) at ^1010 K and this monoclinic—
7, 18]; it is polymorphic and not less than five tetragonal transition has been found to be reversible
distinct crystallographic modifications are known (fig. below 1025 K.
III.l). The phase transitions among the various DTA [35, 38], heat capacity and resistivity [39]
forms of WO3 have been examined using a variety of studies indicate transitions at ~1170 and ~1500 K
techniques. in pure WOa, but no structural changes have been
At room temperature, WOa is monoclinic [1, 5, 7, observed (fig. III.l) [26, 35, 38]; the high temperature
12, 19-22] and this phase is stable in the range 290 phases remain tetragonal. A transformation from
to 583 K [23]. On cooling to 290 K, the room tem- tetragonal to cubic structure of the ideal ReOa type
perature polymorph transforms to a triclinic form; (which seems quite logical) has not been observed
this reversible change is associated with some thermal in pure WOa below the melting point (1700 K).
hysteresis (3-13° depending on the sample), AH Attempts to prepare the cubic phase by doping have
and AS and discontinuities in p, a, 1?#, and p# [18, not been successful.
23-25]. Roth and Waring [26] noted that the mono- WO3 is diamagnetic [18, 42] in the range 77 to 292

117
 250 K 293-303 K 600 K
Monoctinlc Triclinic Monoclinic Orthorhombic
(77-233 K) 230 K (233-290 K) 290 K (290-583 K) 560 K (580-1010 K)

(Ferroelectric) AH = 39cal/mole AH=20 cal/moie AH=330cal/mole

1170 K

Tetragonal ~1500 K Tetragonal Tetragonal

AH=120 cal/moie ~t170 K (1010-1700 K)

AH = 2 80 cal/moie (Antiferroelectric ?)

Figure III.l. Phase relations in WD 8.

K; paramagnetism has been noted at -~1.3 K

feeable deficient WO 3 has been investigated in detail by
in the oxygen deficient WO
3 [18]. It is semiconduc- Sienko and co-workers [18, 24, 25],
ting at low temperatures, but exhibits semimetallic W0 combination with other metal oxides form
3 in
behavior at higher temperatures. As mentioned ear- very interesting mixed oxides called Tungsten bron-
lier, electrical characteristics show anomalous be- zes.’ The physical properties of these bronzes have
havior at the transition points. The mechanism of been examined in great detail and discussed in the
electrical conduction in stoichiometric and oxygen literature [43-46].

Tungsten oxides

Oxide and description Data Remarks and inferences References

of the study

wo 2

Crystal structure and Monoclinic; space group, P2i/c; The structure is that of a dis- [2, 5, 13,
electrical properties. Z = 4; a = 5.5607 ±0.0005 A; b = torted rutile; metal-metal bond- 14].
4.9006 ±0.0005 A; c = 5.6631 ± ing seems to exist and the elec-
0.0005 A; = 120.44°. Metallic
j8 trical properties are consistent
behavior; p (4.2 K)=2.0X10 -4 with this assumption.
12cm; p (300 K) = 2.9 XlO -3 12cm.

w o
18 49

Crystal structure. Monoclinic; a = 18.28 A; 6=3.775 [4, 5, 7].

A; c = 13.98 A; 0 = 115.14°. De-

composes below 860 K
but stable
up to 1970 K. Detailed data are
lacking.

Crystal structure and Monoclinic; a = 16.74 A; 6=4.019 The structure appears to be re- [4, 5, 7, 17,
electrical properties. A; c = 14.53 A; 0 =95.45°. lated to WO 2 and metal-metal 18].

Decomposes below 760 K but bonding seems to be present, p

stable up to 1820 K. Metallic anomaly at ~270 K is not ex-
behavior; p (80 K)~5X10~ 4 plainable at present.
12cm; p-T plot exhibits a maxi-
mum at 270 K. a (90 K)~ — 15
pV/°C; a (240-320 K) 30
pV/°C. n«4XlO*Vcm 3 .

118
 Tungsten oxides —Continued
Oxide and description Data Remarks and inferences References
of the study

W O
50 148 (W02.9#)

Crystal structure Monoclinic; space group, P2/c; a = The structure appears to be re- [
8 ].
11.90 ±0.02 A; 6 = 3.826±0.012 lated to that of WO 3.

A; c = 59.64 ±0.06 A; 0=98.4°. A

high -temperature polymorph with
a unit cell having the formula
W 26 O 74 is found to be stable at
~1520 K. Detailed data are
lacking.

W O
40 119 (WOi.m)

Crystal structure Monoclinic; space group, P2i/m; [8].

Z = 4; a = 7.354 ±0.005 A; 6 =
7.569 ±0.005 A; c = 3.854 ±0.005
A; /3=90.6°. Detailed properties
not known.

wo 8

Crystal structure and Range 77-233 K: Monoclinic; a = WO 3 is the only oxide which shows [1, 5, 7, 12,

x-ray studies. 5.27 A; 6 = 5.16 A; c = 7.67 A; 0 = a wide variety of crystallographic 19-22, 26,
91.72°. This phase can be stabil- transitions in the easily attain- 27-29, 33-
ized at room temperature by able ranges of temperatures; 41].
quenching a solid solution of 2 % many of the transitions are of
Nb 2 C>6 in W0
8 from 1500-1660 K. first order. Surprisingly, the tetra-
Monoclinic to triclinic transition gonal—»cubic transition has not
at 251 K (heating); hysteresis been noticed either in the pure or
~15°. The stabilized solid solu- doped or nonstoichiometric sam-
tion transforms to a tetragonal ples; neither it has been possible
form at ~1010 K; transition re- to stabilize the cubic phase at
versible if the sample is heated any temperature. The effect of
below 1015 K and if heated to nonstoichiometry is pronounced
~1170 K, tetragonal phase in the case of low -temperature
transforms irreversibly to an transitions. Data is lacking for
orthorhombic modification. the high -temperature transitions
Range 233-290 K: Triclinic; a = 7.30 and also the effect of pressure on
A; 6 = 7.52 A; c = 7.69 A; a = 88.83°; the transitions.
0=90.92°; 7=90.93°. Triclinic
phase not encountered in the
solid solutions of 3 with WO
Nb 20 s at any temperature. Tri-
clinic to monoclinic transition at
~293-303 K (heating); hystere-
sis,~3-13°. Reverse transition
(mono.—»tric.) noted on grinding
the specimen at room tempera-
ture. Removal of oxygen from the
lattice of pure WO* reduces the
T t of the two low -temperature
transitions.
Range 290-583 K: Monoclinic;
space group, P2i/n; Z=8 ; a =
7.306 A; 6 = 7.540 ±
± 0.001
0.001 A; c = 7.692 ± 0.001 A;

119
 Tungsten oxides —Continued

Oxide and description Data Remarks and inferences References

of the study

/3=90.881 ±0.005°. Solid solu-

tion with Nb 2 06 retains the
monoclinic structure but slightly
changes the lattice parameters.
Monoclinic to orthorhombic
transition at ~600 K (heating);
thermal hysteresis ~40-50°.
Range 580-1010 K: Orthorhombic;
the lattice parameters remain
the same as in the monoclinic
phase (except for the effect of
thermal expansion) and /3 ap-
proaches 90° at « T According t.

to Rosen et al. [35], the b param-

eter shows an anomaly at T in t

WO 3 The orthorhombic form can

.

be stabilized at room tempera-

ture by heating the 2 Nb 2 06 %
solid solution to 1170 and K
rapid cooling. Orthorhombic to
tetragonal transition at ~1010 K;
hysteresis ~ 10 The solid solu-
°.

tion (of 2 % Nb 06 transforms to

2 )

tetragonal form at a lower tem-

perature.
Range 1010-1700 K: Tetragonal;
space group, P4/nmm;
Z=2 ; a = 5.25 A; c = 3.91 A. A
transition takes place at ~1170
K in WOs but x-ray studies
do not indicate any change
in the crystalsymmetry. Roth
and Waring [26] point out that
it is possible that the tetra-
gonal unit cell has a doubled c
axisbelow 1170 K and only
above this temperature does the
powder pattern yields the correct
unit Melting point of
cell. 3 WO
is 1700 K
and it melts under its
own equilibrium oxygen partial
pressure [12, 41, 47].

Magnetic properties. Diamagnetic in the range 77-300 K; Both stoichiometric and nonstoi- [18, 42].

X m (=300 K) = -21.0±1.7X chiometric samples exhibit simi-

10 _a Below 77 K, oxygen defi-
. lar magnetic behavior.
cient WO* shows decrease in xm
eventually switching to a feeble
paramagnetism (xm = 10 X 10 “ #
cgs u.) at 1.28 A.

120
 Tungsten oxides —Continued

Oxide and description Data Remarks and inferences References

of the study

Electrical properties. Semiconductor behavior; p (200 K) The electrical properties show com- [18, 23-25,
~10 3
12cm; p (400 K)~5 cm;
!2 plex behavior; the actual values 31, 48].
a (300 K) 0.5 mV/°C; pH of p, a and ph vary from sample
(400 K)~10 cm 2 /V s. Discon- to sample and depend on the
tinuities in p, a and ph are en- method of preparation, stoichiom-
countered near the transition etry etc. However, the qualitative
temperatures of the various features are reproducible and p-T
phases encountered with the behavior provides a good tool for
associated hysteresis. In the indicating the phase transitions.
range 400-900 K, p is very small Electrical data on the doped WO3
( 0. 1-0.5 Ocm) and shows (where various high- and low-
slight increase with rise in tem- temperature phases have been
perature (quasi-metallic be- stabilized) are lacking.
havior). Sawada [31] has reported
a resistivity anomaly at ~1500 K
in WO 3 ; this may correspond to a
change in the mechanism of con-
duction or to a new modification.
Details are not known. The
mechanism of electrical conduc-
tion in the range 100-500 K is
interpreted in terms of various
polaron theories.

Optical and dielectric Absorption edge is at 2.7 eV. Re- Accurate dielectric constant data [18, 28, 30,
properties. moval of oxygen from the lattice and the study of ferroelectric and 38, 49, 50].
causes an increase in absorption antiferroelectric properties could
at all wave lengths. Absorption not be carried out because of the
edge shows an anomalous shift at high conductivity effects in pure
the ~250 K transition. In the W0 3 .

range 270-970 K, absorption

edge shows a red shift (~10 -4
eV/K); near 1010 transition, aK
sudden red shift is noted for a
polarized light. The static dielec-
tricconstant at room tempera-
ture is ~10 3 -10 4 (at 1 MHz) and
decreases to ~10 2 [50] at -~250
K. According to Matthias and
Wood [28, 30], the low-tempera-
ture monoclinic phase (in the
range 77-233 K) is ferroelectric.
On the basis of structural studies,
Kehl et al. [38] concluded that
the high -temperature tetragonal
may be antiferroelectric. Levine
et al. [32] reported that WO 3 con-
taining 2-4% TajOs exhibits
ferroelectricity at room tempera-
ture whereas Roth and Waring
[26] do not find this behavior in
the 2% NI^Ob doped sample.

121
 Tungsten oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

DTA studies. All the crystallographic transitions The nature of the high -temperature [18, 31].
are associated with DTA anoma- transitions is not known in de-
lies; in addition, transitions are tail; the transitions seem to be
also indicated at ~1170 and first order.
~1500 K (fig. III.l). Hysteresis
is noted in all cases. AH (cal/
mol): Monocl. (low -temperature)
—triclinic, 39; tricl.—»monocl., 20;
monocl. —»orthorh., 330; orthorh.
—tetra., 450; tetra.—»tetra., 280;
1500 K transition, 120. Removal
of oxygen from the lattice de-
creases T t as well as the AH of
the two low-temperature transi-
tions. Data are not available for
other transitions.

References [26] Roth, R. S., and Waring, J. L., J. Res. Nat. Bur. Stand.
(U.S.), 70A (Phys. and Chem.), No. 4, 281-303 (July-
Aug. 1966).
[1] Hagg, G., and Magneli, A., Arkiv Kemi Mineral. Geol. [27] Foex, M., Compt. Rend. (Paris) 220, 917 (1945); 228,
19A, No. 2 (1944). 1335 (1949).
[2] Magneli, A., Arkiv Kemi Mineral. Geol. 24A, No. 2 [28] Matthias, B. T., and Wood, E. A., Phys. Rev. 84, 1255
(1946). (1951).
[3] H., Braekken, Z. Krist. 78, 484 (1931). [29] Hirakawa, K., J. Phys. Soc. Japan 7, 331 (1952).
[4] Magneli, A., Arkiv Kemi 1, 223 (1949); 1, 513 (1950). [30] Matthias, B. T., Phys. Rev. 76, 430 (1949).
[5] Magneli, A., Andersson, G., Blomberg, B., and Kihlborg, [31] Sawada, S., J. Phys. Soc. Japan 11, 1237 (1956).
L., Anal. Chem. 24, 1998 (1952). [32] Levine, S., Corwin, R., and Blood, H. L., Bull. Am. Phys.
[6] Glemser, O., and Sauer, H., Z. anorg. allgem. Chem. Soc. Ser. II, 1, 255 (1956).
252, 144 (1943). [33] Wyart, J., and Foex, M., Compt. Rend. (Paris) 232,
[7] Phillips, B., and Chang, L. L. Y., Trans. AIME
230, 2459 (1951).
1203 (1964). [34] Ueda, R., and Ichinokawa, T., Phys. Rev. 82, 563 (1951).
[8] Gebart, E., and Ackermann, R. J., Inorg. Chem. 5, 136 [35] Rosen, C., Banks, E., and Post, B., Acta Cryst. 9, 475
(1966). (1956).
[9] Neuberger, M. C., Z. Krist. 85, 232 (1933). [36] Perri, J. A., Banks, E., and Post, B., J. Appl. Phys. 28,
[10] Hagg, G., and Schonberg, N., Acta Cryst. 7, 351 (1954). 1272 (1957).
St. Pierre, G. R., Ebinara, W. T., Pool, M. J., and
[11]
[37] Gado, P., Magy Fiz. Folyoirat 10, 347 (1962).
AIME
Speiser, R., Trans. 224, 259 (1962).
[38] Kehl, W. L., Hay, R. G., and Wahl, D., J. Appl. Phys.
[12] Chang, L. L. Y., and Phillips, B., J. Am. Ceram. Soc.
23, 212 (1952).
52, 527 (1969).
Rogers, D. B., Shannon, R. D., Sleight, A. W., and [39] Sawada, S., Phys. Rev. 91, 1010 (1953).
[13]
Gillson, J. L., Inorg. Chem. 8, 841 (1969). [40] Fiegel, L. J., Mohanty, G. P., and Healy, H., J. Chem.
[14] Israelsson, M., and Kihlborg, L., Mat. Res. Bull. 5, 19 and Engg. Data 9, 365 (1964).
(1970). [41] Chang, L. L. Y., Schroger, M. G., and Phillips, B.,
[15] Chang, L. L. Y., Scroger, M. G., and Phillips, B., J. J. Am. Ceram. Soc. 49, 385 (1966).
Less-Comm. Metals 12, 51 (1967). [42] Sienko, M. J., and Banerjee, B., J. Am. Chem. Soc. 83,
[16] Nygren, M. t and Israelsson, M., Mat. Res. Bull. 4, 881 4149 (1961).
(1969). [43] Sienko, M. J., in Non-stoichiometric Compounds, Adv.
[17] Magn61i, A., Nature (Lond.) 165, 356 (1950). Chem. Ser. 39, 224 (1963).
[18] Berak, J. M., and Sienko, M. J., J. Solid State Chem. 2, [44] Wadsley, A. D., in Non-stoichiometric Compounds, Ed.
109 (1970). L. Mandelcorn, (Academic Press, New York, 1964).
[19 Andersson, G., Acta Chem. Scand. 7, 154 (1953). Dickens, P. G., and Whittingham, M. S., Quart. Rev.
[45]
20 Tanisaki, S., J. Phys. Soc. Japan 15, 573 (1960).
(Lond.) 22, 30 (1968).
21 Loopstra, B. 0., and Boldrini, P., Acta Cryst. 21, 158
[46] Rao, C. N. R., and Subba Rao, G. V., Phys. stat. Solidi
(1966).
(a) 1, 597 (1970).
[22] Loopstra, B. O., and Rietveld, H. M., Acta Cryst. 25B,
1420 (1969). [47] Levin, E. M., J. Am. Ceram. Soc. 48, 491 (1965).
[23] Tanisaki, S., J. Phys. Soc. Japan 15, 566 (1960). [48] Sawada, S., and Danielson, G. C., Phys. Rev. 113, 803
[24] Crowder, B. L., and Sienko, M. J., J. Chem. Phys. 38, (1959).
1576 (1963). [49] Iwai, T., J. Phys. Soc. Japan 15, 1596 (1960).
[25] Crowder, B. L., and Sienko, M. J., Inorg. Chem. 4, 73 [50] Hirakawa, K., and Ueda, I., Mem. Fac. Sci. Kyusyu
(1965). Univ. Bl, 112 (1954).

122
 III. 5. Rhenium Oxides The simple cubic ReOa is important
structure of
from the view point of understanding the structures
In the Re-0 system, ReQ 2, ReOs, and Re 2 t)7 are of perovskites (see fig. III.2) [13]. Goodenough [IS-
the oxides that are well characterized and examined IS] has explained the metallic behavior of ReOa by
in detail. A Re 2 Q 6 has been reported by
tetragonal constructing a one-electron energy band diagram.
Trabalat et The di- and sesquioxides are
al. [1]. Recent band structure calculations on ReOa have
stable ionic compounds whereas Re 2 C>7 is mostly proved that the essential features of the Good-
covalent and has a low melting point (~490 K). enough’s model are correct [16, 17].
Re0 2 is polymorphous and when synthesized below Re 2 C>7 is orthorhombic at room temperature [18-
570 K, the structural modification (a) is that of 20]. It is yellow in color and is supposed to have a

monoclinic Mo0 2 type [2, 3]; above ~570 K, this polymeric structure in the solid state; in the liquid
oxide transforms irreversibly to an orthorhombic and vapor states, monomeric species have been iden-
form (/3) with a structure characterized by zig-zag tified [19, 21]. Infrared and Raman spectra of this

chains of Re atoms propagating along the c axis material have been studied in detail [21, 22] but
of the unit cell. It is also possible to directly synthe- other properties are not known.
size the high temperature form [2, 3] and the ma-
terial is stable in the range 570 to 1320 K. Magnetic
susceptibility studies [4] indicate that both the forms
of Re0 2 are Pauli paramagnetic. Resistivity data
indicate that /3-Re0 2 is metallic [3] and most prob-
ably the low temperature modification also is metal-
lic. Monoclinic Re0 2 forms rutile type solid solu-
tions with V0 2 and Mo0 2 [5].

Re 2 05 is prepared by precipitation from aqueous

solutions and has a tetragonal structure. It ap-
[1]

pears to be stable up to 470 K, but decomposes to

Re 2 C>7 and Re0 2 in vacuum at ^ 520 K. Detailed
properties are not known at present.
Re (>3 is cubic and no phase transformations are
known in the range 1 to 300 K [2, 6-8]; the material
disproportionates to Re0 2 and Re 2 0? in the neighbor-
hood of 670 K. Re0 3 has a red metallic luster and
magnetic susceptibility [6, 8], electrical [6, 8], opti-
cal [9], NMR[10], magneto-thermal oscillation [II], Figure XII.2. Cubic ReOa structure.
and de Hass-van Alphen effect [12] studies confirm Each metal atom is an octahedran of oxygen atoms. This
at the center of
structure is which is obtained by
closely related to the perovskite structure
the typical metallic behavior of ReOs. insertion of a large cation in the center of the cube shown.

Rhenium oxides

Oxide and description Data Remarks and inferences References

of the study

ReOj

Crystal structure and Low -temperature for (T <570 K): The low temperature form is [2, 23].

x-ray studies. Monoclinic: space group, P2i/c; closely related to rutile structure.
Z = 4; a =5.562 A; 6=4.838 A;
c— 5.561 A; /3 = 120.87°. High
temperature form (T>570 K):
orthorhombic; space group,
Pbcn; Z = 4; a =4.810 A; 6 =
5.643 A; c = 4.601 A.

123
 Rhenium oxides —Continued

Oxide and description Data Remarks and inferences References

of the study

Electrical properties. /S-ReOj: Metallic behavior is indicated; data [3].

P (4.2 K)«1.2X10“ 6
ficm; for a-Re 02 are not available.
p (300 K) » 1.0 X 10 -4 ficm.

RejOj

Crystal structure. Tetragonal; Z — 4; a = 5.80 A; c = The substance has been obtained [1].

12.87 A. from aqueous solutions; exact

purity and characterization
doubtful; other properties not
known.
ReOs

Crystal structure. Cubic, space group, Pm3m; Z = 1; This simple cubic structure is [8].

a = 3.7474 ±0.0003 A. closely related to the perovskite

structure since the latter is ob-
tained by insertion of a large
cation in the center of the cube
of the ReOa structure (fig. 1).

Magnetic and electrical Xm (300 K) =74.5X10 -6 emu. Weak paramagnetism is indicated [6, 8].
properties. p (100 K)«6X10~ 7
item; contrary to the earlier data [6].

p (300 K)«lXl0" 6
item.

Optical and NMR studies. Absolute reflection measurements The data confirm the metallic be- [9, 10].
on ReOa give plasma edge at 2.1 havior of ReOs in which the con-
eV; interband transitions domi- duction bands are predominantly
nate the optical spectrum above d like.

the plasma edge, m * (calc.)~

0.86 m 0 k - -(0.25 ±0.02)%.
.

Band structure of ReO». LCAO, APW, and Slater-Kostiner
methods give a band structure
in essential agreement with the
band diagram proposed by Good-
enough [13-15] and in reasonable
agreement with the optical and
Fermi surface data. The conduc-
tion bands are predominantly d
like.
Honig et al. [17] point out that the [16, 17].
band structure scheme will also be
useful in the characterization of
the band structure for perovskites
which have a closely related
structure.

RejO? T = 300 K; Orthorhombic; space The structure consists of strongly [20].

group P2i2i2i; Z = 8; a = 12.508 distorted ReOe octahedra and
A; b = 15.196 A; c = 5.448 A. fairly regular ReO« tetrahedra
which are connected through
corners to form polymeric double
layers in the ac plane. The
double layers have only van der
Waals contacts to neighboring
ones. RejO? is one of the few
known examples where metal
atoms of the same oxidation state
occur with the coordination num-
bers 4 and 6 same struc-
in the
ture. In its structure and bond

124
 Rhenium oxides — Continued

Oxide and description Data Remarks and inferences References

of the study

properties, Re207 represents an

intermediate between the poly-
meric oxides MoOg and WOg and
the more covalently bonded OsO*,
which forms a molecular
structure.

IR of Re 207 . Several bands in the region 400- [21].

1010 cm -1 and assigned
are noted
to various stretching and bending
vibrations.

References III. 6. Osmium Oxides

The dioxide, 0s02 and the tetroxide, Os 04 have ,

[1] Tribalat, S., Dalafosse, D., and Piolet, C., Compt. Rend. been studied exhaustively. Os0 2 forms lustrous yel-
(Paris) 261, 1008 (1965). lowish brown crystals which decompose at T>770
[2] Magneli, A., Acta Cryst. 9, 1038 (1956); Acta Chem.
Scand. 11, 28 (1957). K. Os0 4 is a covalent solid and soluble in nonpolar
[3] Rogers, D. B., Shannon, R. D., Sleight, A. W., and solvents; the crystals are colorless with a low melting
Gillson, J. L., Inorg. Chem. 8, 841 (1969).
point (~310 K) and high vapor pressure.
[4] Gibart, P., Bull. Soc. Chim. France 444 (1967).
[5] Marinder, B.-O., and Magneli, A., Acta Chem. Scand. Os0 2 has a tetragonal rutile structure [1-4] and
11, 1635 (1957). exhibits slight temperature dependent magnetic sus-
[6] Ferretti, A., Rogers, D. B., and Goodenough, J. B., J.
Phys. Chem. Solids 26, 2007 (1965). ceptibility [3]. It has a very low room -temperature
[7| Gukova, Yu. Ya., and Emolaev, M. I., Russian J. Inorg. resistivity, positive temperature coefficient of re-
Chem. (English Transl.) 13, 777 (1968).
sistivity and low negative Seebeck coefficient [1, 3]
[8] Quinn, R. K., and Neiswander, P. G., Mat. Res. Bull.
5, 329 (1970). indicative of metallic behavior. No phase transitions
[9] Narath, A., and Barham, D. C., Phys. Rev. 176, 479 are known in Os0 2 in the temperature range 77 to
(1968).
[10] Feinleib, J., Scouler, W. J., and Ferretti, A., Phys. Rev. 500 K.
165, 765 (1968). Thiele and Woditsch [2] report two forms (black
[11] Graebnev, J. E., and Greiner, E. S., Phys. Rev. 185, 992
(1969).
and brown) of Os0 2 both have tetragonal sym-
;

[12] Marcus, S. M., Phys. Letters 27A, 584 (1968). metry, but the lattice parameters and x values differ
[13] Rao, C. N. R., and Subba Rao, G. V., Phys. Stat. Solidi significantly. The lattice parameters of the brown
(a) 1, 597 (1970).
[14] Goodenough, J. B., J. Appl. Phys. 37, 1415 (1966). form are identical with the data reported by other
[15] Goodenough, J. B., Czech. J. Phys. 17B, 304 (1967). workers on single crystal Os0 2 [3, 4]. It is possible
[16] Mattheis, L. F., Phys. Rev. 181, 987 (1969). that the black form of Os0 2 reported by Thiele
[17] Honig, J. M., Dimmock, J. O., and Kleiner, W. H.,
J. Chem. Phys. 50, 5232 (1969).
and Woditsche is slightly nonstoichiometric or im-
[18] ^ ilhelmi, K.-A., Acta Chem. Scand. 8, 693 (1954). pure.
[19] Krebs, B., and Muller, A., Z. Naturforsch. 23b, 415
OsO* room temperature is a solid and has a
at
(1968).
[20] Krebs, B., Muller, A., and Beyer, H. H., Inorg. Chem. monoclinic symmetry [5]. It is a covalent compound
8, 436 (1969). (mp, 310 K; bp, 374 K) and is soluble in polar
[21] Ulbricht, K., and Kriegsmann, H., Z. Chem. 7, 244
(1967). solvents. The molecule is tetrahedral in vapor state.
[22] Beattie, I. R., and Ozin, G. A., J. Chem. Soc. (Lond.) Infrared and Raman studies of 0 s 04 is nonaqueous
A2615 (1969).
solvents have been carried out by various workers
[23] Magnlli, A., Andersson, G., Blomberg, B., and Kihlborg,
L., Anal. Chem. 24, 1998 (1952). [6, 7]; other physical properties are not known.

125
 ± -

Osmium oxides

Oxide and description Data Remarks and inferences References

of the study

Os0 2

Crystal structure. T = 300 K: Tetragonal; space Recent single crystal study; the [4).

group, P4 2 /mnm; Z = 2; a = values are in agreement with the

4.5000 ±0.0003 A; c = 3.1830 ± data of earlier workers.
0.0009 A.

Magnetic properties. Xii (X10 -6 emu) is 311, 220, and The values of Thiele and Woditsch [2].

204 at 90, 195, and 291 K re- [2] have been corrected for the
spectively. Greedon et al. [1] diamagnetic contribution. These
report a temperature independent authors argue for the presence of
susceptibility (77-500 K) ofxM« a magnetic ground state for
120 X10 -6 emu. Os 4+ in Os0 2 .

Electrical properties. p (4.2K) =3.2 X10" 7 ficm; p (300 The data indicate the typical metal- [1. 3].

K) =6.0X10 -5 (km. a (~300 K) lic nature of Os0 2 ; estimated

~1 pV/K (negative); no Hall carrier concentrations are ~10 22-
voltage could be measured. 10 23 /cm 3p, .
~1.5-15
(calc.)
cm 2 /V s; m* «8 mo. The model
proposed by Goodenough [8] and
Rogers et al. [3] seem to explain
the observed behavior.

O 8O 4

Crystal structure T = 300 K: Monoclinic; space The structure can be described as [5].

group, C2/c; Z = 4;a =9.379 cubic closest packing of oxygen

0.005 A; b =4.515 ±0.002 A; c = atoms, with osmium in tetra-
8.632 ±0.003 A; /3 = 116±0.05°. hedral holes. The intermolecular
0-0 distances exceed 2.98 A and
are consistent with weak inter
molecular forces indicated by the
high vapor pressure and low
melting point.

Infrared studies on solid 0 s 04 . Bands at 965 and 959.5 cm -1 are IR of Os 04 in CCh solution and [
6, 71.

noted. Raman studies are also con-

sistent with the behavior in the
solid state.

References [4] Boman, C.-E., Acta Chem. Scand. 24, 123 (1970).
[5] Ueki, T., Zalkin, A., and Templeton, D. H., Acta Cryst.
Greedon, Willson, D. B., and Haas, T. E., Inorg. 19, 157 (1965).
[1] J. E.,
Chem. 2461 (1968).
7, [6] Krebs, B., and MuUer, A., Z. Chem. 7, 243 (1967).
[2] Thiele, G., and Woditsch, P., J. Less-Comm. Metals 17, [7] McDowell, R. S., and Goldblatt, M., Inorg. Chem. 10,
459 (1969). -625 (1971) and references cited therein.
[3] Rogers, D. B., Shannon, R. D., Sleight, A. W., and [8] Goodenough, J. B., Bull. Soc. Chim. France 4, 1200
Gillson, J. L., Inorg. Chem. 8, 841 (1969). (1965).

126
 III. 7. Iridium Oxides firm the metallic nature of the material; as pointed
out by Butler and Giilson [8], the simple one-band
The phase study of the Ir-0 system by Cordfunke model of Rogers and co-workers [7] may not explain
and Meyer [1] and McDaniel and Schneider [2, 3] the observed behavior. Ryden et al. [6] have found
indicate that Ir0 2 is the only condensed oxide phase that electron-phonon and electron-electron inter-
stable in an air environment. Ir0 2 has a tetragonal band scattering mechanism accounts for the ob-
rutile structure and no phase transformations are served temperature dependence of resistivity.
known in the range 4.2 to 1000 K [4-8]. Ir0 2 forms complete solid solutions with Ru0 2

Magnetic properties of Ir0 2 have not yet been and to a limited extent with Ti0 2 and Sn0 2 [2, 3];
investigated. Electrical resistivity studies [5-8] con- these have the rutile structure.

Iridium oxides

Oxide and description Data Remarks and inferences

of the study

Ir0 2

Crystal structure and T = 298 K: Tetragonal; space TEC is positive in Ir0 2 ; anisotropy
electrical properties. group, P4 2 /mnm; Z = 2; a = is evident. The compound is

4.4980 ±0.0003 A; c = 3.1543± metallic and most probably Pauli

0.0002 A. TEC (X10“ /°C): paramagnetic.
||
e
: 1.7; K)~1.5X
||“: 3.8. p (4.2
10~ 8 Ocm; p (298 K)~3.0X10- 5

Ocm. f?H (77 K) ~ — 3.12; juh

( 77 K) =130 cm /V s; R H (300
2

K) ~ -2.60; mh (300 K)=7.5

cm*/V s.

References III. 8. Platinum Oxides

[1] Cordfunke, E. H. P., and Meyer, G., Rec. Trav. Chim.

81, 495 (1962); 81, 670 (1962).
[2] McDaniel, C. L., and Schneider, S. J., J. Res. Nat. Bur. Although the literature on the Pt-0 system is
Stand. (U.S.), 71A (Phys. and Chem.), No. 2, 119-123 extensive due to the catalytic and electrochemical
(Mar.-Apr. 1967).
[3] McDaniel, C. L., and Schneider, S. J., J. Res. Nat. Bur. applications of the platinum oxides, many of them
Stand. (U.S.), 73A (Phys. and Chem.), No. 2, 213-219 are poorly characterized. Recent careful study by
(Mar.-Apr. 1969).
[4] Hazony, Y\, and Perkins, H. K., J. Appl. Phys. 41, 5130 Muller and Roy [1]has revealed the existence of
(1970). a-Pt0 2 /3-Pt0 2
, , and Pt 3 0 4 as the stable oxides in
[5] Ryden, W. D., Lawson, A. W., and Sartain, C. C., Phys.
Letters 26A, 209 (1968). the Pt-0 system. Contrary to earlier reports [2-6],
[6] Ryden, W. D., Lawson, A. W., and Sartain, C. C., Phys. the existence of PtO and Pt 3 0 3 are doubtful.
Rev. Bl, 1494 (1970).
[7] Rogers, D. B., Shannon, R. D., Sleight, A. W., and Pt 3 0 4 is cubic [1]. a-Pt0 2 has a chain structure
Giilson, J. L., Inorg. Chem. 8, 841 (1969). and is hexagonal; /3-Pt0 2 is orthorhombic and has a
[8] Butler, S. R., and Giilson, J. L., Mat. Res. Bull. 6, 81
(1971). distorted rutile structure [1, 7, 8], a-Pt0 2 transforms

127
to 0-form eitherby heating to 970 K at 3 kbar
KCIO3 or by heating to
pressure in the presence of
1370 K at 65 kbar pressure [7]. DTA, TGA, and
high temperature x-ray studies show that 0 -PtO 2
decomposes to the platinum metal and oxygen at
~860 to 920 K [7, 8].
jS-PtCL appears to be a semiconductor
physical properties of a-Pt 02 and Pta 04 are not
known. Muller and Roy [10] have found that solid
solutions of the form Cui_ x Pt x O possessing the
tetragonal structure can easily be formed. The ex-
trapolated lattice parameters for the hypothetical
TtO’ do not quite agree with the values reported by
[7, 9]. The Moore and Pauling [2].

Platinum oxides

Oxide and description Data 6 Remarks and inferences References

of the study

Pt 0«
3

Crystal structure. Cubic; space group, Pm3m; Z = 2; — [1].

a = 5.585 A .

a-PtCh

Crystal structure. Hexagonal; space group, C6/mmm; Samples are poorly crystallized; [1].

Z = 1; a =3.10 A; c = 4.29-4.41 A. Pt-O-O-Pt-O-O chain structure

in the c direction.

0-PtO 2

Crystal structure and
electrical resistivity.
Orthorhombic; space group, Pnnm; Distortion from the rutile struc- [1. 7, 9].
Z = 2; a =4.487 ±0.0005 A; 6 = ture is small; semiconductor be-
4.536±0.0005 A; c = 3.137± havior (in the range 4.2-300 K).
0.0005 A. p (300 K) *10 ficm;
£0=0.2 eV. Decomposes in air at
~860-920 K.

References III. 9. Gold Oxides

Although Shishakov [1] forma-
earlier reported the

Muller, O., and Roy, R., J. Less-Common Metals 16,

tion of hexagonal AU 3 O 2 on the surface of heated
[1]
129 (1968). gold metal at 770 K, recent studies by Muller and
[2]
[10] Moore, W. J., Jr. and Pauling, L., J. Am. Chem. Soc. Roy [2] indicate AU 2 O 3 to be the only crystalline
63, 1392 (1941).
[3] Suzuki, T., Z. Naturforsch. 12a, 497 (1957).
oxide phase in the Au-0 system. Attempted prepara-
[4] Every, R. L„ J. Electrochem. Soc. 112, 524 (1965). tion of Au 0 2 has not been successful [3].
[5] Fryburg, G. C., J. Chem. Phys. 42, 4051 (1965). Au 0
2 3 is cubic (a = 4.832 A; space group, P43m)
[6] Shishakov, N. A., Andreeva, V. V., and Andruschenko,
N. K., Stroenie i Mekhanism Obrazovaniya Okisnykh [2, 4], The physical properties are not known in
Plenok na Metallakh, Akad. Nauk. SSSR, Moscow, detail. The infrared band's of AU O have
2 3 been re-
1959, Chap. 6. ported in the range 515-660 cm -1 .

[7] Shannon, R. D., Solid State Commun. 6, 139 (1968);

7, 257 (1969).
Schneider, S. and McDaniel, C.
References
[8] J., L., J. Am. Ceram.
Soc. 52, 519 (1969). [1] Shishakov, N. A., Kristallografiya 2, 686 (1957).
Rogers, D. B., Shannon, R. D., Sleight, A. W., and [2] Muller, O., and Roy, R., Am. Ceram. Soc. Bull. 46, 881
[9]
(1967).
Gillson, J. L., Inorg. Chem. 8, 841 (1969).
[3] Suzuki, T., J. Phys. Soc. Japan 15, 2018 (1960).
Muller, O., and Roy, R., J. Less-Common Metals 19, Schwarzmann,
[4] E., and Gramann, G., Z. Naturforsch.
209 (1969). 25b, 1308 (1970).

128
 III. 10. Mercury Oxides with zig-zag -Hg-O-Hg- chains (Hg-O = 2.03 A);
there is only weak bonding between the chains.
HgO is the well known oxide in the Hg-0 system
Laruelle [5] has described a rhombohedral form of
[1-3]. reported the formation of two
Vannerberg [4]
HgO obtained by precipitation from aqueous solu-
different forms (a-and /3-) of the mercury peroxide,
tions; it transforms irreversibly to the orthorhombic
Hg 02 a-Hg 02 has a rhombohedral structure whereas
;

orthorhombic.
form at ~470 K and at this temperature, the trans-
/3-form is
formation is a slow process. HgO is diamagnetic
HgO: HgO exists in the red and yellow forms but [7] and the diamagnetic susceptibility is almost the

these are not polymorphs; they differ in the particle same for both the yellow and red forms. HgO de-
size and give identical x-ray patterns [2], The stable composes at high temperatures to the metal; other
form is orthorhombic [1-3, 5, 6] and has a structure properties are not known.

Mercury oxides

Oxide and description Data Remarks and inferences References

of the study

HgO

Crystal structure and Orthorhombic; space group, Pnma; HgO has a zig-zag structure associ- [1-3,5].
properties. Z = 4; a =6.6129 ±0.0009 A; 6 = ated with considerable covalency
5.5208 ±0.0007 A; c = 3.5219 ± in the Hg-0 bond. Detailed
0.0005 A. A rhombohedral form properties are not known.
can be precipitated from solution
and it transforms irreversibly to
the orthorhombic modification at
~470 K; detailed structure not
known. The red and yellow colors
of HgO seem to be due to the
particle size effect. HgO is dia-
magnetic; x (red form) =
— 0.221 X10 -6 emu/g; x (yellow
form) = — 0.2 16 X10 -6 emu/g.
X increases in the range 298-573
K. x-T plot shows peaks at 323
(red form) and 387 K (yellow
form); the reason is not clear.

Infrared and Raman Low frequency band is at 67 cm -1 ; [8, 9].

spectral studies. Raman bands at 331 and 550

cm -1 The data are interpreted
.

in terms of the chain structure of

HgO.

HgO 2

Crystal structure. a-form: rhombohedral; a =4.74 A; [4].

a ~90°. /3-from: orthorhombic;

space group, Pbca; Z = 4; a=
6.080 A; 6 = 6.010 A; c =4.800 A.
Detailed data on the properties
are lacking.

Compt. Rend. (Paris) 241, 802 (1955).

Laruelle, P.,
References [5]
[6] Rooymans, C. J. M., Philips Res. Rep. Suppl. 1, 1 (1968).
[7] Mikhail, H., Hanafy, Z., and Salem, T. M., J. Chem.
[1] Zachariasen, W., Z. Physik. Chem. 128, 421 (1927). Phys. 35, 1185 (1961).
[2] Roth, W. L., Acta Cryst. 9, 277 (1956). [8] Edmond, D., and Armand, H., J. Chim. Phys. Physico-
[3] Aurivillius, K., Acta Chem. Scand. 10, 852 (1956); 18, chim. Biol. 65, 1030 (1968).
1305 (1964). [9] Cooney, R. P. J., and Hall, J. R., Austr. J. Chem. 22,
[4] Vennerberg, N. G., Arkiv for Kemi 13, 515 (1959). 331 (1969).

129
 IV. Some Recent Studies Recent single crystal studies on V 3Oi 3 [7] confirm a negative
volume change ( — 0.5%), a positive enthalpy change (-f-400
cal/mol) and a semiconductor-metal transition at 150 K.
Titanium Oxides There is no change in the crystal system.
Marezio et al. [8] have studied some structural aspects of
Rao and co-workers [1] have recently found that pressure Vi_* Cr* O 2 in detail.
has no effect on the TuOj transition; this is consistent with
the band-crossing mechanism wherein the a T and e T bands References
cross as the c/a ratio increases.
The very recent study of Marezio et al. [2] published in [1] Honig, J. M., Chandrasekhar, G. V., and Sinha, A. P. B.,
1973 on the three phases of Ti 4 C>7 has clearly established the Phys. Rev. Letts. 32, 13 (1974).
structural aspects of the transitions. The room temperature [2] Caruthers, E., Kleinman, L., and Zhang, H. I., Phys.
)hase is metallic with an average valence of 3.5 for Ti. In the Rev. B7, 3753 (1973).
(ow-temperature insulating nonmagnetic state, there is a [3] Goodenough, J. B., Phys. Rev. B5, 2764 (1972).
separation into strings of Ti 3+ and Ti 4+ with the 3+ sites [4] Honig, J. M., Van Zandt, L. L., Board, R. D., and Weaver,
forming metal-metal bonds. In the intermediate phase, there H. E., Phys. Rev. B6, 1323 (1972).
is no evidence for charge separation or long range order of [5] Kachi, S., Kosuge, K., and Okinaka, H., J. Solid State
bonds. Chem. 6, 258 (1973).
[1] The atomic vacancies in TiO have been discussed by Good-
[6] McWhan, D. B., Remeika, J. P., Maita, J. P., Kinaka,
enough
[2] [3]. H. O., Kosuge, K., and Kachi, S., Phys. Rev. B7, 326
ESR studies on Ti 3 06 have been reported by Schlenker et (1973).
[3]
al. [5]. [7] Saeki, J., Kimizuka, N., Ishii, M., Kawada, I., Nakamo,
[4]
M., Ichinose, A., and Nakahira, M., J. Cryst. Growth
18, 101 (1973).
[5]
References Marezio, M., McWhan, D. B., Remeika, J. P., and
[8]

Viswanathan, B., Devi, S. U., and Rao, C. N. R., Pramana Dernier, D. P., Phys. Rev. B5, 2541 (1972).
1, 48 (1973). [9] Tewari, S., Solid State Commun. 11, 1139 (1972).
Marezio, M., et al., J. Solid State Chem. 6, 213 (1973);
Phys. Rev. Letters 28, 1390 (1973). Nickel Oxides
Goodenough, J. B., Phys. Rev. 135, 2764 (1972). Recent measurements [1] on highly pure NiO crystals gave
Honig, J. M., Wahnsiedler, W. E., and Dimmock, J. O.,
at 300 K; m
=20-50 cm2 / Vs * =
the hole mobility, /u<j/ 1.5m 0 ;
J. Solid State Chem. 5, 452 (1972). =
and <*f* 1.6.
Schlenker, C., Buder, R., Schlenker, M., Houlihan, J. F.,
and Mulay, L. N., Phys. Stat. Solidii (b) 54, 247
(1972).
Reference
[1] Spear, W. E., and Tannhanser, D. S., Phys. Rev. B7,
Vanadium Oxides 831 (1973).

Recent studies of Honig and co-workers [1] on Vo. 99 Cro .01 Niobium Oxides
O in the 200 to 900 K range indicate that the electrical
1.6
anomaly is extrinsic and is caused by the coexistence of phases Recently, measurements of electrical properties of NbO in
over a wide temperature range. If this be the case, much of high magnetic fields have been reported by Honig et al. [1]
the earlier arguments based on the I-M transition will be who have interpreted the results in terms of a nearly free
invalid. electron model in which holes and electrons contribute jointly
Caruthers et al. [2] have recently calculated the band struc- to conduction process; magnetoresistance anomalies have also
ture of VO 2. been examined by these workers.
The influence of atomic vacancies on the band structure of
VO has been discussed by Goodenough [3]. Reference
For a recent ESCA study on V 3 Os, see [4],
For recent data on V 2 O 6 and V n 02n-i, see [5]. [1] Honig, M., Wahnsiedler, W. E., and Ekland, P. C.,
J. J.
Heat capacity studies on V„ Chn-i are given in [6]. Solid State Chem. 6, 230 (1973).

130 U.S. GOVERNMENT PRINTING OFFICE : 1974 0-522-205

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BIBLIOGRAPHIC DATA NBS NSRDS-49 N °-
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TRANSITION METAL OXIDES May 1974
Crystal Chemistry, Phase Transitions and Related Aspects 6. Performing Organization Code

7. AUTHOR(S) 8. Performing Organ. Report No.

C. N. R. Rao and G. V. Subba Rao
9. PERFORMING ORGANIZATION NAME AND ADDRESS 10. Project/Task/Work Unit No.

NATIONAL BUREAU OF STANDARDS

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Library of Congress Catalog Card Number: 73-600267

ABSTRACT (A 200-word or leas /actual summary of moat significant Information. If document includea a significant
bibliography or literature survey, mention it here.)

A survey is made of the data describing the thermodynamics

of phase equilibria, crystal chemistry and phase transformations

of binary oxides of 3d, 4d, and 5d transition metals. Changes in

17.
electrical, magnetic, and other properties which accompany phase

transitions are discussed-Nearly complete coverage of the literature

18. is provided up to 1973.

KEY WORDS (six to twelve entries; alphabetical order; capitalize only the first letter of the first key word unless a proper
name; separated by semicolons)
Crystal structure transformations critical data, transition metal oxides; electronic
;

properties; phase equilibria; phase transitions; magnetic properties.

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