Solar Energy Materials

and Solar Cells

ELSEVIER Solar Energy Materials and Solar Cells 32 (1994) 369-382

Electrochromic oxides: a bandstructure approach

C.G. Granqvist
Department of Technology, Uppsala University,Box 534, S-751 21 Uppsala, Sweden
(Received 15 June 1993; in revised form 17 July 1993)

Abstract

This paper attempts to lay down a foundation for a comprehensive theory of elec-
trochromism among oxides. It is pointed out that crystals of all the well known elec-
trochromic metal (Me) oxides are composed of MeO 6 octahedra in various corner-sharing
and edge-sharing arrangements. In electrochromic thin films there are cluster-type and
columnar microstructures based on the MeO 6 units. The coordination of the ions leads to
electronic bands that are able to explain the presence or absence of cathodic and anodic
electrochromism in numerous defect perovskites, rutiles, and layer structures. Optical
absorption can be due to intraband effects, interband transitions, and polaron hopping.

I. Introduction

This p a p e r is d e d i c a t e d to B e r n i e S e r a p h i n , w h o o f t e n stresses t h e i m p o r t a n c e
o f b a n d s t r u c t u r e e n g i n e e r i n g for t h e design o f n e w m a t e r i a l s with t a i l o r e d o p t i c a l
a n d e l e c t r i c a l p r o p e r t i e s . T h e m a i n goal is to p o i n t o u t t h a t w e a r e now at a s t a g e
w h e r e b a n d s t r u c t u r e c o n s i d e r a t i o n s c a n give insights into t h e e l e c t r o c h r o m i s m o f
k n o w n oxides a n d p e r h a p s l e a d to t h e d e v e l o p m e n t o f n e w e l e c t r o c h r o m i c oxides.
E l e c t r o c h r o m i c devices, such as s m a r t windows, a r e a b l e to c h a n g e t h e i r o p t i c a l
p r o p e r t i e s in a r e v e r s i b l e a n d p e r s i s t e n t m a n n e r u n d e r the a c t i o n o f a v o l t a g e
pulse. T h e devices e m b o d y several s u p e r i m p o s e d layers, a n d t h e o p t i c a l m o d u l a -
tion is r e l a t e d to t h e a m o u n t o f m o b i l e ions in an e l e c t r o c h r o m i c m a t e r i a l . T h e
e l e c t r o c h r o m i c m a t e r i a l s o f i n t e r e s t h e r e a r e m e t a l oxides.
E l e c t r o c h r o m i s m has b e e n k n o w n for several d e c a d e s . A s far as we know, t h e
first c l e a r s t a t e m e n t o f this effect was an e n t r y m a d e 30 July 1953 by Dr. Th. K r a u s
in a l a b o r a t o r y r e p o r t at t h e B a l z e r s A G In L i e c h t e n s t e i n . It r e a d s v e r b a t i m [1]:
A u f Glaspliittchen wurde eine halbdurchliissige Metallschicht (Chrom, Silber), und
darauf eine WO3-Schicht (A / 2) aufgedampft. Wurde diese Schicht in 0.1 n H2SO 4

0927-0248/94/$07.00 © 1994 Elsevier Science B.V. All rights reserved

SSDI 0927-0248(93)E0099-Y
370 C.G. Granqvist / Solar Energy Materials and Solar Cells 32 (1994) 369-382

als Kathode geschaltet ( - 1 . 5 0 V), so fiibte sie sich in der Durchsicht intensiv blau.
Als Anode geschaltet entfiirbte sie sich wieder und sperrt im farblosen Zustand den
Strom. Das Fiirben und Entfiirben der Schicht liisst sich durch Umpolen der Elektro-
den beliebig oft wiederholen. In kathodischer Schaltung tritt hierbei Polarisation auf,
deren EMK gegen Cu-Elektroden > 0.6 Volt betriigt.
The characteristic features of the electrochromism in W oxide films are clearly
spelled out here. Electrochromism, or rather optical modifications during electro-
chemical polarization of passivation layers on metal electrodes, were observed
through ellipsometry in 1933 by Tronstad [2] and in 1965 by Reddy et al. [3]. Also,
a paper on Nb oxide by Palatnik et al. [4] should be noted. This paper quotes
patent specifications and " U S S R Authors' Certificates", and makes it likely that
an electrochromic effect had been observed as early as in 1963. Deb's seminal
papers [5] on the electrochromism in W oxide films then appeared in 1969 and
1973 and started worldwide research on this topic.
Despite all of the interest in electrochromism, which has resulted in hundreds
of scientific and technical papers on W oxide alone [6], the fundamentals of the
phenomenon have eluded understanding. However, as we will see below, one can
pinpoint some basic microstructural features that are of decisive importance for
the electrochromism and show how the microstructure leads to electronic band-
structure models capable of explaining--at least for the majority of the elec-
trochromic m a t e r i a l s - - w h y certain ones become absorbing under ion insertion
while others become transparent under ion insertion. Most of the information in
this p a p e r is drawn from the large, but highly diverse, published literature on
electrochromism, but this information is used in what we think is an original way to
provide a general framework for a theory of electrochromism among the metal
oxides. The present p a p e r is an update on some recent articles [7].
Electrochromism is associated with ion insertion/extraction processes that can
be represented, highly schematically, by
MeO n + x I + - x e - ~ I x M e O n. (1)
H e r e Me is a metal atom, I ÷ is a singly charged small ion such as H ÷ or Li +, e - is
an electron, and n depends on the particular type of oxide. For example, n is 3 for
defect perovskites, 2 for rutiles, 1.5 for carborundums and 1 for rock-salts.
This p a p e r is organized as follows: Section 2 considers the microstructure, and
part 2.1 gives a survey of the bulk crystal structures for most of the metal oxides
known to exhibit electrochromism. These oxides comprise octahedral building
blocks of M e O 6 type that are connected in a plethora of different corner-sharing
and edge-sharing configurations. Part 2.2 regards thin films; it appears that the
ubiquitous octahedral building blocks exist also in the films a n d - - p r o v i d e d that
the film growth takes place under low energy conditions so that long-range
crystallization is i m p e d e d - - a sufficiently loose packing is accomplished so that
small ions can be transported easily within the material. Characteristic micro-
structural features occur on different length scales. Thus part 2.2 is devoted to
MeO6-based clusters of the size 1 to 10 nm as well as to larger columnar features.
Section 3 considers the electronic band structure, and ensuing optical properties,
 C.G. Granqvist / Solar Energy Materials and Solar Cells 32 (1994) 369-382 371

consistent with the octahedral M e O 6 units. Particular attention is given to per-

ovskite-like and rutile-like materials. The schematic bandstructures for these
classes of materials, following ideas originally put forward by Goodenough [8,9],
are used in part 3.1 as a basis for a discussion of the electrochromism in several
oxides. Less detailed treatments are given for some layered oxides. Part 3.2 then
turns to the physical causes of the absorption and points at the importance of
intraband effects, interband transitions, and polaron hopping. A summary and
some concluding remarks are given in Section 4.

2. Microstructures

2.1. The ubiquitous octahedron

The electrochromic oxides can be divided into three main groups with regard to
their bulk crystalline structures: perovskite-like, ruffle-like, and layer and block
structures. They are discussed in this order below, and the general occurrence of
octahedral M e O 6 building blocks is emphasized. Ref. [10] may serve as a standard
source for much of the structural information. Along with the discussion of
structure, we point at characteristic features of the electrochromism.
The perovskite structure, with a general composition C M e O 3, is illustrated in
Fig. 1. As drawn, the Me ions occupy the corners of a primitive unit cell and O
ions bisect the unit cell edges. The central atom, denoted C, is neglected at the
m o m e n t since it is absent in the electrochromic oxides of most interest. The
corresponding (defect) perovskite M e O 3 configuration is often referred to as the
rhenium oxide structure. It should be noted that the R e O 3 structure can be
visualized as an infinite framework of corner-sharing octahedra each with a metal

Perovskite lattice

1
Fig. 1. Unit cell for the perovskite lattice. Octahedral symmetries are emphasized.
372 C.G. Granqvist/ Solar Energy Materials and Solar Cells 32 (1994) 369-382

ion surrounded by six equidistant oxygen ions. In between these octahedra there
are extended tunnels that can serve as conduits and intercalation sites for small
ions.
Tungsten oxide, WO3, was the first discovered material with clear-cut elec-
trochromism as pointed out in the Introduction, and today it still remains the most
viable option for devices. The crystal structure is of perovskite-type, but some
atomic displacements and rotations of W O 6 octahedra normally occur so that,
depending on the temperature, tetragonal, orthorhombic, monoclinic or triclinic
symmetries are found. Tungsten oxide also has a tendency to form substoichiomet-
ric (Magn61i) phases with edge-sharing octahedra and extended tunnels with large
pentagonal or hexagonal cross-sections. It is also possible to form tungsten oxide
with hexagonal and pyrochlore structures comprising open arrangements of W O 6
octahedra. It is very well established [5,6] that disordered tungsten oxide films
transform from an optically transparent to an absorbing state under ion insertion.
This is referred to, in electrochemical terms, as cathodic coloration. The opposite
case, with absorption associated with ion extraction, is called anodic coloration.
Molybdenum oxide, MOO3, has been known as a cathodic electrochromic
material at least since 1974 [11]. Bulk crystals at room temperature have a
structure consisting of corner-sharing chains of M o O 6 octahedra that share edges
with two similar chains; these layers are stacked in a staggered arrangement and
are held together by weak van der Waal's forces. This unique structure is referred
to as the a-phase. There is also a /3-phase, that can be viewed as a metastable
analogue of WO3, which is of perovskite-type. Available data on thin films of
molybdenum oxide [12] strongly indicate that the structure is built from corner-
sharing M o O 6 octahedra in much the same way as for electrochromic tungsten
oxide. Rhenium oxide--obviously a defect perovskite--is not known to exhibit
electrochromism.
The rutile structure, or at least a rutile-like configuration, is present for a whole
series of materials exhibiting cathodic or anodic electrochromism. The ideal
structure can be thought of as built from almost octahedral M e O 6 units forming a
framework with infinite edge-shared chains. These chains are arranged so that they
form an equal number of ideal vacant tunnels.
First titanium oxide, TiO 2, is considered, which can have different crystal
structures, viz. rutile, anatase and brookite. The anatase phase, which so far has
attracted most interest in the context of electrochromism, consists of infinite
planar double chains of TiO 6 octahedra; these chains are connected by corner-
sharing. Empty sites also form double chains, or zig-zag tunnels. Cathodic elec-
trochromism was first reported in 1974 [13] and a large degree of optical modula-
tion has been observed in some more recent work [14].
Manganese oxide, MnO 2, has a crystal chemistry of bewildering complexity.
However, most structures are built from edge-shared M n O 6 octahedra that share
corners with other chains. The most common s t r u c t u r e s - - a t least among the
m i n e r a l s - - h a v e tunnels with sizes (in units of MnO 6 chains on each side) being
1 × 1 i n / 3 - M n O : (rutile, or pyrolusite), 2 × 1 in ramsdellite, and 2 × 2 in a - M n O 2
(hollandite). An intergrowth phase between the pyrolusite and ramsdellite struc-
 c.G. Granqvist/ Solar Energy Materials and Solar Cells 32 (1994)369-382 373

tures is known as ~/-MnO 2 (nsutite). Electrochromism was discovered recently, and

ion insertion was found to lower the absorption [15].
Vanadium dioxide, VO 2, is of rutile-type (tetragonal) above 68°C and is mono-
clinic--albeit with very slight atomic displacements from the ideal rutile structure
- - b e l o w this temperature. Vanadium dioxide films are electrochromic and show a
decrease of the absorptance under ion insertion irrespective of the temperature
being below or above 68°C [16].
Ruthenium oxide, R u O 2, has rutile structure. Ions can be inserted and ex-
tracted, but the material remains absorbing no matter the ionic content [17].
Iridium oxide, IrOz, is another rutile material. It is electrochromic a n d - - i n
contrast with the electrochromic oxides discussed so f a r - - i s clearly anodic and can
go from an absorbing to a transparent state under insertion of one ion per formula
unit [18]. Rhodium oxide, RhO2, shows many similarities with Ir oxide, and ion
insertion is able to lower the absorption significantly [19].
The layer and block structures form a somewhat undefined group of elec-
trochromic materials. Niobium oxide, N b 2 0 5, has complex crystal chemistry. Vari-
ous phases can be thought of as built from blocks (or columns) of N b O 6 octahedra
arranged in a R e O 3 structure; structures conventionally denoted R-Nb205, M-
N b 2 0 5, N - N b 2 0 5 and H - N b 2 0 5 are characterized by blocks of different sizes and
interconnections. A structure derived from corner-sharing rutile blocks is desig-
nated B-Nb205. Niobium oxide is electrochromic and goes from a transparent to
an absorbing state upon ion insertion [20]. Tantalum oxide, Ta205, have many
properties in common with Nb205.
A m o n g the cobalt-oxide-related materials, both H C o O 2 and LiCoO 2 are of
interest. The latter material can be represented as a layered rock-salt with
alternate planes of Co and Li atoms. Both of these species are surrounded by six O
in octahedral coordination; the CoO 6 octahedra are compressed and the LiO 6
octahedra are elongated. H C o O 2 has a similar, though not identical, crystal
structure. Absorption develops upon extraction of protons [21] or lithium ions [22].
Hydrous nickel oxide shows pronounced anodic electrochromism and goes from
an absorbing to a transparent state under proton insertion [23]. The material is
thought to contain layers of NiO 6 octahedra sharing edges, and the protonated
transparent material is probably akin to brucite, Ni(OH) 2.
Vanadium pentoxide, V205, can be described as consisting of distorted V O 6
octahedra or, alternatively and more properly, as consisting of square pyramidal
V O 5 units. The latter representation highlights the layered structure. Vanadium
pentoxide films are electrochromic and show a somewhat increasing overall ab-
sorption upon ion insertion [24]. They are capable of multi-colour electrochromism
due to an apparent bandgap widening when ions are intercalated.

2.2. Clusters and columns in thin films

Bulk crystals of almost all of the well known electrochromic oxides are built
from highly regular arrangements of edge-sharing and corner-sharing M e O 6 octa-
374 C.G. Granqvist / Solar Energy Materials and Solar Cells 32 (1994) 369-382

hedra, as stressed above. Electrochromic thin films of these materials rarely exhibit
long-range order, though. The local microstructure of the pertinent thin films has
been studied in detail only for W oxide, and the discussion below is focused on this
material. It is reasonable to assume that similar, though most certainly not
identical, conditions exist for the other oxides.
When W oxide is evaporated, the liberated species are of molecular type, with a
preponderance of W30 9 [25]. Molecular ejection is important also for sputtering
[26]. Vibrational spectroscopy is useful for elucidating structural features, and
R a m a n spectra gave clear evidence for vibrations in the framework of corner-shar-
ing W O 6 octahedra and of terminal W=O bonds on internal surfaces in evaporated
films [27]. Infrared spectroscopy indicated hydration and hydroxylation.
X-ray scattering is able to provide detailed structural information, and from
Fourier transformations of the scattering data it is possible to extract radial
distribution functions (RDFs) that yield the density correlations in the analyzed
materials. A few years ago, a very ambitious structural model was used by Nanba
and Yasui [28] to model R D F s for evaporated W oxide films. Eight different
crystallographic structures were employed as starting points, and corresponding
R D F s were computed. All of the R D F s yielded peaks at ~ 0.2 nm due to W - O
nearest neighbours and at 0.37 to 0.40 nm due to W - W nearest neighbours and, to
a smaller extent, W - O next-nearest neighbours. All of these features stem from
the octahedral W O 6 building blocks. Peaks at radii > 0.5 nm are of more decisive
importance for the structural models and, in particular, a peak at ~ 0.73 nm could
be reconciled only with a hexagonal structure. Specifically, the preferred structural
model was based on hexagonal W O 3 embracing, three- and six-membered rings of
octahedra. The corresponding cluster size was consistent with electron microscopic
evidence. The three-member rings can be ascribed to the W30 9 molecules pro-
duced during evaporation, and such molecules can be tied together to form
six-member rings. The clusters were arranged in space with consideration of their
hexagonal plate configuration, so that they constituted a "film". Theory and
experiment were found to be in excellent agreement, which gives strong credibility
to the structural model outlined above. Furthermore, an extension of this model
could be applied to films evaporated at elevated substrate temperatures; cluster
growth as well as cluster-cluster linking then were significant. Obviously, the
clusters cannot be entirely separated from each other but are thought to be
connected by hydrogen bonds, bridging water molecules, etc.
The structural model gives clear evidence that a W oxide film should be viewed
as a n a n o c o m p o s i t e - - r a t h e r than a truly amorphous m a t e r i a l - - w i t h a grain size
between ~ 1 nm and ~ 5 nm depending on the deposition conditions. Annealing
at ~ 400°C transforms the W oxide into a long-range-ordered crystalline state.
Film deposition techniques other than evaporation normally produce nanocompos-
ites too, although low-voltage anodization [29] and sol-gel technology [30] seem
capable of yielding more disordered "polymeric" structures, possibly comprising
disordered arrays of individual W O 6 octahedra.
Inhomogeneities on a scale larger than the one discussed above are possible as
well and, in fact, microstructural features occur at all dimensions up to those
 C.G. Granqvist / Solar Energy Materials and Solar Cells 32 (1994) 369-382 375

comparable with the film thickness. Columnar structures can be understood from
models based on ballistic aggregation of structural units and ensuing reaccomoda-
tion of these, as well as from growth instabilities in continuum theories. For films
prepared by normal evaporation--with the vapour flux having perpendicular
incidence towards the substrate--the columns are oriented normal to the sub-
strate. The intercolumnar regions allow easy transport of ions across the films,
which is of large importance for the dynamics of electrochromic devices. The
transport mechanism can be vehicular, Grotthuss-type, or a mixture of these. It is
possible to increase the columnar character by depositing tungsten oxide films at
an oblique angle [31].

3. Optical properties

3.1. Schematic bandstructures, and systematics for the electrochromism

Below it will be shown that highly simplified bandstructures, originally due to

Goodenough [8] and presented in a particularly accessible way by Honig [9], allow
us to understand why certain perovskite-type and futile-type electrochromic oxides
become absorbing under ion insertion, others become transparent under ion
insertion, and still others show some absorptance irrespective of their ionic
content. At least some of the layer structures can be handled in a similar way, as
will be mentioned briefly.
The perovskite structure was shown in Fig. 1. A corresponding energy level
diagram for the defect perovskite, i.e., the rhenium oxide structure here denoted
MeO3, is illustrated in Fig. 2a. The atomic s, p and d levels of Me are indicated, as
well as the 2s and 2p levels of O. For WO 3 and ReO3, the pertinent Me levels are
6s, 6p and 5d. The positions of these levels on the vertical energy scale are
governed by their values for the isolated atoms as well as by the Madelung energies
of the atoms when located in the perovskite lattice. Each Me ion is octahedrally
surrounded by six oxygen ions, and each oxygen is linearly flanked by two Me ions.
As a consequence of this arrangement, the d level is split up into eg and t2g levels
(using the conventional notation) as shown in the left-hand part of Fig. 2a. The
splitting arises because the eg orbitals point directly at the electronegative O
whereas the t2g orbitals point away from the nearest neighbours into empty space
and are hence lower in energy. Similarly, the O2p orbitals are split as indicated in
the right-hand part of Fig. 2a; the 2p~ orbitals point directly at the nearest
electropositive Me ions whereas the 2p~ orbitals point into empty space. In the
perovskite lattice, the incipient molecular energy levels broaden into bands, whose
relative widths and repulsion can be obtained from general arguments.
The number of states available for electron occupancy is fixed for each band.
For example, counted per MeO 3 formula unit, the t2g band has a capacity for six
electrons (allowing for spin degeneracy), and the p~ band has a capacity for twelve
electrons (allowing for spin and electron degeneracy). The pertinent electron
376 C.G. Granqt;ist / Solar Energy Materials and Solar Cells 32 (1994) 369-382

Perovskite structure /~ [ (a)

~. • 26 .,

d {t2g~-'--'----~ e I- ReO 3
" WO a, 13-Mo Oa

i L__r

J 6 I~ - s --S

Me 03

structure
Rutile _ ~ ~ ~ ~ I /~ (b)

P P - - - I Pi RhO2,1r02
s -
d .....
!_g:-
I __ _ ,!i _-
--_
J
~
Mn02 - WO
CrO2,M°u2,
VO2,Nb02
TiO
P~I
2

P
Pb - - - - -
--S

Me 02
Fig. 2. Schematic bandstructures for the MeO 3 defect perovskite structure (a) and for the MeO 2 rutile
structure (b). The incipient atomic and molecular levels are shown, using standard notation. The
numbers in the different bands denote electron capacities. Arrows indicate Fermi energies. (From Ref.
[9]).

c a p a c i t i e s a r e i n d i c a t e d by t h e n u m b e r s in the v a r i o u s b a n d s in Fig. 2a. W O 3 a n d

the i s o - s t r u c t u r a l f l - M o O 3 have 24 e l e c t r o n s in the shown b a n d s , so t h a t t h e F e r m i
e n e r g y lies in t h e gap b e t w e e n the t2g a n d p~ b a n d . T h e b a n d g a p is w i d e e n o u g h
to r e n d e r t h e m a t e r i a l t r a n s p a r e n t . R e O 3 , on the o t h e r h a n d , has 25 e l e c t r o n s so
t h a t the lower p a r t o f t h e t2g b a n d is o c c u p i e d a n d t h e m a t e r i a l is n o n - t r a n s p a r e n t .
W h e n ions a n d e l e c t r o n s are i n s e r t e d a c c o r d i n g to r e a c t i o n (1), t h e F e r m i level
 C.G. Granqvist / Solar Energy Materials and Solar Cells 32 (1994) 369-382 377

is moved upwards in the presumed rigid-band scheme. In the case of W O 3 and

fl-MoO3, the excess electrons must enter the t2g band and the material, in
principle, transforms from a transparent to an absorbing or from a transparent to a
reflecting state depending on whether the electrons occupy localized or extended
states. When the ions and the accompanying electrons are extracted, the material
returns to its original transparent state. In ReO3, the Fermi energy also moves
upwards upon ion insertion, but it remains well within the t2g band irrespective of
the content of mobile ions. Consequently, the optical properties are not expected
to be changed qualitatively, although quantitative changes in the absorptance may
result from density-of-states effects that are outside the realms of the schematic
bandstructure. Clearly, the discussion above explains why W oxide and Mo oxide
are cathodic electrochromic materials, whereas Re oxide is not known to be
electrochromic.
Rutile and rutile-like structures are found among many M e O 2 oxides as pointed
out above. Several of these oxides are e l e c t r o c h r o m i c - - e i t h e r cathodic or anodic
- - a n y may or may not attain a transparent state. The electrochromism can be
understood from the basic bandstructure in Fig. 2b. It deviates from its counter-
part for the perovskites because the M e O 6 building blocks are distorted and
edge-sharing. We start from the atomic s, p and d levels for the Me ions and the s
and p levels for the oxygen ions. Every Me ion is almost octahedrally surrounded
by oxygen ions, and every oxygen ion is roughly trigonally surrounded by Me ions.
Hence the d levels are first split into eg and teg levels, and the oxygen p levels are
split into levels with orbitals Pb in the basal plane of the triangular array (wherein
the oxygen ion is surrounded by three Me ions) and with orbitals p i perpendicular
to that array. A further splitting occurs because the ideal octahedral symmetry is
absent, and the ensuing Me levels--whose origin is not discussed h e r e - - a r e
designated tll , t i , Pb and p ±. In addition, the degeneracy of the eg level is lifted.
When the ions are arranged in the futile lattice, one expects overlap among the tll
and t ± bands as well as among the two eg bands. Hence, the final schematic
bandstructure is in fact quite similar to that of the perovskites. Depending on the
p a r a m e t e r s of the rutile unit cell, the tll band may collapse into an atomic-like
sharp level. Electron band capacities can be deduced as for the perovskites and are
indicated by the numbers in the bands.
The arrows in the left-hand part of Fig. 2b indicate the Fermi levels for several
rutile-like oxides. For TiO2, the Fermi level lies in the gap between the Ti3t2g and
the O2o± bands, and ion insertion is expected to lead to a transformation from a
transparent to an absorbing state in a similar way as for W O 3 and fl-MoO 3. This is
consistent with experimental results on Ti oxide films. For VO 2, M n O 2 and RuO2,
which were discussed earlier, the initial absorbing state cannot be eliminated by
ion insertion. Again this is as expected from the bandstructure. R h O 2 and IrO 2
are especially interesting, since their Fermi levels lie close to the gap between the
t2g and eg bands. Indeed, if ions are inserted up to about one per formula unit in
Ir oxide films, these materials are transformed from an absorbing to a transparent
state. In the bandstructure picture, the transparency is associated with the bandgap
referred to above. One should note that transitions between pure t2g and eg states
378 C.G. Granqvist / Solar Energy Materials and Solar Cells 32 (1994) 369-382

are parity-forbidden. Rhodium oxide films are similar to Ir oxide films, but their
optical properties have not been studied in great detail.
Fig. 2b also lists a number of rutile-type oxides other than those mentioned
above, specifically NbO2, CrO2, M o O 2 and W O 2. Whereas these materials un-
doubtedly can be prepared as thin films, the fabrication is fairly awkward since the
rutiles are not the highest oxides. More specifically, the oxygen partial pressure
would have to be very accurately controlled in a reactive process. It is much easier
to make Nb205, which is an electrochromic block-type material. Contrary to MoO 2
and WO 2 with (almost) rutile structure, it has been discussed at length above that
one can make excellent electrochromic films of perovskite-type Mo oxide and W
oxide.
The layer structures are not amenable to a simple theoretical treatment analo-
gous to the one for the perovskites and rutiles. It is noted, however, that the
bandstructure of LiCoO 2 was studied recently [32] and that the highest occupied
states were of t2g character. V205 has an interesting bandstructure with a filled
O2p band separated from a V3d band with a split-off lower portion [33]. Band
splittings indeed are characteristic features of layer structures. We are not aware
of any detailed bandstructure data for niobium oxide or hydrous nickel oxide.

3.2. Physical causes of the electrochromic absorption and reflection

The schematic bandstructures indicate the fate of the electrons that enter the
electrochromic films together with the ions required to provide overall charge
neutrality. Here, the likely physical mechanisms of the absorption in heavily
disordered oxides are considered.
Fig. 3 surveys the bandstructures of the electrochromic oxides capable of
attaining a fully transparent state. For WO 3,/3-MOO 3, TiO 2 and, possibly, also for
Nb2Os, the Fermi energy lies between the O2p and the t2g bands. Insertion of
electrons makes the lower part of the latter band populated. If the oxide is heavily
disordered, the excess electrons and their lattice polarisation can hop from one
tungsten ion site to another by absorbing a photon, i.e., the materials exhibit
polaron absorption. The peak absorption lies in the near infrared, which renders
the oxides bluish. For a sufficiently well-ordered material it is possible to have
metallic-like properties, i.e., high reflection at wavelengths larger than the plasma
wavelength. Crystalline WO 3 has this property. Well-ordered MoO 3 transforms
into the layered a phase, and well-ordered TiO 2 is too dense for easy ion
insertion.
The t2g band is almost full in IrO 2, RhO2, delithiated LiCoO 2 and, possibly,
deprotonated Ni(OH) 2. These oxides are strongly absorbing. Polaron absorption is
not observed, and we think that intraband absorption in a composite material
characterized by parts having various electron densities (conductivities) and shapes
is a more likely cause for the optical behaviour. In principle, effective medium
theory could account for the optical properties, but in the absence of substantial
evidence for a composite structure the proposed absorption mechanism must be
 C.G. Granqvist/ Solar Energy Materials and Solar Cells 32 (1994) 369-382 379

MxWO3 Hxlr02
I]-MxMO03 HxRh02
MxTi02
MxNb2Os?
Lil-xCO02
HxNi02? V2OS
E E E

eg

t2g -~ t2g V3d

02p 02p 02p

Polaron abs. Intraband abs. Interband abs.

(Metallic Effective Polaron abs?
reflection for medium
c-WO3) properties?
Fig. 3. Schematic bandstructure and suggested absorption mechanisms for several electrochromic
oxides.

regarded as conjectural. Electron insertion, associated with a filling of t2g band,

can lead to optical transparency, as noted above.
V205 shows some absorption of blue light. This is readily explained as a result
of transitions between the top of the O2p band and the split-off lower portion of
the V3d band. Insertion of electrons can fill this split-off band. Since transitions
between the two components of the d band are parity-forbidden, the net effect will
be an apparent widening of the optically observed bandgap, which is then deter-
mined by transitions between the top of the O2p band and the lower part of the
main d band. Hence interband transitions govern the short-wavelength elec-
trochromism in V205. At a larger density of electron insertion, it is reasonable to
expect that polaron absorption could lead to long-wavelength absorption.
We conclude with some comments on (semi)quantitative theoretical descriptions
of the electrochromism in W oxide. If these films are sufficiently disordered, one
can use a theory that predicts that the small polaron absorption C~poI can be
expressed by [34]:

apo,(OJ ) ~ o J - l e x p
I(hw-4Up)
8UphOjph ] ' (2)

where hto is photon energy, Up is polaron binding energy, a n d htOph is typical

phonon energy. It was found by Schirmer et al. [35] that experimental data for
380 C.G. Granqvist / Solar Energy Materials and Solar Cells 32 (1994) 369-382

proton inserted W oxide films could be reconciled with tO2Olpol(t..O).The fitting used
Uv = 0.275 eV and hCOph= 0.098 eV, which are reasonable values. In particular,
theory and experiment were in good agreement at energies lower than that of the
peak absorption. An alternative model for the absorption in disordered W oxide
films is obtained from intervalence charge transfer theory [36].
For crystalline W oxide, the optical and electrical properties are akin to those of
heavily doped semiconductors such as I n 2 0 3 : Sn [37] and ZnO : A1 [38]. Free-elec-
tron theory can be employed to describe the optical properties in this case. Drude
theory can be used for qualitative work but is unable to give quantitative predic-
tions since electron scattering is treated as frequency-independent and is repre-
sented only by a fitting parameter. Instead the Gerlach theory [39] is applicable, at
least to first order, to represent the limiting case when only ionized impurity
scattering is present. Screening of the ions can be accounted for by the Random
Phase Approximation or an extension thereof. Computations showed [40] that the
spectral infrared reflectance was in qualitative, though not quantitative, agreement
with experimental data.

4. Summary and remarks

In this paper we have taken a birds-eye view on electrochromics. It was pointed

out that almost all of the well-known electrochromic oxides can be thought of as
built from MeO 6 octahedra in various corner-sharing and edge-sharing arrange-
ments. The corresponding crystal structures are perovskite-like, rutile-like, and of
layer or block character. The octahedral units are favourable both for ion and
electron transport.
The pertinent crystal structures allow long-range ion diffusion through tunnels
or between layers. This capability exists, at least to some extent, in good crystals,
and it is highly accentuated in thin films produced by standard techniques. Such
films are characterized by cluster-type microstructures and column-type macro-
structures. The ion diffusion may be very complex and, for example, recent data
based on microbalance measurements [41,42] indicated that variously solvated ions
could be inserted in W and Ni oxide films, sometimes with competition among the
mobile species. Fortunately, the complexities of the ion transport are not crucial
for the basics of electrochromism, but the electrons that enter in conjunction with
the ions, in order to obtain overall charge neutrality, cause the optical effects.
Once the ubiquity of the octahedra is realized, one may take the next step and
think of canonical electron bandstructures capable of catching the essentials of the
electrochromism among the oxides. Following Goodenough [8], it is indeed possi-
ble to represent the crystal-field-effects for the pertinent ion coordinations in
terms of schematic bandstructures for the perovskites and rutiles. In this represen-
tation, an insertion of electrons has the sole effect of lifting the Fermi energy. The
model is able explain why oxides of W, Mo and Ti show cathodic electrochromism,
why oxides of Ir and Rh show anodic electrochromism, and why several other
oxides--though capable of ion insertion--are unable to be optically transparent.
 C.G. Granqvist / Solar Energy Materials and Solar Cells 32 (1994) 369-382 381

T h e a b s o r p t i o n c a n b e c a u s e d by p o l a r o n h o p p i n g , i n t r a b a n d a b s o r p t i o n in
composite media, and interband transitions. Small polarons are responsible for the
a b s o r p t i o n in h e a v i l y d i s o r d e r e d W o x i d e . F o r c r y s t a l l i n e W oxide, it is p o s s i b l e to
o b t a i n r e f l e c t a n c e m o d u l a t i o n as a r e s u l t o f f r e e - e l e c t r o n e f f e c t s .

Acknowledgement

Illuminating discussions with Dr G.A. Niklasson and others are acknowledged

w i t h p l e a s u r e . T h e a u t h o r is t h a n k f u l to D r s . R o n G o l d n e r a n d T e r r y H a a s o f
T u f t s U n i v e r s i t y f o r m a k i n g h i m a w a r e o f R e f . [1], a n d to D r . E l m a r R i t t e r o f
B a l z e r s A G f o r a l l o w i n g h i m to u s e it in p r i n t .

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