ARTICLE IN PRESS

Solar Energy Materials & Solar Cells 92 (2008) 245–258

www.elsevier.com/locate/solmat

Invited paper

Opportunities and challenges in science and technology of WO3 for

electrochromic and related applications$
Satyen K. Deb
Center for Materials Science, National Renewable Energy Laboratory, 1617 Cole Boulevard, Golden, CO 8040-33931, USA
Received 15 December 2006; accepted 2 January 2007
Available online 24 October 2007

Abstract

Since the discovery of the electrochromic (EC) effect in transition metal oxides in the mid-1960s, intense research and development
work spanning four decades has led to many exciting developments in the science and technology of this class of materials. Tungsten
oxide (WO3) has emerged as one of the key materials, not only for EC devices, but also for many other related applications. After many
years of technology development efforts, WO3-based EC ‘‘smart windows’’ have finally emerged as a viable commercial product. In spite
of enormous progress being made on the structural, electrical, and optical properties of amorphous and crystalline WO3, a detailed
understanding of the EC effect in this material still remains somewhat qualitative. Although theoretical models based on intervalence
charge transfer and polaron formation have been widely accepted, these models are still unable to explain some of the experimental
results on the coloration phenomena. The coloration in WO3 is a structure-sensitive phenomenon, and excess electrons can be either
localized or delocalized. The presence of structural defects such as oxygen vacancies, impurities, and degree of disorder plays a crucial
role in determining the coloration efficiency. Although significant progress has been made in recent years on the calculation of electronic
structure and defect properties of both amorphous and crystalline WO3, the structural complexity of the material presents many
challenges and opportunities for theoretical computation. The unique ability to induce bistable optical and electrical properties in WO3
by a variety of excitation sources has led to many devices of significant technological interest. Some of the applications currently being
pursued include the photoelectrochemical cell for solar energy conversion and storage; photoelectrochemical splitting of water to
generate hydrogen; chemical and biological sensors based on the gasochromic effect; photo- and electrocatalysts for a variety of chemical
reactions; demonstration of high-temperature (91 K) superconductivity in WO3 doped with H, Na, and K; synthesis of a new class of
hybrid organic/inorganic (WO3) materials; and application in ultra-high-resolution electron beam lithography. The emergence of
nanostructured WO3 in recent years will undoubtedly provide new opportunities and significant impact to many of these technologies.
This paper presents a brief overview of some of the key research issues the author believes will impact the science and technology of this
exciting material.
r 2007 Published by Elsevier B.V.

Keywords: WO3 electrochromics; Fundamental properties; Device applications; Smart window; Photoelectrochromic

1. Introduction

$ Tungsten oxide (WO3), which is one of the do-transition

This work has been authored by an employee or employees of the
Midwest Research Institute under Contract no. DE-AC36-99GO10337
with the US Department of Energy. The United States Government
retains and the publisher, by accepting the article for publication,
acknowledges that the United States Government retains a non-exclusive,
paid-up, irrevocable, worldwide license to publish or reproduce the
published form of this work, or allow others to do so, for United States
Government purposes.
Tel: +1 303 384 6405; fax: +1 303 384 6481.
E-mail address: satyen_deb@nrel.gov
metal oxides, has many interesting optical, electrical,
structural, and defect properties. The interest in this
material goes back to 1837 when Wohler first observed
intense metallic luster in LiWO3. He thought the luster was
due to the formation of metallic alloys and coined the term
‘‘tungsten bronzes.’’ Mott, Sienko, and others performed a
significant amount of experimental and theoretical work in
the 1950s and 1960s on single crystals of Na–tungsten

0927-0248/$ - see front matter r 2007 Published by Elsevier B.V.

doi:10.1016/j.solmat.2007.01.026
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246 S.K. Deb / Solar Energy Materials & Solar Cells 92 (2008) 245–258
bronzes because of their unusual electrical properties such
as metal–insulator phase transitions and superconductivity
at very low temperature. In an effort to find an inorganic
material that will show reversible coloration and bleaching
effect (photochromism), we began to investigate thin films
of MoO3 and WO3 in the mid-1960s [1–3]. This led to the
discovery of photochromism, followed by the electrochro-
mic (EC) effect in highly disordered thin films of these
materials. The EC effect was first demonstrated by using
surface electrode geometry, which is an interesting device
configuration that can be very useful for studying the
dynamics of the coloration processes. This was soon
followed by a completely reversible, thin-film sandwich
structure, consisting of M-SiO-WO3-TCO, which led to
many of the device structures that have been studied since
then [4–7]. Extensive technological developments have led
to a number of interesting devices, most notably the first
commercially available EC ‘‘smart window,’’ which has the
potential to make a huge impact in energy conservation
areas. The work on WO3 has stimulated extensive research
on a number of other transition metal oxides, and several
books [8,9] and review articles have been written on this
subject [10,11]. Among all the materials studied thus far,
WO3 has emerged as the most extensively studied material,
not only for chromogenics, but also for a variety of other
device applications. Beyond the technology development,
enormous work on the physical and chemical properties of
WO3 as a prototypical material has been done that is of
immense scientific interest. In this paper, an attempt will be
made to give a brief overview of some of the key research
challenges and opportunities in the science and technology
of WO3 for chromogenic and related applications.
2. Fundamental understanding of chromogenic phenomena
in WO3
Despite the copious amount of work that has been done
over several decades on the coloration phenomena in thin
films of amorphous and crystalline WO3, many contra-
dictions still exist on the interpretation of experimental
results. In a recent review article devoted exclusively to the
coloration of WO3 films, Bange [10] did an admirable job
in compiling the vast amount of work that has been done in
this field. It would be instructive at this point to
recapitulate what we know about the coloration phenom-
ena in WO3. Some of the key experimental results are: a
variety of excitation processes such as thermal, optical,
electrical, ionizing radiation, heating in vacuum, inert and
reducing atmosphere, etc., can be used; spectrum of
coloration is essentially similar in all cases with small
variations in peak position and half-width; coloration is
structure sensitive (peak absorption at 1.2 eV for amor-
phous and 0.7 eV for crystalline); coloration occurs most
efficiently in highly disordered amorphous films; fully
oxidized crystalline films do not show any coloration
except for films formed at high temperature under a
reducing atmosphere (vacuum, Ar, H2, etc.); optical
coloration occurs when irradiated with photon energies
within the bandgap (maximum at 3.6 eV); both optical and
electrical coloration are sensitive to ambient condition—
efficiency increases in the presence of H2O (optical); no
electrical coloration occurs in vacuum, but thermal,
optical, electron- and ion-beam-induced coloration can
still occur; doping with impurities can affect coloration
dynamics; optically induced coloration generally cannot be
bleached with light, but can be bleached electrically; color-
center-induced photoconductivity is observed at high
electric field at elevated temperature; double injection and
extraction of electrons and compensating ions is required
for reversible electrical coloration; coloration can be
bleached by heating in oxygen, but the coloration efficiency
progressively goes to zero; coloration is associated with a
proportional increase in electrical conductivity (semicon-
ductor-metallic); electrical coloration leads to generation
of an internal emf that opposes the externally applied
field—bleaching is enhanced on shorting the device; ESR
signal characteristic of the W5+ ion may appear in virgin
film, which can increase with coloration; thermal colora-
tion on heating (80–330 1C) in vacuum that bleaches on
annealing in air—loss of oxygen is observed during some
coloration processes; dynamics of optical (slower) and
electrical coloration (faster) are very different and greatly
influenced by film properties (structure and composition),
excitation energy, and ambient conditions; ion beam (H+,
N+, He+, Ar+, Na+, etc.) induced coloration is generally
irreversible and absorption increases with oxygen defi-
ciency; coloration and bleaching occur in hydrogen- and
oxygen-containing gases, respectively, in the presence of a
catalyst (Pt, Pd, or Rd) and kinetics of coloration depend
on oxygen deficiency and PH2O; and color center peak
position and half-width changes with density of coloration
and film properties.
Clearly, to reconcile many of these seemingly contra-
dictory results into one unifying model is a formidable
task, and it will be a challenging opportunity to develop
such a model. Starting with our original model that
recognized the critical role of defects such as oxygen
vacancies (analogous to F centers and their derivatives) in a
mostly ionic solid such as WO3, at least four other
mechanisms have been proposed: (i) intervalence charge
transfer (IVCT), (ii) polaronic absorption, (iii) interband
excitations, and (iv) transitions from the valence band to
split off the W5+ state.
Among these four models, the IVCT and polaronic
model (which in some respects are similar) have been
widely accepted as mechanisms for coloration. The IVCT
model for WO3 was first proposed by Faughnan et al. [12]
and is based on the assumption that the injected electrons
are localized on W6+ ions to form W5+, and the coloration
is due to transferring electrons from W5+ to the adjacent
W6+ sites. However, unless these two W sites are non-
equivalent, the two configurations are energetically equiva-
lent. In addition, it fails to explain why there is no
coloration in WO3x when xo0.3.
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An alternative model is based on the concept of polaron
formation, an idea introduced by Landau in 1933 when he
argued that displacing atoms or ions in a material from
their carrier free equilibrium position produces a potential
well that will bind a charge carrier by self-trapping [13]. In
a multidimensional system, several distinct type of polar-
ons (e.g., electron and hole polarons, small and large
polarons, and bipolarons) can be formed [14,15]. These
concepts are shown schematically in Fig. 1. It has been
suggested that the coloration in amorphous WO3 is due to
small polaron formation [16,17]. In that case, the small
polaron binding energy (Ep) is given by the relation:
 
1 e2 1 1 Both of these models fail to recognize the pivotal role of
E p ¼  ,
2 rp a o
where ep and Ao are optical and static dielectric constants,
respectively, and rp (polaron radius) is given by
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 ffi
rp ¼ 12 3 p ð6N p Þ, where Np is the polaron number density
per unit volume [18]. This suggests that as Np increases, Ep
also increases, which supports the observation that the
color center peak moves to higher energy with increasing
coloration density. However, there are some conceptual
difficulties in small polaron formation in WO3.
A small polaron is formed in a covalent system in which
only a short-range electron–lattice interaction occurs. On
the other hand, in a largely ionic solid such as WO3, long-
range electron–lattice interaction will most likely lead to
formation of large polarons that extend over many sites.
This is contrary to the belief that small polaron formation
is typical of WO3. It is possible to distinguish between these
two possibilities by measuring the electrical conductivity
Fig. 1. Schematics of polaron formation in ionic solids.
247
where small polarons lead to thermally assisted hopping
conductivity, whereas large polarons result in moving
itinerantly. They also differ in their effective masses. Apart
from electrical conductivity, the shapes of the asymmetric
optical absorption spectra usually observed in WO3 are
characteristic of large polarons [19].
In materials such as WO3, which is easily polarized and
whose eob2ea ð/ ¼ 6:52; o 450Þ, the formation of bipo-
larons is more likely. A bipolaron is formed when two
carriers are self-trapped in a common potential well. It is
interesting to note that formation of bipolarons may lead
to superconductivity, which has been observed in Na- and
K-doped WO3.
oxygen vacancy such as the decrease in coloration
efficiency with decrease in oxygen deficiency. This brings
us back to the original idea of electron trapping by oxygen
vacancies analogous to F-center formation in ionic solids.
A new model shown in Fig. 2 based on the presence of
oxygen vacancies with associated W4+ ion is consistent
with a modified charge transfer and polaronic model [20].
According to this model, when a V 0O (W4+ or 2W5+)
defect state is created, the defect levels are expected to be
inside or near the valence band holding two electrons.
When one electron is removed from this level, V 0O converts
5+
to V þ O (W ). The positively charged vacancy exerts
coulombic repulsion to the nearest W-ions, which results
in a displacement of the neighboring W-ions and an
upward shift of the defect level into the bandgap, thereby
creating a color center. The optical transition from V þ O to
5+
V 2þ
O or W to W6+ (a state within the conduction band)
contributes to coloration.
A theoretical study on this model is now under way to
perform a more rigorous analysis. WO3 has a defect
perovskite structure that is closely analogous to ABO3
compounds such as niobate and titanate (MNbO3 and
SrTiO3). In both of these materials, the color center
formation has been interpreted in terms of F and F1
centers with considerable delocalization of the electron
density from oxygen vacancy toward the nearest-neighbor
cationic sites (Nb5+/Ti4+) [21,22].
In recent years, there have been a number of theoretical
studies on the electronic structure of crystalline WO3, with
and without oxygen vacancies, and also in amorphous
phase, using self-consistent, first-principles calculations
[23–26]. Crystalline WO3 shows a number of phases,
simple cubic to monoclinic to orthorhombic to tetragonal
to triclinic, which makes calculations much more complex.
Therefore, many of these calculations have been done on
the simple cubic structure. The calculated bandgaps for
different structures are generally in the range of 0.66 eV
(tetragonal) to 1.73 eV (monoclinic) and typically under-
estimate the experimentally observed bangaps. Fig. 3
shows a few representative examples of such calculations.
It is generally agreed that the top of the valance band arises
from oxygen p states, and the bottom of the conduction
band is mainly W5d states with some mixing with oxygen
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248 S.K. Deb / Solar Energy Materials & Solar Cells 92 (2008) 245–258
Fig. 2. Proposed new model for coloration in WO3 involving oxygen vacancies.
2p states. The bandgap is a sensitive function of W–O bond
length. Therefore, in WO3 containing oxygen vacancies,
there is a structural relaxation resulting in an increase of
W–W distance and changes in W–O splitting. Conse-
quently, the energy gap increases with the presence of
oxygen vacancies, which is consistent with the experimental
observation that in an amorphous system, the bandgap is
significantly larger. The structural distortion in WO6
octahedra can lead to the displacement of W-ion from
the center of the octahedron. This off-centering results in
lowering of the valence band and raising the conduction
band with a consequent increase in energy gap [27].
It is instructive to note that the calculation of oxygen-
deficient amorphous WO3 shows a significant number of
in-gap states, which may be responsible for coloration.
This is further substantiated by the experimental results
using electron energy loss spectroscopy [28] and X-ray
photoelectron spectroscopy [29] measurements, which
clearly show the presence of a localized state below the
Fermi level that is associated with the color center
formation (Fig. 4). It is also interesting that in a recent
study on valence-band PES spectra of Na.025WO3, there is
a peak at 2.5 eV below the Fermi level that disappears at
temperatures above 200 K. This is interpreted as due to
polaron formation at the valence-band edge of WO3 [30].
Clearly, there is a need for more theoretical work to
achieve better accuracy and to understand the role of
defects such as oxygen vacancies in a complex system such
as WO3.
3. Applications of WO3 for EC and related devices
Numerous applications of WO3 for EC and related
devices make it one of the most versatile materials. Some of
the applications that are addressed here include: (i) PV-
powered EC-smart windows, (ii) photoelectrochromic
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S.K. Deb / Solar Energy Materials & Solar Cells 92 (2008) 245–258
Fig. 3. Electronic structures and density of states in WO3: band structure of (a) monoclinic WO3 [24], (b) monoclinic WO3 containing oxygen vacancies
[24], (c) cubic WO3 [25], and (d) density of states in amorphous WO3 with two oxygen removed and two sodium added [23].
(PEC) devices, (iii) gas sensors, (iv) solar energy conversion
and storage cells (SECSC), (v) EC displays, (vi) nanoscale
WO3, (vii) high Tc superconductivity, (viii) hybrid
WO3–organic devices, (ix) tunable EC photonic crystals,
(x) electron and ion-beam lithography, and (xi) optical
recording and image storage.
3.1. PV powered EC-smart windows
An estimated 1.5% of the total cooling energy needs in
US buildings and 10–30% of the peak electric utility power
needs are caused by solar heat gain through windows. A
large fraction of the approximately 2 billion m2 of building
windows in the United States could benefit from the use of
a solar-gain control device such as an EC smart window. A
retrofit EC window with no external wiring and power
source provides the most desirable option. An integrated
photovoltaic-powered (PV–EC) window is the obvious
choice, particularly since PV technology is making a strong
inroad in building facades. Moreover, the operational
characteristics of both PV and EC technologies are
generally compatible. A small area of PV cells can provide
sufficient electric power to operate a large-area EC
window. During the past several years, we have been
exploring two different design options: (1) a side-by-side
PV–EC design [31] and (2) a monolithic PV–EC device [32].
It is relatively straightforward to connect a PV array to an
EC device in the side-by-side configuration, but a tandem
249
structure offers more technological challenge in terms of
functional parameters of the device.
3.2. Monolithic PV–EC device
The monolithic, tandem PV–EC device, shown in Fig.
5(a), requires a transparent PV coating that still outputs
enough voltage to drive the EC device and enough current
to operate the device at a reasonable speed. For the EC
device currently employed, a 25-mC/cm2 charge is required
to finish a darkening or bleaching process. To darken the
window in 5 min requires only about 0.1 mA/cm2 current
density from the PV device. This gives room to increase the
bandgap and reduce the thickness of a standard terrestrial
PV device in order to reach a reasonable bleached-state
transparency. The device employs a wide-bandgap aSiC:H
n-i-p PV cell as a semitransparent power source and a Lix
WO3/LiAlF4/V2O5 EC device as the optical modulator.
Fig. 5(b) shows the transmittance spectra of a 16-cm2
monolithic PV–EC device. It is colored by short circuiting
the top and bottom transparent electrodes under 1-sun
illumination and is bleached by applying 2 V with a
polarity that forward biases the PV device. These spectra
are shown in the two upper curves of Fig. 5(b). The bottom
curve shows a more deeply colored state obtained by
applying 0.6 V of external coloring voltage to augment the
1-sun PV voltage. Our PV–EC device shows a relative
transmittance change of more than 60% at 670 nm under
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250 S.K. Deb / Solar Energy Materials & Solar Cells 92 (2008) 245–258
Fig. 4. (a) Energy loss spectra of WO3, — sputtered and . . . . . evaporated
[28]. (b) XPS of WO3 films colored by UV irradiation [29].
1-sun illumination and an 80% change when the small
external voltage is applied. The deeper coloration with the
external voltage indicates potential to improve the device
contrast by either designing for higher PV voltage or
improving the EC device. The absence of a middle
conductor in this device requires that both coloring and
bleaching current flow through the PV and EC device all
the time. Therefore, the 2 V bleaching voltage includes the
part required to overcome a built-in potential from the PV
device (about 0.8 V). In the final retrofit EC window
structure, a middle contact layer will be inserted for user
control and the option of PV battery charging.
3.3. PEC device
A dye-sensitized solar cell electrode was recently
combined with an EC film to produce what is known as
a PEC window [33]. In this case, rather than combining an
essentially complete PV cell with a complete EC cell (as in
the tandem arrangement discussed above), a much simpler
configuration was possible. Because of the complementary
Fig. 5. Monolithic PV–EC smart window: (a) schematic structure and (b)
coloration and bleaching spectra.
nature of the two technologies, we were able to combine
just one-half of a typical dye-sensitized solar cell with one-
half of a typical EC cell, as shown in Fig. 6(a). The EC film
was deposited on the counterelectrode of a dye-sensitized
solar cell and lithium ions were added to the electrolyte
solution. The I2 required in the electrolyte for high-power
solar cells was eliminated in order to maximize the
photovoltage, and a low concentration of a more trans-
parent dye was employed as the sensitizer. In this
configuration, the photovoltage produced by the dye-
sensitized electrode drives electrons and compensating Li+
cations into the WO3 film, resulting in a colored EC film, as
shown in Fig. 6(b). The coloration process is equivalent to
charging a battery; the photovoltage generated by the dye-
sensitized electrode is used to charge the EC layer.
The self-powered PEC cell has several advantages over
the use of conventional PV for large-area window or
display applications. It is a simple device that is easily
assembled without electrical short circuits. The light-
absorbing dye layer can be made optically thin by either
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S.K. Deb / Solar Energy Materials & Solar Cells 92 (2008) 245–258
Fig. 6. Photoelectrochromic device using dye-sensitized TiO2 and
electrochromic WO3: (a) schematic diagram and (b) spectra of colored
and bleached state [33].
reducing the thickness of the TiO2 layer or by decreasing
the concentration of the adsorbed dye. However, because
there are only two terminals, there would be lesser user
control compared with the EC window device reported
above. Another significant advantage of this device is that
it can be used as a pure photochromic device, as an EC
device, or as a hybrid of the two.
3.4. Gas sensors
Hydrogen fuel holds the greatest promise of all because
it is an abundant, non-polluting source of energy. H2 will
find a wide range of applications ranging from electric
power generation to fueling the future generation of
transportation vehicles. From the safety point of view in
the generation and handling of H2, it is important to have a
reliable, sensitive, and economical detector system. It is
well known that atomic H reacts with WO3 in a reversible
manner and changes its optical and electrical properties
somewhat analogously to the EC phenomenon in WO3. Ito
and coworkers first suggested the use of this chemichromic
effect for the design of a fiber-optic H2 detector system [34].
Based on this idea, NREL has carried out a systematic
study of the reaction of WO3 with H2 gas under different
conditions and concluded that a detector system based on
251
the induced absorption changes will not be sensitive
enough for most applications. However, it was possible
to significantly enhance the response characteristic of the
WO3 film by configuring it in such a way that a surface
plasmon resonance (SPR) occurs at a certain wavelength
[35]. The sensor coating consists of 40 nm Au or Pt/600 nm
WO3/3 nm Pd. The atomic H2 produced by the catalytic
effect of the Pd film produces a change in the dielectric
properties of the WO3 film, which shifts the wavelength of
the resonance absorption peak. The intensity of the
reflected light measured at or near the resonance wave-
length enhances the response speed of the detector. At the
resonance wavelength, the electric field of the incident light
interacts resonantly with the free electrons in the Au film
and initiates an electric charge oscillation at the glass/Au
interface. The wavelength at which the resonance occurs
depends on the dielectric constant of Au and WO3. When
the H2 reacts with the WO3, its refractive index changes
due to induced absorption, which results in the shift of the
resonance frequency. The reaction rate is enhanced
significantly by the Pd film due to its catalytic action. A
self-contained, portable fiber-optic sensor has been de-
signed and built at NREL. Light reflected from the sensor
coating on the distal end of the fiber is returned to the
instrument, and half of its power is directed through one of
the coupler legs to a dichroic mirror. The mirror splits the
return light beam into a short- and long-wavelength region
that falls separately on two different photodiode detectors.
When WO3 film reacts with H2, it develops an absorption
band in the new infrared region and remains unaffected in
the blue region of the spectrum. Thus, the long-wavelength
portion of the spectrum carries the H2 signal, whereas the
short-wavelength portion does not and can be treated as a
reference signal. Besides H2, a number of other environ-
mentally sensitive gases such as H2S, NOx, Cl2, O2, O3,
NH3, and organic vapors can be monitored using WO3 as
the sensor. The sensors are designed based on either the
changes in electrical conductivity or optical properties of
WO3 in the presence of different gases, and a large amount
of work has been done on this subject in recent years.
3.5. Chemichromic WO3 film for biosensor
Photobiological production of H2 by green algae is
actively pursued at NREL for the Hydrogen Energy
Program. One key research activity involves genetically
selecting mutants of the green alga Chlamydomonas
reinhardtii, which produce H2 from water under increasing
oxygen pressure. The current method for testing and
characterizing these mutants is laborious and is limiting
progress to develop a commercial biohydrogen organism.
Based on the chemichromic effect of WO3 film (coloration
and bleaching in the presence of H2 and oxygen,
respectively), we have developed a screening procedure
that rapidly identifies those H2-producing mutants with
enhanced O2 tolerance [36]. We have successfully used this
technique to screen large numbers of C. reinhardtii colonies
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252 S.K. Deb / Solar Energy Materials & Solar Cells 92 (2008) 245–258
and obtained clones with increased rates of H2 evolution
and greater tolerance to O2. This is our first step toward
identifying an H2-producing algal clone that is fully active
under atmospheric oxygenic conditions.
3.6. SECSC
In the past, a typical EC display device used white TiO2
pigment dispersed in ethylene glycol and H2SO4 as a
background electrolyte material. While studying the optical
response characteristic of this device, we observed that on
irradiation with UV light, the WO3 film in contact with
TiO2 turns blue even without applying an external electric
field, which was attributed to transfer of photogenerated
electrons in TiO2 to WO3 film. This led to an extensive
research and development effort on a solar energy
conversion and storage device involving TiO2 and WO3,
and the results were documented in several US patents
Fig. 7. Some early developments of photoelectrochemical solar cells based
on TiO2 and WO3: precursors to Graetzel Cell (a) dye-sensitized TiO2 cell
(US Patent 4,080,488, 1978), (b) TiO2 thin-film cell (US Patent 4,117, 210,
1978), and (c) triple electrode storage cell (US Patent 4,118,546, 1978).
issued to Deb et al. in 1978. The energy conversion
efficiency of such devices was significantly enhanced by dye
sensitization of TiO2 and this, in many respects, is the
precursor of what is widely known as the Graetzel Cell [37].
Several device configurations of TiO/WO3 photoelectro-
chemical (PEC) solar cells described in US patents are
shown in Fig. 7. Recent successes in achieving high-
efficiency, dye-sensitized TiO2 solar cells have stimulated
interest in other oxide materials, such as WO3, which has a
very similar energy gap [38]. The interest is focused on two
types of PEC structures: one for photoelectrochemical
power generation and the other for splitting water for
hydrogen generation (see Fig. 8). In process one, the
photogenerated electron–hole pair is separated at the
interface, and electrons move through the semiconductor
electrode to the electrode and the external circuit. The hole
oxidizes the reduced form of the redox couple, which, in
turn, gets oxidized by electrons reaching the counter
electrode. As a result, no net chemical changes occur,
and this is the mechanism for all regenerative PEC devices,
including dye-sensitized TiO2 cells. Because the relative
position of the valence band and conduction band of WO3
is similar to TiO2, it is, in principle, possible to design a
PEC device similar to the TiO2-based system using WO3 as
Fig. 8. Operational principle of photoelectrochemical solar cells: (a)
photogeneration of electricity and (b) photogeneration of hydrogen by
water splitting.
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S.K. Deb / Solar Energy Materials & Solar Cells 92 (2008) 245–258
the electrode material. The second type of device uses two
redox systems in which one reacts with the holes at the
semiconductor surface and the other gets reduced by
electrons at the counter electrode. In the example cited, the
water is used as a redox system, in which case H2O is
oxidized to O in semiconductor electrodes and gets reduced
Fig. 9. Tandem cell involving TiO2 and WO3 for photocatalytic water
decomposition [38].
Fig. 10. Hybrid photoelectrode device incorporating sputtered WO3 film and amorphous silicon tandem cell: (a) tandem device structure and (b) solar to
hydrogen conversion efficiency [39].
253
to hydrogen in the other electrode. An alternative
approach shown in Fig. 9 involves a tandem cell of WO3
and TiO2 in which the top cell is nanocrystalline WO3,
which absorbs near UV photons; the bottom cell is dye-
sensitized TiO2 which absorbs visible photons; and the net
result is splitting H2O into H2 and O2. Another interesting
device is the one developed by Miller et al. [39], who
developed a hybrid photoelectrode device incorporating
sputtered WO3 film and amorphous silicon (in a config-
uration shown in Fig. 10) and achieved solar to H2
conversion efficiency of 3.1%. A very interesting aspect of
this work is that the bandgap of WO3 can be modulated
from 3 to 2.1 eV by alloying with a small percentage (3%)
N2 or by alloying WO3 with MoS2. This can have a
significant effect on the use of WO3 as a photoelectro-
chemical energy conversion and an energy storage device.
A small concentration of N2 in III–V semiconductors also
shows a similar bandgap modulation and understanding
the effect of N2 doping has been a topic of great scientific
interest in recent years.
3.7. EC displays
Significant advances were made in EC display technol-
ogy in the 1970s and 1980s with primary emphasis on
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254 S.K. Deb / Solar Energy Materials & Solar Cells 92 (2008) 245–258

developing watch and clock displays. The EC display is one
of the most superior displays and is ideal for many
applications. As shown in Fig. 11, we fabricated in the
mid-1970s an EC display for watches and then made the
first digital watch. However, major limitations were speed
and lifetime. Cycling lifetime of more than 5 million
cycles and response time of a fraction of a second were
achieved. This is adequate for many display applications in
areas that do not require very rapid updating of display
information.

Fig. 11. Typical electrochromic display or digital watch applications.

Fig. 12. (a) TEM image of HWCVD-generated WO3 nanoparticles; (b) SEM image of WO3 nanoparticle films deposited by electrophoresis; (c)
current–voltage characteristic of a PEC device; and (d) stability characteristics [41].
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S.K. Deb / Solar Energy Materials & Solar Cells 92 (2008) 245–258 255

3.8. Nanoscale WO3

Crystalline nanoparticles consisting of nanorods and

nanospheroids have been successfully fabricated by a hot-
wire chemical vapor deposition (HWCVD) process [40] and
also by a chemical hydrothermal process. Thin films of
crystalline WO3 nanoparticles have been deposited by
electrophoresis on substrates suitable for large-area EC
applications. Compared with conventional amorphous
WO3 films, the crystalline WO3 nanoparticle films show
greater charge density for proton intercalation and
comparable coloration efficiency. The improvements in
the EC properties of these nanoparticle thin films have
been attributed to a larger active surface area and to the
low density of the films. The nanoparticle films exhibit
excellent cycling stability in 1 M H2SO4, with values greatly
surpassing those for amorphous WO3 films (Fig. 12). These
nanoparticle oxide materials have improved response times
because of their stability related to proton insertion when
compared to conventional EC electrode materials [41].
These results will significantly impact current EC technol-
ogies and have promising implications for the development
of novel batteries.

3.9. High Tc superconductivity

It is well known that single crystals of NaxWO3 show

metallic behavior when xX0.3 and become superconduct-
ing at sub-liquid helium temperature. Sheet superconduc-
tivity at 3 K in WO3x single crystals was discovered by
Aird et al. [42]. It has recently been found that single
crystals of WO3 doped with Na at a concentration of 7%
show the formation of a superconducting phase at the
surface at a critical temperature of 91 K (Fig. 13) [43]. This
is quite exciting, because high-temperature surface super-
conductivity has been observed in a non-cuprate system for
the first time. Single crystals of WO3 can be doped with
alkali metals over a wide range of concentration to achieve
semiconductor-to-metal transition and also exhibit high
dielectric constants at low temperature. Therefore, it is not
surprising that surface superconductivity is observed in this
material. In fact, two-dimensional superconductivity was
predicted in materials having this property by Ginzburg
[44]. It would be very interesting to see if surface-induced,
high-temperature superconductivity can be observed in
thin film of crystalline WO3 doped with alkali metals.
3.10. Hybrid WO3/organic devices
A multicolor EC hybrid device consisting of WO3/
[Ru(bpy)3]2+/polystyrenesulfonate (PSS) was recently fab-
ricated by [45] on an ITO substrate electrodeposition from
a colloidal triad solution of orthotungstic acid [Ru(b-
py)3]2+ on PSS. This exciting approach opens up a new
vista of opportunities to fabricate a wide range of WO3-
based film hybridized with organic EC systems exhibiting
multiple color for displays and related applications.
Fig. 13. (a) Superconducting transition at 91 K in Na-doped WO3 single
crystal and (b) magnetic moment vs. temperature in bare- and gold-coated
single crystal of WO3 [43].
3.11. Tunable EC photonic crystals
Periodic modulation of the refractive index in a spatially
ordered dielectric material having a periodicity comparable
to the wavelength of light can create a photonic bandgap
(PBG) material, which can be designed to selectively
control the light transmission in any given wavelength
range. PBG materials that can operate in the visible and
near infrared, and whose bandgaps can be tuned con-
tinuously, are of great interest for many novel optical
devices. EC WO3, whose optical constants can be changed
continuously by the intercalation process, is particularly
suitable for fabricating such a tunable PBG material.
Recently, such a structure was fabricated by creating a
hexagonal close-packed arrangement of micropores in
amorphous thin films [46] and crystalline [47] WO3 by
using polystyrene template (Fig. 14). The ability to
continuously tune the PBG by intercalating WO3 with
Li+ ions was clearly demonstrated for the first time. This
exciting new development should be of great interest to the
photonic industry for designing novel optical devices.
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256 S.K. Deb / Solar Energy Materials & Solar Cells 92 (2008) 245–258
Fig. 14. SEM images of WO3 inverse opels: (a) No. 300, (b) No. 760, (c) reflection spectra, and (d) reflection peaks in (a) as a function of Li intercalation
[46].
Another interesting development, coupling of TiO2-
based photonic crystals to dye-sensitized solar cells to
enhance the photocurrent in the long wavelength region,
was demonstrated [48]. Tunable PGB in WO3 could be
used more advantageously for such a device.
3.12. Electron and ion-beam lithography
During the early days of our work on EC display devices
using thin films of amorphous WO3, we observed that the
colored film of WO3 is significantly less soluble, either in
acidic or alkaline solution, than the uncolored film.
Therefore, this can be the basis for a lithographic process
using thin films of WO3 as the resist material, particularly
for ultra-high-resolution devices. It has also been recently
observed that structural transformation of WO3 thin film
from amorphous to crystalline and vice versa by electron or
ion-beam irradiation can result in differential solubility of
WO3 thin film. Because the coloration in WO3 is an atomic-
scale phenomena, nanometer-scale resolution can, in
principle, be achieved using this phenomena limited only
by the wavelength of the exciting radiation or by the size of
the focused ion beam. In recent years, several papers have
been written on electron beam [49] and focused ion beam
lithography [50] using WO3 and MoO3 as the negative and
positive resist material, respectively. Features as low as
15 nm with aspect ratios up to 10 have been demonstrated.
Another application of this technique will be in the
fabrication of nanostructures for studies on quantum size
effects, as well as the fabrication of photonic lattices.
These, as yet, remain largely unexplored.
3.13. Optical recording and image storage
High-density and reversible optical recording of infor-
mation was the original driving force for developing
photochromic and EC phenomena in inorganic materials
such as transition metal oxides. The first such devices
involved a combination of EC and photoconductive
(EC–PC) thin films, which led to a novel high-resolution
electrophotographic image recording system. It was also
shown that a write-once image could be recorded by
applying an electric field through a fine-probe in WO3 thin
film deposited on a conducting substrate. In recent years,
there has been renewed interest in developing optical
recording systems that use either magneto-optical or phase-
change phenomena in the recording medium. It has been
shown recently that an amorphous WO3 thin film can be
colored by a single pulse of KrF excimer laser at 248 nm
and bleached by a single pulse of Nd-Y-Al-garnet laser at
1.06 mm in air [51]. It is interesting to note that a purple
color (instead of the usual blue color) was formed in WO3
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S.K. Deb / Solar Energy Materials & Solar Cells 92 (2008) 245–258
film during this excitation process. Another approach that
takes advantage of the optical transmission changes
between the as-deposited and annealed states of WO3 film
has been used for optical recording of a write-once disk,
and a maximum storage density of 25 GB was demon-
strated [52]. Recently, we also reported a novel memory
effect in a proton-based WO3 EC device consisting of ITO/
WO3/Ta2O5/NiO2Hy/ITO [53]. We observed that visible
images can be recorded and can be repeated many times
over a period of months. This phenomenon has been
interpreted as due to enhanced H+-ion concentration in
the UV-irradiated area, which remains localized for a
long time, but eventually outdiffuses with loss of the
memory effect.
These are some of the diverse applications that are
related to the photochromic, EC coloration, and gaso-
chromic phenomena exhibited by WO3. Moreover, WO3
and its mixed oxides have been extensively studied as
heterogeneous catalysts for a large number of chemical
reactions, the dynamics of which can be changed by the
coloration phenomena.
4. Future research issues and opportunities
The opportunities for research on this unique material
can be conveniently discussed under two categories: (1)
fundamental research and (2) applied research. Some key
research issues under fundamental research are: (i) more
accurate EC structure calculations of both amorphous and
crystalline materials; (ii) understanding the mechanism of
the coloration phenomena; (iii) quantitative understanding
of the role of structural defects and impurities; (iv)
dynamics of the coloration processes using advanced
characterization tools; (v) transport properties associated
with the coloration and intercalation processes that lead to
insulating-semiconducting-metallic-semiconducting
transitions; (vi) fundamental understanding of materials
and device properties; and (vii) growth of high-quality
single crystals of WO3 (stoichiometric and non-stoichio-
metric) for baseline studies. In the realm of applied
research, key issues are: (i) modeling of the diverse range
of devices discussed above; (ii) novel device designs for
specific applications; and (iii) performance optimizations
and device stability.
5. Conclusion
After four decades of extensive R&D on the EC
properties of a variety of metal oxides, WO3 still remains
the leading EC material. Major advances have been made
on the fabrication and characterization of structural,
optical, and electrical properties of WO3-based EC
materials and devices. The mechanism of EC effect in
WO3 is still not definitively understood, even though
several models have been developed. After decades of
technology development effort, the EC smart window has
finally reached the marketplace. WO3 is one of the most
257
versatile materials, and offers a wide range of applications
and intriguing opportunities for both basic and applied
research.
Acknowledgment
The work presented here is supported by the US DOE/
Offfice of Energy Efficiency and Renewable Energy under
Contract #DE-AC-36-99GO1033.
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