ARTICLE IN PRESS

Vacuum 82 (2008) 730–735

www.elsevier.com/locate/vacuum

Switchable windows with tungsten oxide

Andreas Georg, Anneke Georg, Wolfgang Graf, Volker Wittwer
Fraunhofer Institute for Solar Energy Systems, Heidenhofstr. 2, 79110 Freiburg, Germany
Received 18 March 2007; received in revised form 15 October 2007; accepted 31 October 2007

Abstract

Tungsten oxide can change its colour reversibly upon electron injection. It can be produced by sputtering, evaporation, chemical
vapour deposition or other processes. In addition to its high colouration efficiency and fast reaction kinetics, the redox potential of the
electron injection is low enough to allow various switchable systems, such as electrochromic, gasochromic, photoelectrochromic or
photochromic glazing. In this paper, electrochromic devices with a redox electrolyte are introduced. This is related to the
photoelectrochromic device, which is an electrochromic device with redox electrolyte and an additional dye-sensitised layer of TiO2,
which generates the energy for the colouration of the device by sunlight. The photochromic device is in principal a photoelectrochromic
device, where the catalytic layer for the reaction of the redox electrolyte is in direct contact with the electrochromic layer. In gasochromic
devices, tungsten oxide reacts with diluted hydrogen and oxygen gases. This paper aims to give an overview of these different approaches.
r 2007 Elsevier Ltd. All rights reserved.

Keywords: Gasochromic; Electrochromic; Photoelectrochromic; Photochromic; Tungsten oxide; Smart windows

1. Introduction absorption in the near-infra-red [10]. In both cases, the

Tungsten oxide, WO3, is well known for its electro-
chromic property, i.e., to change its colour from transpar-
ent to blue, reversibly, upon electron injection [1,2].
Mostly, vacuum-coating processes such as sputtering,
evaporation or chemical vapour deposition [3–5] are used
to prepare thin layers with thicknesses of about 400 nm [6],
but other processes like sol–gel dip-coating are also
possible [7]. All these methods allow the generation of a
porous structure, which is important for a fast reaction,
and allow a modification of the redox potential, which is
important for the degree of colouration. The main reaction
of the colouration is a reduction of WO3, where the
additional electrons can be attributed to the tungsten
atoms [8]. In the case of amorphous or nanocrystalline
structure, the electrons are located close to the W atoms
and form small polarons, which create a broad absorption
band, centred in the near-infra-red [9]. In crystalline WO3,
the electrons are delocalised and form a free electron gas,
which causes high reflectance in the infra-red, and
Corresponding author. Tel.: +49 761 4588 59 93;
fax: +49 761 4588 59 81.
E-mail address: andreas.georg@ise.fraunhofer.de (A. Georg).
material appears blue and especially for mixed materials
with crystallites and amorphous phases, it may be difficult
to distinguish between these two mechanisms [11]. In
addition to the injected electron, a second charge transfer
has to occur in order for the material to remain neutral.
In the case of electrochromic devices, this is done by
incorporating a positive ion, usually H+ or Li+, from an
electrolyte. In the case of gasochromic devices, hydrogen as
a gas reacts with the layer and introduces electrons and
protons, where it is believed that the protons react with
oxygen, forming water and oxygen vacancies [12]. The
photoelectrochromic [13] and photochromic [14] systems
are special electrochromic systems, where the power for the
electron injection is generated by an additional photo-
voltaic layer, i.e. dye-sensitised TiO2.
2. Gasochromic devices
In gasochromic devices, a film of WO3 with a typical
thickness of about 400 nm is coated by a thin layer of a
catalyst like Pt with a thickness of about 1–5 nm. A high
porosity is beneficial for a fast switching. Fig. 1 shows a
SEM image of such a gasochromic coating. When flushed

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doi:10.1016/j.vacuum.2007.10.020
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A. Georg et al. / Vacuum 82 (2008) 730–735 731

100 without Al2O3

H
H H
H O O with Al2O3
O O
80

back reflectance / %
transmittance / %
transmittance
Pt Pt 60
Pt Pt

40
back reflectance
H
H O
O 20

h68.opj
0
HH++ ee -
-
400 500 600 700 800 900 1000 1100
wavelength / nm

Fig. 3. Transmittance and reflectance spectra of a gasochromic coating

(WO3) with and without an additional anti-reflecting layer (Al2O3).

600 type A
ISE 5.0kV 8.9mm x50.0k SE(U) 1.00um
type B
Fig. 1. SEM image of the edge of a gasochromic WO3 layer with a porous 400 type C

EMF vs. SHE / mV

microstructure. Also shown is the basic mechanism of colouring in type D
hydrogen (dissociation of H2, ionisation of H; left) and bleaching in
oxygen (dissociation of O2). 200

0
1.0 uncoated double glazed unit
Tsol=84.5%, Tvis=84.8%

0.8 -200
transmittance

0.00 0.05 0.10 0.15 0.20

0.6 bleached Tsol=76.3% Tvis=76.5%
X

0.4 Fig. 4. Electromotive force (EMF) or redox potential vs. standard

glass WO3 cat.
0.2
H2 / O2
0.0
0.5 1.0 1.5
wavelength in µm
Fig. 2. Typical transmittance spectra of a gasochromic double glazing
unit in the coloured and bleached states.
with diluted hydrogen, H2 is dissociated into H atoms on
the surface of the catalyst, which are ionised to form
protons and electrons at the interface between the catalyst
and the WO3. The electrons lead to a reduction of the
tungsten and in consequence to colouration. The protons
are believed to react with oxygen to form water and oxygen
vacancies [12]. For sputtered films, it is important to create
a high water content and porosity [15]. As the layer
configuration is very simple, this device allows high
transmittances (Fig. 2), which can be increased even
further by adding an anti-reflecting layer, such as Al2O3
(Fig. 3). It should be noted that for a thermally insulating
window, a low-e coated pane will usually be added,
forming a triple glazing unit, which reduces the transmit-
tance in the infra-red region. Also, when coming closer to a
real mass production with its higher priority on production
costs, the thickness of the WO3 layer may be kept thinner
glass
hydrogen electrode (SHE) for sputtered (types A–C) and evaporated
coloured
films (type D) of WO3, measured electrochemically, as a function of the
Tsol=5.0% Tvis=5.9
degree of colouration, where X represents the number of injected electrons
per W atom.
2.0
as it is possible from the technical point of view, which
reduces the depth of colouration. Typical values of the
transmittance for such a prototype close to mass produc-
tion are 67% and 38% for visual and solar transmittance in
the bleached state, respectively, and correspondingly, for
the coloured state, 12% and 7% for visual and solar
transmittance, respectively [16]. For such a device, the total
solar energy transmittance was measured to be 47% for the
bleached state and 17% for the coloured state.
It is possible to evaporate or sputter this gasochromic
coating selectively onto certain areas of microstructures,
which allows specific switching properties to be designed
[17]. Mixtures of tungsten oxide with molybdenum oxide
lead to a more neutral colour, i.e. grey-blue. It should be
observed that the redox potential of the gasochromic layer
must be above the normal hydrogen electrode, otherwise
colouration by hydrogen gas is not possible thermodyna-
mically. Most of the electrochromic materials have a lower
redox potential and therefore cannot be coloured
with hydrogen gas. Different methods of preparation of
the WO3 film allow a modification of the redox potential
(Fig. 4) [18]. A higher content of O–H, H2O, W–O–H and
 ARTICLE IN PRESS
732 A. Georg et al. / Vacuum 82 (2008) 730–735
W ¼ O bands, as visible by IR spectroscopy, are correlated
with a lower redox potential, which, in principle, leads to a
lower degree of colouration in equilibrium. The series of
films in Fig. 4 (A–D) follow this order of content of
impurities. Details of the film preparation are given in [18].
However, the kinetics is too slow for the films with low
water content, types C and D, due to the diffusion of
protons along the internal surfaces of pores being too slow
[15]. The degree of colouration in equilibrium is determined
by the equilibrium of the redox potential of the film and the
chemical potential of the hydrogen gas, which depends only
weakly, i.e. logarithmically, on the hydrogen partial
pressure. Reduction of the hydrogen concentration by a
factor of 10 reduces the chemical potential only by roughly
30 mV. This allows strong colouration to be achieved also
for low hydrogen concentrations, well below the combustion
limit, in particular. Gasochromic windows were installed in
various facades together with gas supply units, which
include an electrolyser and a pump and can be incorporated
into the facade. The simple coating configuration is most
advantageous for large areas, whereas for small areas the
need for a gas supply device may be disadvantage.
3. Electrochromic devices
Usually, the layer configuration for electrochromic
devices is considered analogous to a battery, consisting
of: substrate/TE/WO3/electrolyte/CE/TE/substrate, where
TE represents a transparent electrode such as F:SnO2 or
ITO, CE represents a counter-electrode with similar
properties to WO3, like V2O5 or NiOxHy. The electrolyte
usually conducts Li+ ions, which are shifted reversibly
from the left to the right electrode by application of an
external voltage. In this paper, we want to focus on a
special system with a redox electrolyte, as this is related to
the photoelectrochromic and photochromic devices to be
presented below. The principle is shown in Fig. 5. An
external voltage injects electrons into the WO3 layer via a
transparent electrode. The incorporation of Li+ ions from
Glass TE WO3 electrolyte Pt TE Glass
I-
I3-
Li+
Fig. 5. Layer configuration and mechanism of an electrochromic device
with a redox electrolyte with I/I
3 as the redox couple (TE: transparent
electrode).
the electrolyte keeps the WO3 layer neutral. On the
counter-electrode, iodide emits electrons, forming tri-
iodide. This reaction is catalysed by Pt. Here again, thin
layers of 1–5 nm are sufficient, which keep the device
transparent. In principle, the tri-iodide may react back to
iodide, taking electrons from the WO3 layer. However, this
reverse reaction is very slow. The diffusion kinetics of the
Li+ ions in the WO3 are important for a fast reaction, and,
additionally, the rate of the reverse reaction has to be kept
low. It turned out that a certain sol–gel process yields good
layers [19], but sputtered coatings with good properties can
also be produced. Fig. 6 shows the transmittance spectra of
such an electrochromic device with a sputtered layer of
tungsten oxide, which was produced with similar para-
meters as for the gasochromic coatings. The electrochromic
setup allows to apply high voltages which lead to very deep
colourations, which is limited, generally, by the long-term
stability especially of the electrolyte. Especially, this high
contrast is typical for an electrochromic device with redox
electrolyte. In the more common battery-type devices, the
overall charge (and therefore also the overall colouration)
depends mostly on the charge capacity of the counter
electrode, as tungsten oxide has a very high charge
capacity. The charge capacity of the redox electrolyte
is much higher and therefore allows very high contrasts.
Fig. 7 shows the kinetics and the degree of colouration in
dependence on the applied voltage. Higher voltages lead to
a faster rate of reaction and a deeper colouration. As the
charge, which is incorporated into the WO3 layer during
colouring, has to be removed completely during bleaching,
the bleaching time increases with increasing voltages of
colouring. Already for the size of the sample, which was
used in Fig. 7 300  300 mm2, the limited conductivity of
the transparent electrode (pyrolitical F:SnO2 with a sheet
resistance of 12 O/square) becomes dominating for the
kinetics of the device, which is a common feature for
electrochromic devices. The general technological challenge
of electrochromic devices for window applications is that
bleached with +0.5V, Tvis=63%, Tsol=46%
coloured with -2.0V, Tvis=1.2%, Tsol=0.7%
0.7
0.6
0.5
Transmittance
0.4
0.3
0.2
0.1
0.0
0.5 1.0 1.5 2.0
Wavelength / nm
Fig. 6. Transmittance spectra of an electrochromic device with a redox
electrolyte in bleached and coloured state.
 ARTICLE IN PRESS
A. Georg et al. / Vacuum 82 (2008) 730–735 733

4 TCO WO3 TiO2 electrolyte TCO

with dye with Pt
voltage / V

2 I-

e-
0 I3-

Li+
70
60 I-
transmittance (655nm)

50 Li+ e-
40 I3 -

30
20
e-
10
0
0 10 20 30 40 50
Fig. 8. Work function of a photoelectrochromic device shown on SEM
time / min images of nanoporous WO3 and TiO2 layers produced by a sol–gel
method. The thickness of the electrolyte is not to scale.
Fig. 7. Measurement of the transmittance as a function of the time for
cycling at different voltages. Electrochromic device with redox electrolyte
of the size 300  300 mm2. 70

60
two electrodes have to be kept isolated over a large area, bleached
Tvis=62%, Tsol=41%
transmittance / %

avoiding a contact for electrons, but generating a good 50

contact for ions, which leads to thin electrolyte layers. The 40
gasochromic and photochromic devices avoid this demand.
30
4. Photoelectrochromic devices 20
coloured
10
In a photoelectrochromic device, an electrochromic and Tvis=1.6%, Tsol=0.8%
pecsol.opj
a dye-sensitised solar cell are combined. The layer 0
configuration is shown in Fig. 8. A layer of tungsten oxide 400 600 800 1000 1200 1400
is coated onto a transparent electrode such as F:SnO2. On wavelength / nm
top of this, there is a layer of titanium oxide. Both layers
Fig. 9. Typical transmittance spectra of a photoelectrochromic device in
are nanoporous. This can be achieved by sol–gel methods the bleached state (short circuit, no illumination) and in the coloured state
[13], but also by sputtering or evaporation. In all cases, the (open circuit, illuminated with solar simulator, intensity corresponding to
redox potential of the tungsten oxide must be adjusted to AM1.5).
the needs of the device. The counter-electrode is formed by
a thin layer of Pt on a transparent electrode such as
F:SnO2. The Pt layer can be sputtered in a similar way as As for gasochromic devices, only a few electrochromic
for the gasochromic device. Located between the electro- materials can be used in this device, as the redox potential
des, there is an electrolyte with Li+, I and I 3 ions. The must be above the Fermi level of the TiO2 in the dye solar
mechanism is similar to the electrochromic device as cell. WO3 turned out to be a suitable material, as its redox
described above, but now the energy for the process is potential is not too low to allow colouring but it is also not
provided by illumination, which excites the dye to inject too high compared to the I/I 3 couple, if it is prepared in
electrons via the TiO2 to the WO3. In parallel, I is the right way. Furthermore, the loss reactions due to the
oxidised on the dye and Li+ ions are incorporated from the reverse reaction of the I3 are slow.
electrolyte into the WO3. This process can be reversed by No external power supply is needed, but the same
closing the connection to the Pt counter-electrode, where technological demands apply as for electrochromic devices,
the reverse reaction, i.e. the reduction of I 3 to I

is i.e. one has to separate two electrodes over a large area by a
catalysed. In this way, the device colours under illumina- small distance such that they are electronically isolated but
tion, but can be bleached by closing the connection ionically connected.
between the two electrodes. This device can work as an
electrochromic device, i.e. being coloured and bleached by 5. Photochromic devices
an external source of power. The corresponding transmit-
tance spectra with and without illumination (corresponding This problem does not occur if the two electrodes are
to AM1.5) are shown in Fig. 9. connected intentionally, forming a photochromic device.
 ARTICLE IN PRESS
734 A. Georg et al. / Vacuum 82 (2008) 730–735

One possible implementation is with the Pt layer between
the F:SnO2 layer and the WO3 layer of the photoelec-
trochromic device. Of course, other configurations are
possible, in which the dye, the TiO2, the WO3 and the
electrolyte are mixed within one layer. Fig. 10 shows the
first case in action, i.e. the change of the transmittance,
plotted logarithmically, upon illumination (corresponding
to AM1.5) and in darkness, compared with a photoelec-
trochromic device with similar layers. The colouring
process is identical, as could be expected. It is astonishing
that the equilibrium for colouration of the photochromic
device is not far below that of the photoelectrochromic
device. The bleaching is slightly slower for the photo-
chromic device, which could be expected, but is not as slow
as could be feared.
One important disadvantage of other photochromic
materials, as used, e.g. in sunglasses, is that the colouration
depends strongly on the temperature. This is especially
disadvantageous for window applications, as in summer,
when the temperature is high, the colouration is weak, and
in winter, when the temperature is low, the colouration is
high. This cannot be avoided totally, as the colouration of
a photochromic device is always determined by the ratio of
the rates of colouring and bleaching reactions, which
depends on temperature. However, for our photochromic
system, the temperature dependence was shown to be quite
moderate, as demonstrated in Fig. 11. Therefore, this
device is suitable for window applications, both for vehicles
and for buildings. Of course, the advantage of a simple
layer configuration has its price in constituting a device,
which cannot be influenced arbitrarily.
6. Conclusion

Different types of switchable windows including WO3 as

the electrochromic material have been presented. Typical
photochromic
values for tranmittance in bleached and coloured state are
photoelectrochromic
summarised in Table 1. The gasochromic device is most
1.5 advantageous for large areas, as the coating structure is
-log (transmittance)

very simple. Electrochromic and photoelectrochromic

devices have to separate two electrodes, preventing an
electron-conducting contact but allowing an ionic contact.
1.0
Electrochromic device allow high contrasts, as high
potentials may be applied. This is especially true for
electrochromic devices with redox electrolyte, where
0.5 counter electrode layer not limits the overall colouration.
Photoelectrochromic devices do not need any external
power supply, as they use the energy of the sunlight.
0 5 10 15 20 25
Photochromic devices based on WO3 are simple in their
time / min
coating structure and are applicable for windows in cars or
Fig. 10. Colouring and bleaching of a photochromic device in comparison buildings. In particular, their colouration is only weakly
with a photoelectrochromic device using similar layers. dependent on temperature, which is in contrast to common
photochromic materials. However, they cannot be switched
arbitrarily. For all devices, the WO3 can be produced by
70 physical vapour deposition processes. Especially for the
60 gasochromic, photoelectrochromic and photochromic de-
bleached
vices, it is of importance to adjust the redox potential of the
transmittance / %

50 WO3 layer by the coating process.

40

30 Table 1
Typical transmittance values for visual and solar transmittance for
20 coloured 40°C different devices
10 coloured 0°C
Tvis Tsol Tvis Tsol
0 bleached bleached coloured coloured
(%) (%) (%) (%)
400 600 800 1000
wavelength / nm Gasochromic double glazing 77 76 6 5
Gasochromic triple glazing 61 38 12 7
Fig. 11. Transmittance spectra of a photochromic device at different (with low-e coating)
temperatures in the bleached state (no illumination, Tvis ¼ 60%, Electrochromic glazing 63 46 1.2 0.7
Tsol ¼ 40%) and the coloured state upon illumination (corresponding to Photoelectrochromic 62 41 1.6 0.8
AM1.5) at high temperature (ambient air 40 1C, window 57 1C, Tvis ¼ 6%, glazing
Tsol ¼ 2.4%) and low temperature (ambient air 0 1C, window 16 1C, Photochromic glazing 60 40 6 2
Tvis ¼ 4%, Tsol ¼ 1.8%).
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A. Georg et al. / Vacuum 82 (2008) 730–735
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