Energy Efficiency through Electrochromism and Gasochromism of

Tungsten Oxide Films

Justin Ritchie EECE 580 03.17.2010

Abstract – Options for energy efficiency through
modulating thermal throughput into built structures
by harnessing the electrochromic and gasochromic
properties of tungsten oxide films are surveyed.
Commercially available electrochromic windows are
analyzed based on reported performance.
I – Purpose
As the net energy available to society from inexpensive
oil extraction rapidly declines in North America [1] and
internationally [2][3], an important focus must be placed
on developing robust technologies that can enable a fast
transition towards successful and necessary local
resilience [4].
Smart windows (SW) are devices harnessing
electrochromic properties, gasochromic properties and
liquid crystals to vary throughput of solar radiation and
visible light. [6] 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. [7]
Figure 1 - Demonstration SW Tinting [8]
Considering that efficiency gains cascade up the chain of
electricity distribution, a quick calculation demonstrates
the importance of reducing energy use “from windows”.
The average North American home uses approximately
12,000kWh/year and about a third of that goes towards
air conditioning use.
energy is heavily subsidized by cheap oil. The need for
energy efficiency has never been greater.
II - Electrochromism
Chromic materials can change color or opacity reversibly
when their environment changes. A material exhibits
electrochromism when its optical properties change
reversibly as an external potential is applied.
This phenomena was discovered in 1953 but did not
receive widespread scientific interest until 1969 [9] The
general form of the reaction by which electrochromic
materials change their optical properties is through
switching between their oxidized and reduced form,
a material absorbs an electron and
is reduced or is oxidized losing an electron.
Typical electrochromic devices consist of a glass or
plastic coated with a transparent conductive film on
which several electroactive layers are added (Figure 2).
[10] The center of this device is made of an electrolyte
which must be a good conductor for H+ or Li+ ions. The
electrolyte contacts the electrochromic layer and an
electrode. When a voltage is applied between the outer
layers, ions diffuse from the electrolyte and draw
electrons into the porous electrochromic oxide layer. The
introduction of electrons to the electrochromic oxide is
considered the simplistic mechanism for modifying its
optical properties.

Converting this value into Joules, we see that an 80%

efficient air conditioning unit operated through an
electrical grid that is 90% efficient and a power plant
that is 30% efficient requires 66,853 MJ to supply
4,000kWh with centralized distribution, transmission
and generation. Commonly burned bituminous coal has
an energy density of approximately 20MJ/kg leaving us
to estimate that 3.43 metric tons of coal is burned to
supply a single year of air conditioning to a single house.

This magnitude of annual coal consumption for a large

portion of North America‟s households has serious
Figure 2 - Typical Electrochromic Device [10]
implications for anthropogenically exacerbated climate
change and for sensitivities to price shocks from
disrupted oil supplies because fossil fuel generated
Electrochromism is commonly found in the transition
metal oxides. (Figure 3) This property is not only useful
for smart windows but also variable reflectance mirrors
and information displays when a white pigment is
present on the backside of the electrochromic material.
Incorporating electrochromism into a device is heavily
dependent on the principle of intercalation, the
reversible inclusion of a molecule between two other
molecules. [12] For commercial application in
electrochromic windows (ECW), optical properties are
modified by ion intercalation or ion deintercalation
Figure 3 - Periodic Table Overlaid with Electrochromic
Materials [10]
For electrochromic materials in general, the class of
electrochromic material is determined by whether
coloration is driven by intercalation or deintercalation. If
the material darkens under ion intercalation then it is
classified cathodic coloration, under ion deintercalation
then it is anodic coloration.
III – Performance Metrics of Electrochromic
Devices
The key performance metric for an electrochromic film is
obtaining high coloration efficiency, meaning that for a
practically realizable change in electron density, the
change in optical modulation must be large enough.
While liquid crystal chromic devices are field driven by
µC cm-2, electrochromic devices are driven by charges on
the order of mC cm-2 [14]
The coloration efficiency at a particular wavelength can
be calculated as,
( )
where ε is the molar extinction coefficient in (L M-1 cm-1),
n is the electron stoichiometry (H+/e− ratio) and F is
Faraday‟s Constant (96485.3399 C mol-1)
The main limiting factor in building large scale
electrochromic devices is maintaining low resistivity
over the transparent conductor.
Transmittance is a measure of the fraction of incident
light at a specified wavelength that passes through a
given sample. (Figure 4)
and
IV - Electrochromic Tungsten Oxide
The most frequently investigated electrochromic
material is tungsten oxide (WO3) and was the source of
the original discovery of the phenomena.
Figure 4 - Visual Depiction of Beer-Lambert Law the
Beer-Lambert Law States I=Io e-αl
For a typical 1um-thick tungsten oxide film deposited on
glass, the application of a DC electric field of 104 V cm-1 at
room temperature will drive coloration originating at the
cathode, propagating slowly towards the anode.
Migration of the coloration is on the range of 3.0 x 10-7
cmV-1 s-1. No electrocoloration occurs by this method in a
vacuum so it is theorized that moisture plays a role in the
phenomena. Electron mobility is highly dependent on
the degree of coloration; electronic conductivity is small
compared to the ionic conductivity.
Coloration is highly structure sensitive with a peak
absorption at 1.2eV for amorphous WO3 and .7eV for
crystalline. The highest coloration efficiency occurs in
highly disordered amorphous films while fully crystalline
films fail to show any coloration unless they were
prepared under high temperature in a vacuum.
Reversible color changes in WO3 can also be induced by
thermal, optical, ionizing radiation, heating in a vacuum
along with others. [7] The sheer number of contradicting
circumstances for coloration in WO3 films makes the
actual mechanism very difficult to place in a single
model.
The simplistic mechanism for coloration can be
represented by the reaction, ( )
 ( ) where M+ can be H+,
Li+, Na+ or K+, 0<x<1 and e- represents electrons.
Undoped WO3 turns blue. [6]
If the window area is small, the EC will switch faster
because the distance between the transparent conductor
layers is small. For an 18-inch distance between bus
bars, the fastest switching time is between 1-4 minutes
under sunny and/or hot conditions.
In an ECW device a voltage is applied between
transparent conductors providing a distributed electric
field moving ions in and out of the electrochromic WO3.
To balance the charge, electrons flow through WO3 layer
providing the coloration change. A poorly conducting
ionic electrolyte yields an open circuit memory for a
device. The rate of intercalation depends largely on the
film structure as well as the mobility of the inserted
atoms. The rate limiting step during the coloration
period is proton transfer across the barrier at the
electrolyte-W03 interface.
Polaron formation may be the mechanism of
electrochromism in WO3, first proposed in 1933 by
Landau. [13] The electron together with its
accompanying polarization field is known as a polaron.
Small polarons are formed when excess electrons
polarize their surrounding lattice so that localization of
the wave function takes place essentially to one lattice
site. Ion intercalated disordered tungsten oxide films
contain W atoms in W6+ and W5+ states. Absorption
occurs as polarons hop between neighboring W sites, in
this case denoted i an j,
Excess energy during this photon-assisted hopping is
given off as phonons. A phonon is the quantization of the
modes of lattice vibrations of periodic of a crystal.
Optical absorption can be explained using the potential
energy of the electron-lattice system shown in Figure 5.
Figure 5 – Plot of energy v. lattice configuration [7]
These parabola represent energy along a coordinate (q)
passing through W sites (i,j). Up is the energy gained by
polarizing the lattice and v represents the energy spread
caused by inequivalence along the energy sites resulting
from the presence of polarons. Optical transitions are
represented by the heavy arrow in this diagram
corresponding to an energy 4Up using the Franck-
Condon principle, that transitions between electronic
states correspond to vertical lines on an energy vs.
internuclear distance diagram.
The bulk unit structure of WO3 is of WO6 octahedra with
the central metal atom surrounded by equidistant
oxygen atoms. The spacing of the crystal lattice must be
such that ions can reside in the spaces between the WO6
octahedra.
WO3 has a number of phases from simple cubic to
monoclinic to orthorhombic to tetragonal to triclinic
which makes all modeling incredibly complex. WO3 is a
semiconductor and superconducting behavior at 91K has
been observed in Na and K doped WO3. Bandgaps for
WO3 generally range between .66eV (tetragonal) to
1.73eV (monoclinic).
For commercial applications, WO3 films are prepared
via condensation of a vapor produced by sublimation
from a hot WO3 powder and crystalized as amorphous.
Glass substrates are nearly always used but similar
methods can evaporate WO3 onto a flexible polymer.
Typically deposition rates are between 3nm/s – 7nm/s
[12] Tungsten oxide films can also be prepared through
sputtering and chemical vapor deposition. [7]
Figure 6 - WO6 Hexagonal Structure [12]
Electrochromic devices incorporating WO3 have
coloration efficiencies on the range of 20-40 cm2 C-1.
Transmittance tends to range for large devices between
Tsol .74-.18.
V – Gasochromic WO3
As mentioned briefly above, the coloration mechanism of
WO3 is not limited to applied electric potential. WO3
can reach a colored or bleached state by applying H2 gas.
The incorporation of gasochromism avoids the need for a
transparent conductor. As shown in Figure 7,
dissociation of H2 into 2H is catalyzed by Pt. The
reaction leading to the formation of color centers occurs
on the internal pore surfaces after diffusions by protons
along the pores in the presence of water. Color centers
are atomic and electronic defects of various types which
produce optical absorption bands in otherwise
transparent crystals and arise from variations in
localized states. These localized states are brought about
by the association of H+ with O in the following picture.
Small amounts of water form in this reaction. Bleaching
is brought about by exposing the film to oxygen,
restoring the structure.
2-3 10-24
Memory 1-12 hours
Cycle Lifetime >104-106 cycles (5-20yrs)
The price must be in the range of $500/m2 and the size
must be able to approach 3 x 2 m2. No gasochromic
windows are currently commercially available.
SAGE Electrochromics (NY, USA), Econtrol-Glas
(Germany) and Gesimat (Germany) all use WO3 as an
electrochromic material in their commercially available
smart windows.
VII – Commercial Performance
SAGE and EControl-Glas both can produce large area
windows of 1.6 and 2.6m2 but fall short of the desired 2-
3m2. These ECW operate at 5V DC with a power
consumption of .5Wh/m2 so they are suitable for energy
conservation purposes. These devices meet requirements
for Tvis but tend to be a little dark. SAGE and Gesimat
offer 10 year guarantees on their windows while
EControl-Glas guarantees 105 cycles.

The solar factor (SF or g-value) measures the percentage

of heat that passes through the glass. A g-value is a ratio
of primary transmittance plus secondary transmittance;
the ratio of solar insolation flux through the window‟s
Figure 7 - Mechanism for Gasochromism in WO3
surface area plus the percentage of solar insolation
absorbed in the window frame.
( ) ( )
Size
Tsol Tvis SF Cycles
Using this method, devices of .6 x 1.1m2
have been built (cm2)
SAGE
.40- <.62-
and tested across 20k cycles over three years. 108 x 150
.015 .035
.48 105
Transmittances of Tvis=.77-.06 have been achieved and
.26-
can be cycled between the two states over 20 seconds. EControl 120 x 220 .50-.15 N/A 10yr
.12

VI –Commercially Available ECW Gesimat 80x 120 .52-.06 .75-.08 N/A N/A
Commercially viable ECW must adhere to the following
requirements as established by industry surveys and
decades of experience: [6] VIII –Transparent Conductors
The primary factor holding back ECW deployment
Bl Col centers around dependence on indium-tin-oxide (ITO)
Tsol .50-.70 .10-.20 as the primary transparent conductive (TC) electrode.
Solar Transmittance
Tvis .50-.70 <.10-.20 Because supplies of ITO are limited, the global economy
could run out of indium (which is a by-product of zinc
Solar Reflectance Rnir .10-.20 >.70
mining) in the next 10 years [6][18]. Responding to such
a shortage, the price of ITO has risen from
approximately USD $100/kg to nearly USD $1000/kg in
the past 6 years.
Switching Voltage Small Large
Developing a widespread SW market will require TC
solutions. An alternative to ITO includes Poly(3,4-
ethylene-dioxythiophene) (PEDOT) which has a high
transmittance (.90) and a sheet resistance of less than
400Ω/, PEDOT tends to degrade under light and heat
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