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ANNUAL
REVIEWS Further Electrochromic Materials
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Roger J. Mortimer
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Other articles in this volume Department of Chemistry, Loughborough University, Loughborough, Leicestershire,
Top cited articles LE11 3TU, United Kingdom; email: R.J.Mortimer@lboro.ac.uk
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Annu. Rev. Mater. Res. 2011. 41:24168 Keywords


First published online as a Review in Advance on metal oxides, viologens, conjugated conducting polymers, metal
March 30, 2011
complexes, Prussian blue
The Annual Review of Materials Research is online at
matsci.annualreviews.org Abstract
This articles doi: Electrochromic materials have the property of a change, evocation, or
10.1146/annurev-matsci-062910-100344
bleaching of color as effected either by an electron-transfer (redox) process or
Copyright  c 2011 by Annual Reviews. by a sufcient electrochemical potential. The main classes of electrochromic
All rights reserved
materials are surveyed here, with descriptions of representative examples
1531-7331/11/0804-0241$20.00 from the metal oxides, viologens (in solution and as adsorbed or polymeric
lms), conjugated conducting polymers, metal coordination complexes (as
polymeric, evaporated, or sublimed lms), and metal hexacyanometallates.
Examples of the applications of such electrochromic materials are included.
Other materials aspects important for the construction of electrochromic de-
vices include optically transparent electrodes, electrolyte layers, and device
encapsulation. Commercial successes, current trends, and future challenges
in electrochromic materials research and development are summarized.

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MR41CH10-Mortimer ARI 27 May 2011 14:1

INTRODUCTION
Electrochromic materials have the property of a change, evocation, or bleaching of color as effected
Electrochromic either by an electron-transfer (redox) process or by a sufcient electrochemical potential (1).
materials: materials Electrochromism has a history dating back to the nineteenth century (1). However, only in the
that have the property last quarter of the twentieth century did the study of electrochromism gain real impetus, and
of a change, evocation,
several research monographs and reviews that detail the science and applications of electrochromic
or bleaching, of color
as effected either by an materials are available (111). Electrochromic materials were last reviewed in this publication
electron-transfer 25 years ago (12).
(redox) process or by a Many chemical materials exhibit two or more redox states with distinct electronic (UV/visible)
sufcient absorption spectra, which arise from either a moderate-energy internal electronic excitation or
electrochemical
an intervalence optical charge transfer in which different oxidation states are available. Although
potential
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materials are considered to be electrochromic when light is modulated by reectance or absorbance


ECD: electrochromic
in the visible region of the electromagnetic spectrumcolor changes perceptible to the human
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device
eyerecent interest in electrochromic devices (ECDs) for multispectral energy modulation has
Type I
extended the working denition (13). Chemical materials and devices are now also being studied
electrochromic
materials: materials for modulation of radiation in the infrared (1418) and microwave (19) regions. However, the
that are soluble in both present review focuses on modulation of radiation in the visible region.
the reduced state and Using a simple classication system developed from that of Chang et al. (20) at IBM, we have
the oxidized state distinguished electrochromic materials as being of three simple types on the basis of the solubility
MV: methyl viologen of each redox state (2). In a given electrolyte solution, type I electrochromic materials are soluble
[N,N  -dimethyl-4,4 - in both the reduced state and the oxidized state. Examples are the prototype viologen, N,N  -
bipyridylium]
dimethyl-4,4 -bipyridylium [methyl viologen (MV)] and numerous metal complex and organic
Type II redox indicators. Type II electrochromic materials are soluble in one redox state but form a
electrochromic
solid lm on the surface of an electrode following electron transfer. Examples are N,N  -bis(n-
materials: materials
that are soluble in one heptyl)-4,4 -bipyridylium [heptyl viologen (HV)] in water and the reversible electrodeposition of
redox state but that metals. In type III electrochromic materials, such as tungsten oxide (WO3 ), polymeric viologens,
form a solid lm on conjugated conducting polymers, metallopolymers, and the metal hexacyanometallate Prussian
the surface of an blue (PB), both or all redox states are solid, and these systems are studied as thin lms on electrode
electrode following
surfaces. For types II and III, once the redox state has been switched, no further charge injection is
electron transfer
needed to retain the new electrochromic state, and such systems have optical memory. In contrast,
HV: heptyl viologen
for type I electrochromic materials, diffusion of the soluble electrochemically generated product
[N,N  -bis(n-heptyl)-
4,4 -bipyridylium] material away from the electrode occurs, and it is necessary to keep current owing until the whole
solution has been electrolyzed. When more than two redox states are electrochemically accessible
Type III
electrochromic in a given electrolyte solution, the electrochromic material may exhibit several colors and thus be
materials: materials polyelectrochromic, a property of many conjugated conducting polymers (5, 911).
that are solid in both Commercial applications (6, 21) of electrochromic materials in devices include antiglare car
or all redox states mirrors; smart windows (Figure 1) (based on modulation of either the transmitted or the re-
PB: Prussian blue ected solar radiation) for use in cars, aircraft, and buildings; electrochromic strips as battery
Contrast ratio: state-of-charge indicators; and electrochromic sunglasses. Proposed applications include reusable
the ratio of the price labels, protective eyewear, controllable aircraft canopies, glare-reduction systems for ofces,
transmittance of the devices for frozen-food monitoring, camouage materials, chameleonic fabrics, spacecraft ther-
electrochromic
mal control, an optical iris for a camera lens, and (nonemissive) controllable light-reective or
material in its bleached
(colorless) state to the light-transmissive display devices for optical information and storage.
transmittance in the Although a vast number of chemical species exhibit electrochromic properties (1), only those
colored state with favorable electrochromic performance parameters (1) are potentially useful in commercial
applications. Thus, most applications require electrochromic materials with a high contrast ratio,
coloration efciency, write-erase efciency, and cycle life. Some performance parameters are

242 Mortimer
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Figure 1
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Switching sequence of a laminated electrochromic glass manufactured by Gesimat GmbH, Berlin, Germany. This electrochromic
device uses tungsten oxide and Prussian blue as complementary electrochromic layers and ion-conducting poly(vinylbutyral) as the
Annu. Rev. Mater. Res. 2011.41:241-268. Downloaded from www.annualreviews.org

polymer electrolyte. Photograph reproduced with permission from A. Kraft & M. Rottmann.

application dependent, with display devices needing low response times, whereas smart windows
can tolerate response times of up to several minutes.
This review surveys the main classes of electrochromic materials, namely, metal oxide lms
(especially tungsten oxide); viologens (4,4 -bipyridylium salts, in solution and as polymer lms);
conjugated conducting polymers; metal coordination complexes as polymeric, evaporated, or sub-
limed lms; and PB. Throughout, we provide examples of instances in which such materials have
been used to construct devices. Next, the operating principles of ECDs are briey discussed be-
fore consideration of the other materials required for their construction, with a focus on optically
transparent electrodes, electrolyte layers, and device encapsulation. In conclusion, commercial
successes, current trends, and future challenges in electrochromic materials research and devel-
opment are summarized.

Coloration
METAL OXIDES efficiency: the ratio of
the absorbance change
Background and Color-Switching Properties to the charge injected
per unit electrode area
The oxides of the following (transition) metals are electrochromic: cerium, chromium, cobalt, cop-
Write-erase
per, iridium, iron, manganese, molybdenum, nickel, niobium, palladium, praseodymium, rhodium,
efficiency: the
ruthenium, tantalum, titanium, tungsten, and vanadium (1). Most of the electrochromic colors fraction (percentage)
derive from intervalence charge-transfer optical transitions; the more highly colored form of most of the originally
metal oxide electrochromic materials are in the range of blue or gray through black. The oxides of formed colored state
tungsten, molybdenum, iridium, and nickel show the most intense electrochromic color changes. that can subsequently
be electrochemically
Other metal oxides of lesser colorability are however useful in ECDs as the optically passive sec-
bleached
ondary electrode material. Those metal oxides that are available as (essentially) colorless thin lms
Cycle life: the
and that can be chemically or electrochemically reduced to a nonstoichiometric redox state with
number of write-erase
an intense electronic absorption band have the most applicability to ECDs. cycles that can be
The literature describing metal oxide electrochromism is extensive, with review chapters in performed before any
research monographs (1, 2) and the 1995 standard text of Granqvist (of Uppsala University) signicant extent of
(3). Granqvists reviews include those that describe progress made during 19931998 (22) and degradation occurs
(with coauthor Niklasson) an in-depth feature article that summarizes recent advances in metal Response time: the
oxide electrochromism, with emphasis on materials chemistry (23), and an introduction to smart time required for some
fraction of the color to
windows technology (24). Tungsten trioxide (WO3 ), a high-bandgap d0 semiconductor, is the
form or be bleached
most widely studied electrochromic material. As early as 1815, Berzelius (25) had reported that

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pure WO3 (which is pale yellow) changed color on reduction when warmed under a ow of dry
hydrogen gas, and in 1824, Wohler (26) effected a similar chemical reduction with sodium metal.
The rst recorded color change following electrochemical reduction of WO3 , as an electrode
IVCT: intervalence
charge transfer coating immersed in aqueous acid, was in 1930 (27). The color generation reaction followed:
+
WO3 + x(H + e ) = Hx W(1x)
VI
WxV O3 . 1.
colorless deep blue

The rst widely accepted suggestion of an ECD is attributed to Deb (then at Cyanamid in the
United States) in 1969 (28). In his device, electrochromic coloration occurred on application of
104 V cm1 across a thin lm of highly disordered, vacuum-deposited WO3 on quartz. [Deb
termed the effect electrophotography, wording that may derive from his study of thin-lm MoO3 ,
which acquired color following UV irradiation (29).] Unlike modern ECDs, Debs lm of WO3
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was open to the air rather than immersed in an ion-containing electrolyte solution, suggesting
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that the mobile countercations may have come from simultaneous ionization of interstitial and/or
adsorbed water. At the time, it was suggested the color arose from F centers, much like the color
formed by heating or irradiating crystals of metal halides in a eld. Nowadays, most researchers
cite Debs later paper (30) as the true birth of electrochromic technology. The background to
Debs work was recounted in 1995 (31), and in 2008 Deb (32) reviewed the opportunities and
challenges in the science and technology of WO3 not only for electrochromic smart windows
and displays but also in related applications including photoelectrochromic devices, gas sensors
(especially for H2 ), solar energy conversion and storage cells, and optical recording and image
storage.
Thin-lm WO3 with all tungsten sites in oxidation state W VI is colorless or very pale yellow.
On electrochemical reduction, W V sites are generated to give the electrochromic effect. Although
there is still controversy about the detailed coloration mechanism, it is generally accepted that the
injection and extraction of electrons and protons or univalent inert metal cations play a key role.
In the case of Li+ cations, which are often employed as the electrolyte cation, the reaction can be
written as
WO3 + x(Li+ + e ) = Lix W(1x)
VI
WxV O3 . 2.
colorless deep blue

At low x the lms have a deep blue color likely caused by photo-effected intervalence charge
transfer (IVCT) between adjacent W V and W VI sites. At higher x, insertion irreversibly forms
a metallic bronze that is red or golden. [Wohler (32) rst coined the term tungsten bronze in
1837, when he misinterpreted the intense metallic luster of LiWO3 as being due to the formation
of metallic alloys.] Deb (32) has discussed the challenges of forming one unifying model for the
interpretation of the coloration phenomena in thin lms of amorphous and crystalline WO3 owing
to the many contradictions that still exist in the interpretation of experimental results. Following
his original model that recognized the critical role of defects such as oxygen vacancies in a mostly
ionic solid such as WO3 , at least four other mechanisms have been proposed: (a) IVCT (as noted
above), (b) polaronic absorption, (c) interband excitations, and (d ) transitions from the valence
band to split off the W V state.
As noted above, many other thin-lm metal oxides (13), for example, the oxides of molybde-
num and vanadium (13), are electrochromic:

MoO3 + x(M+ + e ) = Hx MoVI V


(1x) Mox O3 , 3.
colorless deep blue

V2 O5 + x(M+ + e ) = Mx V(1x)
IV
VxV O5 . 4.
brown-yellow very pale blue

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In these examples, the more intensely absorbing redox state is produced on reduction, with con-
current cation insertion. In contrast, group VIII metal oxides become colored on electrochemical
oxidation, as in the case of hydrated iridium oxide (iridium hydroxide). The mechanism of col-
oration is uncertain; both proton extraction and anion insertion routes are proposed:
Ir(OH)3 = IrO2 H2 O + H+ + e , 5.
colorless blue-gray

Ir(OH)3 + OH = IrO2 H2 O + H2 O + e . 6.
colorless blue-black

Another commonly studied anodically coloring electrochromic material is hydrated nickel oxide
(nickel hydroxide), a material more commonly known for its use in secondary batteries. Hydrated
nickel oxide in basic electrolytes switches from pale green to brown-black:
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Ni(OH)2 + OH = NiO OH + H2 O + e . 7.
pale green brown-black
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Preparation of Thin-Film Metal Oxides


For ECD application, metal oxides must be deposited on a conducting substrate as a thin, even
lm, typically in the range of 0.20.5 m. Such thin lms are either amorphous or polycrystalline,
sometimes both admixed, and the morphology depends strongly on the mode of lm preparation.
Granqvists book (3) and reviews give extensive detail on the preparation of metal oxide lms.
Deposition methods have been outlined (1) and comprise chemical vapor deposition, electrode-
position, sol-gel techniques (spray pyrolysis, dip and spin coating), sputtering in vacuo (using
dc magnetron, electron beam, and radio frequency radiation), thermal deposition in vacuo, and
Langmuir-Blodgett deposition.

VIOLOGENS

Background and Early Viologen Electrochromic Devices


Viologens are salts of quaternized 4,4 -bipyridine and, in addition to electrochromic properties,
have applications as herbicides, redox indicators, and electron-transfer mediators (33). The ready
availability of 4,4 -bipyridine and the ease of varying the nature of the quaternizing reagent have
allowed intensive research into the electrochromic properties of viologens (33). As noted above, the
prototype viologen is MV; other simple symmetrical bipyridylium species are named substituent
viologen. Of the three common viologen redox states (Equation 8 for the MV system), the dication
is colorless when pure unless optical charge transfer with the counteranion occurs. Reduction forms
the radical cation, the stability of which is attributable to the delocalization of the radical electron
throughout the framework of the bipyridyl nucleus; the N,N  substituents commonly bear some
of the charge.

e e
H3 C N N CH3 H 3C N N CH3 H3 C N N CH3
-e -e
dication: colorless radical cation: blue (as a monomer) neutral species 8.
Viologen radical cations are intensely colored, with high molar absorption coefcients, owing
to optical charge transfer between the (formally) +1-valent and zero-valent nitrogens. Suitable
choice of nitrogen substituents in viologens to attain the appropriate molecular orbital energy
levels can, in principle, allow color choice of the radical cation. For example, alkyl groups pro-
mote a blue-violet color, whereas the radical cation of N,N  -bis(4-cyanophenyl)-4,4 -bipyridylium

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(cyanophenyl paraquat) in acetonitrile has an intense green color. The intensity of the color ex-
hibited by direduced viologens (Equation 8) is low because no optical charge transfer or internal
transition corresponding to visible wavelengths is accessible.
ITO: tin-doped
indium oxide The rst viologen-based ECD was reported in 1973 after research at the Philips Laboratories
in Holland (34). Philips (1970) and Imperial Chemical Industries (1971) had submitted patents
using HV and cyanophenyl paraquat, respectively. At this time, IBM (35) and Texas Instruments
(36) were investigating other displays based on HV. A 64 64pixel integrated display with eight
levels of gray tone on a 1-inch square silicon chip that was capable of giving quite detailed images
was reported (37). It is likely that these displays were not exploited further owing to liquid crystal
display (LCD) competition, although they may still have a size advantage in large-area devices.
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Solution-Phase Viologen Electrochromic Device Systems


Solution-phase ECDs (38) operate by electrolysis of type I electrochromic materials and were rst
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described in the open literature in 1977 (3941). Gentex Corporations commercialized automatic-
dimming Night Vision Safety (NVS R
) mirrors employ viologen electrochromism (42). In the
system, a tin-doped indium oxide (In2 O3 :Sn) (ITO)-glass surface (conductive side inward) and
a reective metallic surface, spaced a fraction of a millimeter apart, form the two electrodes of
the cell, with a (proprietary) gel formulation containing two electrochromic materials, without
additional supporting electrolyte. The exact composition of the Gentex NVS R
mirror is protected
by patents, but it is possible to infer that the two electroactive chemical species are a cathodically
coloring substituted (cationic) viologen and an anodically coloring, negatively charged thiazine or
a phenylene diamine species. After the mirror is switched on, the species migrate to their respective
electrodes. Once the dual electrochromic coloration process has begun, the products diffuse away
from their respective electrodes and meet in the intervening solution, where a mutual reaction re-
generating the original uncolored species takes place. This type of ECD therefore requires passage
of a continuous small current for replenishment of the colored electroactive species lost by their
mutual self-erasing solution redox reaction. A solution-phase electrochromic system in acetoni-
trile comprising nine solution-phase electrochromic thin-layer cells based on HV perchlorate and
N,N  ,N,N  -tetramethyl-1,4-phenylenediamine (TMPD) has been investigated for display applica-
tions (43). Equation 9 shows the spontaneous reaction between the radical cations that is associated
with bleaching, whereas the electrolytic reverse reaction generates an intense blue coloration:

+
C7H15 N N C7H15 + N N C7H15 +N N C7H15 + N N

HV radical cation: blue TMPD radical cation: blue HV dication: colorless TMPD: colorless 9.

Cells were arranged in three rows and three columns and were matrix addressed without cross talk
with six inputs (Figure 2). Cross talk is absent because the voltage communicated to the pixels
peripheral to the one intended for coloration never exceeds the threshold voltage for coloration.
The inuences of operating voltage and cell gap have been investigated in a solution-phase
ECD containing HV and TMPD in propylene carbonate, with 0.5 mol dm3 tetrabutylammonium
tetrauoroborate as supporting electrolyte (44). Reversible electrochromism was achieved only
when the cell gap was kept at 0.28 mm. On/off application of 1.0 V was sufcient to observe the
color change.

Polymeric Viologen Systems


The write-erase efciency of an ECD using type I viologens such as aqueous MV is low be-
cause both the dicationic and radical cation states are very soluble. Improved MV-based systems

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a
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b
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Figure 2
Photographs of a 3 3 array of solution-phase electrochromic pixels based on heptyl viologen perchlorate
and N,N  ,N,N  -tetramethyl-1,4-phenylenediamine (TMPD) (0.05 mol dm3 each). Pixel area is 1.57 cm2 ;
pixel thickness, 190 m. (a) Steady-state addressing of pixel (2,2) with a 0.5-V bias. (b) Typical matrix
addressing: A pattern is displayed by scanning the rows repetitively one line at a time, whereas addressing for
the columns is recongured for every row. Adapted from Reference 43 with permission from The
Electrochemical Society.

may be made by retarding the rate at which the radical cation product of electron transfer dif-
fuses away from the electrode by use of an anionic polyelectrolyte such as poly(2-acrylamido-
2-methylpropane-sulfonic acid) (polyAMPS) (45, 46) or the sulfonated peruorinated polyether
Naon R
(47, 48). Alternative approaches include the surface modication of an electrode using
silanization methodology (49), a preformed polymeric viologen salt (50), or oxidative electropoly-
merization of a pyrrole-substituted viologen (51) and a pyrrole-disubstituted viologen, N,N  -
bis(3-pyrrol-1-ylpropyl)-4,4 -bipyridylium (52, 53). Polyelectrolyte multilayers of poly(butanyl
viologen) dibromide and poly(styrene sulfonate) (PSS) sodium salt have been prepared (54) us-
ing an alternating polyion solution deposition technique. In this technique, the ITO substrate
is alternatively exposed to positive and negative polyelectrolytes, with spontaneous polymer de-
position via coulombic interactions between the surface and polyion of opposite charge. In this
layer-by-layer deposition technique, all redox material is electrochemically addressable, with good
electrochromic performance characteristics.

Electrochromic Devices Based on Viologens Adsorbed


on Nanostructured Titanium Dioxide
Recent progress in viologen-based electrochromism has focused on the use of nanostructured
wide-bandgap TiO2 (anatase)-coated electrodes for the enhancement of contrast ratio and
coloration efciency. Such electrodes were rst developed for dye-sensitized solar cells (55). The

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MR41CH10-Mortimer ARI 27 May 2011 14:1

ratio between the internal surface area and the smooth geometrical area (the roughness factor)
approaches 1,000 for a 4-m-thick lm, meaning that a high number of electrochromic viologen
molecules can occupy a relatively small area, leading to a high coloration efciency. Furthermore,
as they are surface conned, the viologen molecules need not diffuse to the electrode surface,
which leads to shorter switching times. On the basis of these principles (56), NTERA Limited
(http://www.ntera.com) has developed NanoChromicsTM Ink Systems that enable cost effec-
tive manufacturing of printed electronic (micropatterned) displays on a variety of exible sub-
strate materials using industry standard printing (screen, exographic and inkjet) techniques and
equipment. Many thousands of switches are possible in such displays before there is signicant
degradation of performance. After switching, some open circuit memory persists; color remains
for more than 10 min after the voltage is switched off, but the color is readily regenerated.
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NanoChromicsTM displays are of a monolith construction and consist of a multilayer printed


structure on a single substrate. A conducting ITO on poly(ethylene terephthalate) (PET) substrate
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acts as the negative electrode (the cathode on coloration) and is coated with a 4-m-thick TiO2
lm, followed by a monolayer of self-assembled, chemisorbed, phosphonated viologen molecules.
The positive counterelectrode (the anode on coloration) carries a 3-m-thick lm of high-surface-
area antimony tin oxide (SnO2 :Sb) on a conductive carbon/PET substrate. Application of 1.0 V
reversibly reduces the dicationic viologen to its blue radical cation. Placing an ion-permeable
nanostructured TiO2 layer (as diffuse reector) between the electrodes results, on coloration, in
the visual effect of ink on pure white paper. The counterelectrode has a high capacitance, which
assists charge storage during coloration. Without the intermediate TiO2 layer, the ECD display is
transparent while retaining readability. In such a conguration, if a monolayer of self-assembled,
chemisorbed, phosphonated phenothiazine molecules (red on oxidation) is applied to the coun-
terelectrode, the overall color changes from colorless to a blue-red purple. Different colors can
be achieved, depending on the nature of the substituent(s) on the viologen molecule. Further de-
tails, applications, and developments based on viologen-adsorbed nanostructured electrochromics
technology have been summarized from the available literature (1). In a development of this tech-
nique, mesoporous TiO2 with vertical pores has been structured and used with an adsorbed leuco
dye in a high-speed/high-resolution electrochromic passive-matrix display that reversibly switches
from white to black on application of 3.0 V (57). The vertical pores of the electrode can support
effective diffusion of leuco dyes perpendicular to the electrode and can prevent the diffusion of
the dye around the electrode.

CONJUGATED CONDUCTING POLYMERS

Introduction
Chemical or electrochemical oxidation of resonance-stabilized aromatic molecules, such as thio-
phene, pyrrole, aniline, furan, carbazole, azulene, indole, and their derivatives, produces elec-
troactive conjugated conducting polymers (58). Many of these materials are electrochromic as
thin lms, and this property has been frequently reviewed (1, 2, 4, 5, 911). Polymeric thiophenes
and pyrroles have received the most attention in recent years and are considered below. Reynolds
and his group at the University of Florida have been especially inuential in this eld (see below).
In the conducting oxidized state, conjugated conducting polymers have positive change car-
riers, are charge balanced with counteranions ( p doped) and have delocalized -electron-band
structures. Electrochemical reduction, with concurrent counteranion egress to, or cation ingress
from, the electrolyte, removes the electronic conjugation to yield the undoped electrically neutral
insulating form. For the undoped polymer, the optical bandgap (Eg ) between the highest-occupied

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MR41CH10-Mortimer ARI 27 May 2011 14:1

-electron band (the valence band) and the lowest-unoccupied band (the conduction band) deter-
mines the electrochromic properties. The color change or contrast between doped and undoped
forms of a polymer depends on the bandgap magnitude. Thin lms with Eg > 3 eV (400 nm)
PEDOT: poly[3,4-
are colorless and transparent in the undoped form, whereas in the doped form they generally (ethylenedioxy)
absorb visible radiation. Those with Eg 1.71.9 eV (650730 nm) are highly absorbing in the thiophene]
undoped form, but after doping, the free carrier absorption is relatively weak in the visible region
because it is transferred to the near infrared. Polymers with intermediate bandgaps have distinct
optical changes throughout the visible region and can exhibit several colors.

Poly(thiophene)s
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Poly(thiophene)s are of particular interest as electrochromic materials due to their relative ease
of chemical and electrochemical synthesis, environmental stability, and processability. Thin poly-
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meric lms of the parent poly(thiophene) are blue (max = 730 nm) in the doped (oxidized) state
and red (max = 470 nm) in the undoped form. A vast number of substituted thiophenes have been
synthesized, and this has led to the study of numerous novel poly(thiophene)s, with particular em-
phasis on poly(3-substituted thiophene)s and poly(3,4-disubstituted thiophene)s. Tuning of color
states is possible by suitable choice of thiophene monomer, which represents a major advantage
of using conjugated conducting polymers for electrochromic applications. Subtle modications
can signicantly alter spectral properties; for example, poly(3-methylthiophene) is purple when
neutral and turns pale blue on oxidation. Colors available with polymer lms prepared from
3-methylthiophene-based oligomers are strongly dependent on the relative positions of methyl
groups on the polymer backbone and include pale blue, blue, and violet in the oxidized form and
purple, yellow, red, and orange in the reduced form.
Study of the effects of steric factors is provided by the electronic properties of poly(thiophene)s
with 3,4-dialkyl substituents. In principle, disubstitution at the 3 and 4 positions should provide
the synthetic basis to perfectly stereoregular polymers. However, this approach is severely limited
by the steric interactions between substituents, which lead to a decrease in polymer conjuga-
tion length. In fact, poly(3,4-dialkylthiophene)s have higher oxidation potentials, higher optical
bandgaps, and lower electronic conductivities than poly(3-alkylthiophene)s. Cyclization between
the 3 and 4 positions relieves steric hindrance in thiophenes, but many thiophenes are harder to
electropolymerize than, say, 3-methylthiophene. The electron-donating effect of alkoxy groups
offers a solution here, and alkoxy-substituted poly(thiophene)s are intensively investigated for
their electrochromic properties (59, 60).
Figure 3 shows in situ visible and near-infrared spectra as a function of applied electrode
potential for an alkylenedioxy-substituted thiophene polymer, poly[3,4-(ethylenedioxy)thiophene]
(PEDOT), which exhibits a deep-blue color in its neutral state and a light-blue transmissive state
upon oxidation (61). The strong absorption band of the undoped polymer, with a maximum at
621 nm (2.0 eV), is characteristic of a - interband transition. Upon doping, the interband
transition decreases, and two new optical transitions (at 1.25 and 0.80 eV) appear at lower
energy, corresponding to the presence of a polaronic charge carrier (a single charge of spin 1/2).
Further oxidation leads to formation of a bipolaron, and the absorption is enhanced at lower
energies. The characteristic absorption pattern of the free carrier of the metallic-like state then
appears when the bipolaron bands nally merge with the valence and conduction bands.
Materials based on PEDOT have a bandgap lower than those of either poly(thiophene)
or alkyl-substituted poly(thiophene)s owing to the presence of the two electron-donating oxy-
gen atoms adjacent to the thiophene unit. The bandgap of PEDOT is 0.5 eV lower than
that of poly(thiophene), which results in an absorbance maximum in the red region of the

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MR41CH10-Mortimer ARI 27 May 2011 14:1

1.2
S max
x to * 1.2

Absorbance at max
1.0
O O Eg Eb2 ~Eo'
1.0 0.8
+0.87 V Eb1
0.6
0.4
Neutral Bipolaron
polymer states 0.2
0.8 1.0 0.5 0.0 0.5 1.0
Potential (V) versus SCE
Eb1
Absorbance (a.u.)

0.6
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0.4

0.2

0.93 V
0.0
Eg ~ 1.61.7 eV

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5


Energy (eV)

Figure 3
Spectroelectrochemistry for a poly[3,4-(ethylenedioxy)thiophene] (PEDOT) lm on tin-doped indium oxide
(ITO)/glass. The lm was electrochemically deposited from 0.3 mol dm3 3,4-(ethylenedioxy)thiophene and
0.1 mol dm3 tetrabutylammonium perchlorate/propylene carbonate and switched in 0.1 mol dm3
tetrabutylammonium perchlorate/acetonitrile. Inset shows absorbance versus potential. The bandgap is
determined by extrapolating the onset of the -to- absorbance to the background absorbance. The Eb1
transition is allowed and is visible at intermediate doping levels. Adapted from Reference 61 with permission
from the author.

electromagnetic spectrum. Compared with other substituted poly(thiophene)s, PEDOT mate-


rials exhibit excellent stability in the doped state, which has a high electronic conductivity. Bayer
AG research laboratories in Germany rst developed PEDOT in an attempt to produce an easily
oxidized, soluble, and stable conducting polymer (59). To aid in processing, the insolubility of
PEDOT can be overcome by the use of a water-soluble polyelectrolyte, PSS, as the counterion
in the doped state, to yield a PEDOT:PSS dispersion in water. PEDOT:PSS-based inks, coating
formulations, and coated lms are commercially available as OrgatronTM from AGFA Gevaert.
As PEDOT and its alkyl derivatives are cathodically coloring electrochromic materi-
als, they can be used with anodically coloring conjugated conducting polymers as the sec-
ondary electrode material in the construction of dual-polymer ECDs (62). Changes in the
size of the alkylenedioxy ring and the nature of the substituents on the alkyl bridge have
led to polymers with faster electrochromic switching (6365), higher contrast ratios (6366),
and better processability through increased solubility (6771). The color palette of solution-
processable conjugated conducting polymers continues to expand; orange-to-transmissive and
red-to-transmissive color switching were reported for poly[3,4-di(2-ethylhexyloxy)thiophene] and

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MR41CH10-Mortimer ARI 27 May 2011 14:1

poly[3,4-di(2-ethylhexyloxy)thiophene-co3,4-di(methoxy)thiophene], respectively (72). Green-


to-transmissive switching is especially challenging, as two-band (red and blue) absorption is
necessary. Donor [3,4-(propylenedioxy)thiophene (ProDOT)]-acceptor (benzothiadiazole) het-
erocyclic polymers have been synthesized via polymerizable pentamers to yield conjugated and
processable green polymers that exhibit fast switching and highly transmissive oxidized states (73).
The donor-acceptor approach toward low-bandgap polymers has also been used to make neutral-
state black (74) and blue (75) processable polymeric electrochromic materials that reversibly switch
to colorless transmissive oxidized states.

Poly(pyrrole)s
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Poly(pyrrole)s are likewise extensively studied and can be easily synthesized chemically or electro-
chemically, with a varying range of optoelectronic properties available through alkyl and alkoxy
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substitution. Thin lms of the parent poly(pyrrole) are yellow-green (Eg 2.7 eV) in the undoped
insulating state and blue-violet in the doped conductive state.
As for dialkoxy-substituted thiophenes, the addition of the oxygen at the 3 positions low-
ers the bandgap of the resulting polymer by raising the highest-occupied -electron band. This
fact, combined with the already relatively low oxidation potential for poly(pyrrole), gives the
poly(alkylenedioxypyrrole)s (76) the lowest oxidation potential for p-type doping in conducting
electrochromic polymers (77). Poly[3,4-(ethylenedioxy)pyrrole] (PEDOP) exhibits a bright-red
color in its neutral state and a light-blue transmissive state upon oxidation, with a bandgap of
2.05 eV, 0.65 eV lower than that of the parent pyrrole (78). Furthermore, increasing the ring
size of the alkyl bridge generates another colored state at low doping levels (77). For poly[3,4-
(propylenedioxy)pyrrole] (PProDOP), the neutral state is orange and, on intermediate doping,
passes through brown and nally to light gray-blue upon full oxidation (77). Such polyelec-
trochromism is also seen in the substituted PProDOPs and poly[3,4-(butylenedioxy)pyrrole]
(PBuDOP) (77). Under separate potentiostatic control, lms of PProDOP have been paired
with PEDOT and (spray-processable) dihexyl-substituted poly[3,4-(propylenedioxy)thiophene]
(PProDOT) in a stacked polymer arrangement (79). Coupling these polymers logically by a bipo-
tentiostatically controlled dual-polymer electrochromic lm characterization technique provides
new colors (Figure 4) that are not observed when these polymers are studied separately.
More recently, the rst conjugated conducting polymerbased deep-blue/black-to-
transmissive and multicolored ECD was constructed (80). Color choice was by transmission of
light through two bipotentiostatically controlled, independent stacked working electrodes (coated
with different substituted PProDOT lms) and two counterelectrodes, each coated with a non-
electrochromic yet electroactive polymer.
By substitution at the nitrogen in poly(3,4-alkylenedioxypyrrole)s (PXDOPs), higher-bandgap
polymers that retain their low oxidation potentials can be created (81). Substitution induces a
twist in the polymer backbone, which results in a decrease in the effective conjugation and
an increase in the polymers bandgap. This bandgap increase results in a blueshift in the -
transition absorbance, with the intragap polaron and bipolaron transitions occurring in the visible
region. The nature of the substituent has an effect on the extent to which the - transition
is shifted. For N-methyl-PProDOP, the bandgap occurs at 3.0 eV compared with 2.2 eV for
PProDOP, and the purple color in the neutral state becomes blue when the polymer is fully
oxidized after having passed through a dark-green color at intermediate oxidation (81). Both N-
[2-(2-ethoxy-ethoxy)-ethyl] PProDOP (N-Gly PProDOP) and N-propanesulfonate PProDOP
(N-PrS PProDOP) are colorless when fully reduced but are colored upon full oxidation and
exhibit multiple colored states at intermediate extents of oxidation (81). These two polymers

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0.85 PProDOT-Hx2 (V) 0.15

0.65 0.45 0.25 0.05

1.35 L* = 56 L* = 54 L* = 54 L* = 55 L* = 66 L* = 72
a* = 21 a* = 23 a* = 23 a* = 22 a* = 27 a* = 24
*
b = 16 *
b = 16 *
b = 15 *
b = 14 *
b = 33 b* = 39

L* = 55 L* = 55 L* = 55 L* = 54 L* = 67 L* = 72
1.20 a* = 21 a* = 22 a* = 22 a* = 24 a* = 26 a* = 24
b* = 15 b* = 16 b* = 15 b* = 16 b* = 35 b* = 38

L* = 55 L* = 53 L* = 52 L* = 55 L* = 68 L* = 72
1.05 a* = 20 a* = 22 a* = 22 a* = 22 a* = 26 a* = 22
b* = 13 b* = 15 b* = 13 b* = 14 b* = 32 b* = 37
PProDOP (V)

L* = 52 L* = 52 L* = 52 L* = 53 L* = 65 L* = 70
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0.90 a* = 16 a* = 18 a* = 17 a* = 18 a* = 20 a* = 17
b* = 2 b* = 1 b* = 1 b* = 3 b* = 21 b* = 26
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L* = 54 L* = 53 L* = 54 L* = 55 L* = 68 L* = 73
0.75 a* = 9 a* = 11 a* = 10 a* = 11 a* = 9 a* = 4
b* = 21 b* = 18 b* = 17 b* = 14 b* = 2 b* = 2

L* = 57 L* = 56 L* = 57 L* = 59 L* = 72 L* = 76
0.60 a* = 7 a* = 7 a* = 7 a* = 7 a* = 5 a* = 0
b* = 28 b* = 27 b* = 25 b* = 22 b* = 6 b* = 3

0.45 L* = 60 L* = 58 L* = 59 L* = 60 L* = 74 L* = 79
a* = 7 a* = 8 a* = 7 a* = 8 a* = 4 a* = 1
b* = 28 b* = 28 b* = 27 b* = 24 b* = 7 b* = 4

Figure 4
Commission Internationale de lEclairage (CIE) L a b color coordinates and photography for
poly[3,4-(propylenedioxy)pyrrole] (PProDOP)/poly[3,4-(propylenedioxy)thiophene] (PProDOT)-dihexyl
(Hx2 ) in 0.1 mol dm3 lithium perchlorate/propylene carbonate. The polymer lms were deposited on
separate stacked tin-doped indium oxide (ITO)/glass electrodes and were separately addressed using a
bipotentiostat. Adapted from Reference 79 with permission from The American Chemical Society.

are thus anodically coloring in that they change from a colorless state to a colored one upon
oxidation, in contrast to cathodically coloring polymers that are colored in their reduced state and
become colorless upon oxidation. These N-substituted polymers work effectively in dual-polymer
high-contrast-ratio absorptive/transmissive ECDs as the anodically coloring material due to their
electrochemical and optical compatibility with various PXDOT polymers (82).

METAL COORDINATION COMPLEXES

Introduction
Metal coordination complexes show promise as electrochromic materials because of their intense
coloration and redox reactivity (1, 8). Chromophoric properties arise from low-energy metal-to-
ligand charge transfer (MLCT), IVCT, intraligand excitation, and related visible-region electronic
transitions. Because these transitions involve valence electrons, chromophoric characteristics are
altered or eliminated upon oxidation or reduction of a complex. Although these spectroscopic and
redox properties would be sufcient for direct use of metal coordination complexes in solution-
phase ECDs, thin-lm systems, often as polymers, are frequently investigated for their possible
MLCT: metal-to- application in type III all-solid-state devices. The preparation and electrochromic properties of
ligand charge transfer thin lms of transition-metal polypyridyl complexes and metallophthalocyanines are described
below.

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MR41CH10-Mortimer ARI 27 May 2011 14:1

Transition-Metal Polypyridyl Complexes


Good examples of metal coordination complexes with the potential for use in ECDs include the
[MII (bipy)3 ]2+ (M = iron, ruthenium, osmium; bipy = 2,2 -bipyridine) series, which are red, LMCT: ligand-to-
orange, and green, respectively, in the MII redox state due to the presence of an intense MLCT metal charge transfer
absorption band (83). Electrochromicity results from loss of the MLCT absorption band on
switching to the MIII redox state.
Reductive electropolymerization of suitably substituted [MII (bipy)3 ]2+ complexes is one ap-
proach that allows the preparation of electrochromic redox-active polymer lms (84, 85). This
technique relies on the ligand-centered nature of the three sequential reductions of complexes such
as [Ru(4-vinyl-4 -methyl-bipy)3 ]2+ , combined with the anionic polymerizability of suitable ligands
(84). Vinyl-substituted pyridyl ligands are generally employed, although metallopolymers have
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also been formed from complexes of halo-substituted pyridyl ligands such as 4-(bromomethyl)-
4 -methyl-bipy via electrochemically initiated carbon-halide bond cleavage (86). In either case,
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electrochemical reduction generates radicals, which lead to carbon-carbon bond formation and
oligomerization. Oligomers above a critical size are insoluble, and thus thin lms of the elec-
troactive metallopolymer are produced on the electrode surface. As noted above, the color of such
metallopolymer lms in the MII redox state may be selected by suitable choice of the metal.
Oxidative electropolymerization of suitably substituted [MII (bipy)3 ]2+ complexes is a second
approach to the preparation of electrochromic redox-active polymer lms. This has been described
for FeII and RuII complexes containing amino-substituted (87) and pendant anilinesubstituted
(88) 2,2 -bipyridyl ligands and amino- and hydroxy- substituted 2,2 :6 ,2 -terpyridinyl ligands (89).
Metallopolymer lms have also been prepared by oxidative polymerization of complexes of the
type [M(phen)2 (4,4 -bipy)2 ]2+ (M = Fe, Ru, or Os; phen = 1,10-phenanthroline; 4,4 -bipy =
4,4 -bipyridine) (90). Such lms are both oxidatively and reductively electrochromic; reversible
lm-based reduction at negative potentials leads to dark-purple lms (90), the color and potential
region of which are consistent with the viologen dication/radical cation electrochromic response.
A purple state at high negative potentials has also been observed for polymeric lms pre-
pared by reductive electropolymerization from tris(ligand) RuII complexes of 2,2 -bipyridines
substituted with N-styryl-aza-15-crown-5 (91). Electropolymerized lms prepared by oxidation of
[Ru(4,4 -bis(ferrocenylvinyl))(bipy)2 ][PF6 ]2 (92) and by reduction of [RuL3 ][PF6 ]2 [L = 4-(benzo-
l5-crown-5)vinyl-4 -methyl-bipy (Figure 5) or bismethoxyphenyl-vinyl-bipy] (93, 94) exhibit re-
versible orange/colorless electrochromic behavior associated with the RuII /RuIII interconversion.
A third approach is the drop-casting of polymer thin lms from solutions of soluble
metallopolymers, such as [Ru(terpy)-(box)PVP20 ]PF6 [terpy = 2,2 :6 ,2 -terpyridine; box =
2-(2-hydroxyphenyl)benzoxazole; PVP is poly(4-vinylpyridine), with 1 in 20 of the monomer units
labeled with the Ru(terpy)(box)] (95, 96). This metallopolymer undergoes a ruthenium-based
reversible oxidation, switching color from wine red to red-orange (mixed redox composition)
to light green. Oxidation at more positive potentials produces an irreversible change in the
near-infrared region, most likely a ligand-to-metal charge transfer (LMCT) transition between
phenolate and RuIII . Such metallopolymers, based on preformed backbones, offer the advantages
of synthetic exibility, ease of characterization, and absorbance change tuning through control
of ruthenium loading.

Metallophthalocyanines
The porphyrins are highly colored, naturally occurring pigments containing a porphine nucleus
with substituents at the eight positions {2, 3, 7, 8, 12, 13, 17, 18} of the pyrroles and/or the four
meso positions {5, 10, 15, 20} between the pyrrole rings. The natural pigments are metal chelate

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1,000 a 1,000 b
200
800 800
600 600 100

400 400 50

200 200 20
i (A)

i (A)
0 0
200 200
400 400
600 600
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800 800
1,000 1,000
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0.0 0.4 0.8 1.2 1.6 2.0 2.0 1.6 1.2 0.8 0.4 0.0
E versus SSCE (V) E versus SSCE (V)

Figure 5
(a) Fifteen sequential cyclic voltammograms at 100 mV s1 in an acetonitrile solution containing 1.33 mmol
dm3 [RuL3 ][PF6 ]2 [L = 4-(benzo-l5-crown-5)vinyl-4 -methyl-bipy] and 0.1 mol dm3
tetrabutylammonium tetrauoroborate. The initial scan direction is negative. (b) Cyclic voltammograms as a
function of scan rate (mV s1 as labeled on each) for the poly[RuL3 ] modied electrode from panel a in
supporting electrolyte. The polymer lm exhibits reversible orange/colorless electrochromic behavior
associated with the RuII /RuIII interconversion. Adapted from Reference 93 with permission from The Royal
Society of Chemistry.

complexes of the porphyrins. Phthalocyanines are tetra-azatetrabenzo derivatives of porphyrins


that have highly delocalized -electron systems, with many technological applications (97). The
metal ion in metallophthalocyanines lies either at the center of a single phthalocyanine ligand or
between two rings in a sandwich-type complex. Phthalocyanine complexes of transition metals
usually contain only a single Pc (dianion of phthalocyanine) ring, whereas lanthanide-containing
species usually form bis(phthalocyanines), in which the systems interact strongly with each other.
Since the discovery of the electrochromism of lutetium bis(phthalocyanine) [Lu(Pc)2 ] thin lms
(98), the electrochromic properties of numerous (mainly rare-earth) metallophthalocyanines have
been investigated. Lu(Pc)2 thin lms are polyelectrochromic; the initially deposited, vivid green
lms are oxidized through a yellow-tan form to a red form. Upon reduction, the green state can
be switched rst to a blue redox form and then to a violet-blue form. Although Lu(Pc)2 lms can
therefore exhibit ve colors, only the blue-green transition has been used in prototype ECDs.
There are mechanical problems associated with the use of Lu(Pc)2 -based lms, but in spite of
such difculties, ECDs with good reversibility, fast response times, and little degradation over
>5 106 cycles have been described.
The electrochromic properties of metallophthalocyanine lms are generally investigated using
low-molecular-weight sublimed (physical vapor deposition) lms, although studies have also
been carried out on lms prepared using the Langmuir-Blodgett technique. The preparation of
polymeric thin lms of phthalocyanines has also been investigated. Such materials are attractive
because of their rigidity; high stability; and strong, well-dened coupling of the electronic
systems. Because polymeric phthalocyanines are insoluble and cannot be vaporized, new
methods of thin-lm formation have been developed. For complexes with pendant aniline
and hydroxy-substituted ligands, oxidative electropolymerization is a useful route to the
preparation of metallophthalocyanine electrochromic lms. Although polymer lms prepared

254 Mortimer
MR41CH10-Mortimer ARI 27 May 2011 14:1

from [Lu(4,4 ,4 ,4 -tetra-aminophthalocyanine)2 ] monomers show loss of electroactivity on


cycling to positive potentials, in dimethyl sulfoxide the electrochemical response at negative
potentials is stable, with the observation of two broad, quasi-reversible, one-electron redox
couples (99). Spectroelectrochemical measurements reveal switching times of <2 s for the
observed green-gray-blue color transitions in this region. The oxidative electropolymerization
technique using pendant aniline substituents has also been applied to monophthalocyaninato
transition-metal complexes (100). Blue-green/yellow-brown/red-brown polyelectrochromism
and green/blue/purple polyelectrochromism for cobalt and nickel complexes, respectively, have
been reported. The rst reduction in the cobalt-based polymer is metal centered, resulting in
the appearance of a new MLCT transition; the second reduction is ligand centered. For the
nickel-based polymer, in contrast, both redox processes are ligand based.
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Electrochromic green polymer lms have been prepared by oxidative electropolymerization


of the monomer tetrakis(2-hydroxyphenoxy)phthalocyaninato cobalt(II) (101). Cyclic voltammo-
Annu. Rev. Mater. Res. 2011.41:241-268. Downloaded from www.annualreviews.org

grams during polymer growth showed the irreversible phenol oxidation peak at +0.58 V and a
reversible phthalocyanine ring oxidation peak at +0.70 V. Polymer-modied electrodes gave two
distinct redox processes with half-wave potentials at 0.35 [CoII /CoI ] and 0.87 V (reduction of
the ring). Color switching was from transparent light green [CoII state] to yellowish green [CoI
state] to dark yellow (reduced ring).
The synthesis and electropolymerization of tetrakis(2-pyrrol-1-ylalkoxy)phthalocyanines (102)
were reported, and the electrical and spectroscopic properties were discussed. Such reports were
the rst example of the electropolymerization of a phthalocyanine in which the electropolymeriz-
able group (pyrrole) is electronically isolated from the phthalocyanine. More recently, polymeric
thin lms of 4-(2,5-di-2-thiophen-2-yl-pyrrol-1-yl) (SNS) phthalocyanine [as the zinc complex
poly(ZnPc-SNS) and metal-free poly(H2 Pc-SNS)] were prepared by electropolymerization (103).
These SNS assemblies, with two external thiophenes and a central pyrrole ring, make electropoly-
merization easy due to the lower oxidation potential of the monomers. Both the poly(ZnPc-SNS)
and poly(H2 Pc-SNS) lms were green in their neutral states, with reversible and stable switching
to the respectively black- and turquoise-green oxidized forms.

PRUSSIAN BLUE

Introduction and Thin-Film Preparation


Prussian blue (PB), the earliest modern synthetic pigment (C.I. Pigment Blue 27) (104), has
an extensive history of use in the formulation of paints, lacquers, printing inks, typewriter rib-
bons, and carbon paper. The intense blue color of the iron(III) hexacyanoferrate(II) chromophore
arises from IVCT between the mixed-valence iron oxidation states (105) and can be removed by
oxidation or reduction. PB is the prototype of a number of polynuclear transition-metal hexa-
cyanometallates that form an important class of insoluble mixed-valence compounds (106). These
materials have the general formula M k [M (CN)6 ]l mH2 O (k, l, m integral), where M and M
are transition metals with different formal oxidation numbers. Since the rst report (107) con-
cerning the electrochemistry and electrochromism of PB as a thin lm, such materials have been
intensively investigated. PB-based ECDs that employed PB as the sole electrochromic material
were soon reported. These include a seven-segment display using PB-modied optically transpar-
ent electrodes at 1-mm separation (108), a solid-state system in which a PB-containing Naon R

composite lm was sandwiched between two ITO/glass substrates (109), and an ECD that uti-
lized a single lm of PB, without the addition of a conventional electrolyte (110). Several PB
analogs have been reported as thin lms in modied-electrode studies. Although the majority are

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MR41CH10-Mortimer ARI 27 May 2011 14:1

also expected to be electrochromic, absorption spectra as a function of redox state have rarely
been reported, and only ruthenium purple [iron(III) hexacyanoruthenate(II)] and osmium purple
[iron(III) hexacyano-osmate(II)] have been used in prototype (seven-segment) ECDs.
The electrochemistry of PB and its analogs was reviewed as early as 1986 (111), with more
recent surveys of electrochromism appearing as chapters in two research monographs (1, 2). Early
studies involved the preparation of thin-lm PB by galvanostatic (112), potentiodynamic (113), and
potentiostatic (113) electrochemical reduction of solutions containing iron(III) and hexacyano-
ferrate(III) ions. Reduction of the brown-yellow soluble complex, iron(III) hexacyanoferrate(III),
present as an adduct in equilibrium with the iron(III) and hexacyanoferrate(III) ions, is the principal
electron-transfer process in PB electrodeposition,
[FeIII FeIII (CN)6 ] + e = [FeIII FeII (CN)6 ] . 10.
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Charge-compensating cations are present in the PB lm for electroneutrality (114). Other early
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PB thin-lm formation methods have included electroless deposition, use of a sacricial anode,
extensive redox cycling of hexacyanoferrate-containing solutions, and use of catalytic silver paint.
Nanostructured PB thin lms have recently been created with a ner degree of control us-
ing assembly-based processing techniques. Thus, polymer nanocomposite lms of anionic PB
nanoparticles and cationic linear poly(ethyleneimine) have been fabricated (115, 116) using layer-
by-layer assembly, a process that involves the sequential adsorption of oppositely charged ma-
terials onto charged, electrically conducting substrates. In a variant of layer-by-layer assembly,
PB, ruthenium purple, and PB/ruthenium purple lms were prepared (117) by alternate exposure
of substrates to transition-metal cations and hexacyanometallate anions to create fully inorganic
metal hexacyanometallate lms through directed assembly. Because metal hexacyanoferrates have
a cubic crystal lattice structure, layering of metal cations and hexacyanoferrate anions is highly un-
likely, and multiple sequential deposition is perhaps a better description of the formation process
than layer-by-layer assembly (118).

Color Switching and Spectral Properties


Following transfer to pure supporting electrolyte solution, partial electrochemical oxidation of
the PB chromophore yields a green color state:

[FeIII FeII (CN)6 ] = {FeIII [FeIII (CN)6 ]2/3 [FeII (CN)6 ]1/3 }1/3 + 2/3e . 11.
blue green

Although in bulk form the green state is believed to have a xed composition with anion com-
position as above, for thin lms there is a continuous composition range between PB and the
fully oxidized golden yellow state. The latter may be obtained by electrochemical oxidation of a
particularly pure form of PB (113, 114).
[FeIII FeII (CN)6 ] = [FeIII FeIII (CN)6 ] + e . 12.
blue yellow

Reduction of PB yields the colorless redox state:


[FeIII FeII (CN)6 ] + e = [FeII FeII (CN)6 ]2 . 13.
blue colorless

For all the electrochromic redox reactions above, there is concomitant ion ingress/egress in the
lms for electroneutrality.
Figure 6 shows the spectra (114) of the yellow, green, blue, and colorless forms of PB and its
redox variants. Spectra of two intermediate states between the blue and the yellow forms are also
shown.

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MR41CH10-Mortimer ARI 27 May 2011 14:1

1.0
a

0.8 c

Absorbance (a.u.)
0.6 d

0.4 e
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0.2
f
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b
0
400 600 800 1,040 1,200
(nm)
Figure 6
Spectra of iron hexacyanoferrate lms on tin-doped indium oxide (ITO)/glass at various potentials:
(a) +0.50 V (blue), (b) 0.20 V (colorless), (c) +0.80 V ( green), (d ) +0.85 V ( green), (e) +0.90 V ( green), and
( f ) +1.20 V ( yellow) (potentials versus SCE) with KCl 0.2 mol dm3 + HCl 0.01 mol dm3 as supporting
electrolyte. Wavelengths (abscissa) are in nanometers. Adapted from Reference 114 with permission from
The Royal Society of Chemistry.

The intense blue color in the [FeIII FeII (CN)6 ] chromophore of PB (at +0.50 V; Figure 6a)
due to the IVCT absorption band is centered at 690 nm. The yellow absorption band corresponds
with that of [FeIII FeIII (CN)6 ] in solution; both maxima are at 425 nm and coincide with the (weaker)
[FeIII (CN)6 ]3 absorption maximum. On increase from +0.50 V to more oxidizing potentials, the
original 690-nm PB peak continuously shifts to longer wavelengths with diminishing absorption,
whereas the peak at 425 nm steadily increases owing to the increasing [FeIII FeIII (CN)6 ] absorption.
One broad voltammetric peak is usually seen for the overall blue-to-yellow process, in contrast
with the sharp blue-to-colorless transition. This contrasting voltammetric behavior, supported by
ellipsometric measurements (119), may imply continuous mixed-valence compositions over the
blue-to-yellow range.

MATERIALS FOR ELECTROCHROMIC DEVICE CONSTRUCTION

Principles of Electrochromic Device Operation


ECDs operate as rechargeable electrochemical cells, with each containing a minimum of two
electrodes separated by a layer of ion-containing electrolyte. A liquid, gel, or solid electrolyte is
sandwiched between the primary electrochromic electrode and a charge-balancing secondary elec-
trode. Color switching takes place on charge/discharge by application of an appropriate electrical
potential. ECDs are designed to operate in either absorptive/transmissive or reective modes.
For absorptive/transmissive devices, the secondary electrode redox reaction is chosen to be a
system in which there is imperceptible visible color change or as an electrochromic system in which
the change in color is complementary to the color at the primary electrochromic electrode, thus
providing enhancement of the colored/bleached contrast. Complementary coloring ECDs that
have been investigated include, for example, those with PB (colorless to blue on oxidation) as the
anodically coloring electrochromic material and WO3 (120122) (colorless to blue on reduction),

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MR41CH10-Mortimer ARI 27 May 2011 14:1

PEDOT (123) (light-blue transmissive to deep blue on reduction), and poly(butyl viologen) (124)
(colorless to purple on reduction) as cathodically coloring electrochromic materials.
For reective devices, traditionally one of the electrodes is silver backed, or polished platinum
FTO: F-doped tin
oxide is used to act as both the mirror and the supporting electrode. More recently, reective-type ECDs
on metallized substrates have been investigated (125128). In such ECDs, patterned electrodes
are prepared using line-patterning, screen-printing, and metal vapor deposition techniques. For
these devices, the secondary electrode color change is hidden.

Optically Transparent Electrodes


All ECDs require at least one optically transparent electrode. Devices operating in an absorp-
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tive/transmissive mode, such as spectacles, goggles, visors, or smart windows, require a second
optically transparent electrode as the rear electrode, unlike devices operating in a reective mode,
Annu. Rev. Mater. Res. 2011.41:241-268. Downloaded from www.annualreviews.org

such as information displays and antiglare mirrors. Electrode substrates comprise an optically
transparent, electrically conducting lm coated onto glass or exible PET. The optically trans-
parent, electrically conducting lm is usually a transparent conducting oxide such as ITO, F-doped
tin oxide (In2 O3 :F) (FTO), or antimony-doped tin oxide. Transparent conducting oxides are de-
generately doped semiconductor oxides that are transparent to visible light and have been the
subject of frequent reviews (129133). Although ITO is ubiquitously used worldwide in numer-
ous optoelectronic applications, including at-panel LCDs, the indium used in ITO is scarce,
and alternative materials with lower indium content, such as zinc-indium-tin oxide, are being
investigated (133). In all-polymer ECDs, a further option (134), PEDOT:PSS as the optically
transparent, electrically conducting lm, is spin coated onto commercial plastic transparency lm.
Films of pure single-walled carbon nanotubes have also emerged as an alternative to ITO, with
comparable transparency in the visible region and higher transparency in the 25-m infrared
region (135). Absorptive/transmissive polymer-based ECDs have been assembled using single-
walled carbon nanotubes on glass as electrode substrates (136, 137). Films of planar sheets of
carbon one atom thick (graphene) on PET, recently prepared as large (76-cm-diagonal) transpar-
ent electrodes, work in a touch-screen panel device (138). Such materials are likely to be useful
for ECDs.

Electrolyte Layers
The layer of electrolyte between the two electrodes in an ECD must be ionically conductive but
an electronic insulator. Further requirements are transparency in the wavelength range used, a
wide electrochemical window, and low volatility. In type I and type II ECDs, the electrochromic
material is dissolved in a liquid electrolyte, which can be either aqueous or a polar organic solvent
such as acetonitrile or a variety of other nitriles, dimethylformamide, propylene carbonate, or -
butyrolactone. The dissolved electrochromic material approaches the working electrode through
this medium during electrochromic coloration. Solutions may also contain a dissolved supporting
electrolyte in a high concentration to suppress migration effects. A thickener, such as acrylic
polymer, poly(vinylbutyral), or colloidal silica (139), may be added to the solution to increase its
viscosity. This practice improves the appearance of an ECD because the coloration develops at
different rates in different areas in a fast device. Hence, articially slowing the rate of coloration
helps ensure an even coloration intensity. Thickening also improves the safety of a device should
breakage occur and helps minimize mass transport by convection. Gelling the electrolyte, e.g., by
adding a polyether such as poly(ethylene oxide), can also enhance electrochemical stability.

258 Mortimer
MR41CH10-Mortimer ARI 27 May 2011 14:1

In type III systems, although the electrolyte contains no soluble electrochromic material, it
now has two roles. First, during coloration and bleaching, for electroneutrality it supplies the
mobile counterions that enter and leave the facing solid-electrochromic material layers. But sec-
ond, the electrolyte still effects the accompanying conduction between the electrodes. Type III
ECDs operating with protons as the mobile ions can contain aqueous acids. In Debs (30) early
ECD, for example, the electrolyte was aqueous 0.1 mol dm3 sulfuric acid. Liquid acids are now
rarely used because of their tendency to degrade or dissolve electrochromic materials and because
of fears that the device will leak. A majority of reported type III ECDs employ inorganic solids or
viscoelastic semisolid organic polymers; the latter are exible and resistant to mechanical shock.
Such type III cells are designed to remain solid during operation as all-solid-state devices, and a
wide range of multilayered device structures and geometries have been contemplated. Many solid
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inorganic materials with high cationic conductivity serve as electrolytes for ECDs. Examples are
thin layers of LiNbO3 for a WO3 /V2 O5 system (140); hydrogen uranyl phosphate tetrahydrate
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(HUO2 PO4 4H2 O or HUP) in a WO3 system (141); and MgF2 (142), again for a WO3 sys-
tem. Semisolid organic electrolytes have also been used for ECDs, and these materials fall into
two general categories: polyelectrolytes (143) and polymer electrolytes (144). Polyelectrolytes are
polymers containing ion-labile moieties at regular intervals along the backbone. Popular examples
are poly(AMPS), Naon R
, polystyrene sulfonic acid, and poly(acrylic acid) in which the proton-
donor moiety is an acid. The ionic conductivity of polyelectrolytes such as poly(AMPS) depends
critically on the extent of water incorporation; wholly dehydrated poly(AMPS) is not conductive,
but conductivity increases rapidly with water content. Polymer electrolytes are effectively solu-
tions of ionic salts, including lithium perchlorate (LiClO4 ) and lithium triuoromethanesulfonate
(LiCF3 SO3 H), with neutral macromolecules such as poly(ethylene oxide), poly(methyl methacry-
late), poly(propylene glycol), or poly(vinyl alcohol) as the immobile solvent. The viscosity of such
polymers increases with molecular weight, so polymers range from liquid at low molecular weight
to longer polymers that behave as rigid solids. It is quite common for polymeric electrolytes to
have an opaque white ller powder such as TiO2 added to enhance the contrast ratio in displays. A
white layer also dispenses with any need to tailor the optical properties of the secondary electrode,
the color and reectivity of which are unimportant when the secondary electrode is positioned
behind the layer of electrolyte containing the opaque ller.
Interest in the use of room-temperature ionic liquids in (polymer) ECDs, producing devices
with enhanced lifetimes and faster switching speeds, has recently grown. An early example is the use
of a thin layer of 1-butyl-3-methylimidazolium tetrauoroborate ([BMIM][BF4 ]) in the fabrication
of prototype alphanumeric displays and 5 5cm electrochromic windows with poly(aniline)
as the anodically coloring electrochromic material and PEDOT and/or poly(3-octylthiophene)
as the cathodically coloring electrochromic materials (145). Ionic liquids can be used both as
the electrolyte medium for the electropolymerization of electrochromic conjugated conducting
polymers and as the electrolyte layer in ECDs.

Device Encapsulation
The process of assembling the components of a commercial or prototype ECD, and the mounting
materials, is as important as (and perhaps more important than) the operation of the parts taken
individually. In ECDs containing a liquid or semisolid electrolyte, the separation between the two
electrodes can be maintained by introducing at or spherical spacers, which act in a manner similar
to that of the minute spherical beads of constant diameter employed in fabricating an LCD, to
maintain the precisely dened distance between the two parallel electrodes.

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MR41CH10-Mortimer ARI 27 May 2011 14:1

Finally, the device must be sealed. The fabrication of a robust, leakproof seal to encapsulate
a type I or type II ECD is not a trivial problem: In 2001, Byker (at that time of Gentex) stated,
Polymer sealant materials are often critical to the life of an EC device, and may represent as big
a R&D challenge as the EC system itself in a device commercialization effort (139). One of the
principal problems is chemical durability; a second problem is the hydrostatic pressures that form
in large devices containing liquid electrolytes because the weight of liquid causes the bottom of
the device to swell, yet such weight can push the tops of the panes together until they break. The
sealant around an ECD must be chemically stable. It is regrettablebut perhaps inevitable in view
of industrial competitivenesshow many reports of actual devices (prototype and in production)
fail to divulge details of device encapsulation. In a life cycle analysis of the environmental impacts
associated with all the basic materials used during the manufacture of a WO3 -based electrochromic
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glazing, properties of the acetic silicone sealant are discussed (146). Acetic silicone sealants are
based on poly-dimethyl siloxanes, typically contain a cross-linker and methyl triacetoxy silane, and
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are cured by atmospheric moisture. The long-lasting seal is resistant to the effects of sunlight, rain,
snow, ozone, UV radiation, and temperature extremes. Electrochromic reective displays (147)
TM
based on nanocrystalline metal oxide/viologens are encapsulated with the DuPont thermoplastic
Surlyn R
.

CONCLUSIONS
Electrochromic materials research and development continue to expand in terms of both the range
of reported electrochromic materials and device structures and the proposed novel applications.
Commercial applications include Gentexs NVS R
mirrors, which automatically dim to eliminate
glare in several million automobiles, and the electrochromic adjustable-darkening windows that
reduce cabin glare in the new Boeing 787 Dreamliner. A major ultimate goal of many contem-
porary electrochromism studies is the provision of large-scale electrochromic windows for light
attenuation in buildings at modest expenditure. If applied widely, such technology would save ex-
tensive air-conditioning energy costs and improve ofce comfort (21). Display systems are a further
major goal, but universally used LCDs present formidable rivalry. However, large-scale screens
offer an attractive possibility where liquid crystal technology may struggle, and electrochromic
technology would almost certainly be much more economical than plasma screens.
Tailoring the color of electrochromic materials is an active research area, particularly with
conjugated conductive polymers (11). Electrochromic colors are now routinely measured by spec-
trocolorimetry using Commission Internationale de lEclairage (x,y) chromaticity coordinates (as
in Figure 4). Color quantication is useful for the comparison of the electrochemical and optical
properties of conjugated conducting polymers and for gaining control of the color of dual-polymer
ECDs (148). In situ colorimetry has also been used to dene the hue, saturation, and luminance
properties of PB lms (149) and the HV system (150).

SUMMARY POINTS
1. The study of electrochromism dates back to the nineteenth century. However, only in
the last quarter of the twentieth century did such study gain real impetus.
2. Commercial applications of electrochromic materials include Gentex Corporations
NVS R
mirrors, which automatically dim to eliminate glare in several million automo-
biles, and the electrochromic adjustable-darkening windows that reduce cabin glare in
the new Boeing 787 Dreamliner.

260 Mortimer
MR41CH10-Mortimer ARI 27 May 2011 14:1

3. A major ultimate goal of many contemporary electrochromism studies is the provision of


large-scale electrochromic windows for light attenuation in buildings at modest expen-
diture. If applied widely, such technology would save extensive air-conditioning energy
costs and improve ofce comfort.
4. Electrochromic display systems are a further major goal.
5. The main classes of electrochromic materials are metal oxides, viologens, conjugated
conducting polymers, metal coordination complexes, and Prussian blue.
6. Although a vast number of chemical species exhibit electrochromic properties, only those
with a favorable contrast ratio, coloration efciency, write-erase efciency, cycle life, and
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response time are potentially useful in commercial applications.


7. Electrochromic devices operate as rechargeable electrochemical cells, with each cell con-
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taining a minimum of two electrodes separated by a layer of ion-containing electrolyte.


8. Electrochromic devices are designed to operate in either absorptive/transmissive or re-
ective modes.

FUTURE ISSUES
1. Can smart windows be developed with a color-neutral (gray) electrochromic state?
2. Can color-switching response times be reduced, especially with metal oxidebased
devices?
3. What is the long-term photostability of organic-based electrochromic systems?
4. What is an acceptable coloration efciency for the widespread adoption of ECDs?
5. Are there any other options in the development of electrochromic materials/devices that
switch from colorless to black states?

DISCLOSURE STATEMENT
The author is not aware of any afliations, memberships, funding, or nancial holdings that might
be perceived as affecting the objectivity of this review.

ACKNOWLEDGMENTS
Where the author has cited his own work and that with coworkers and/or collaborators, this was
in some cases supported by the Engineering and Physical Sciences Research Council. Fruitful
collaboration over many years with D.R. Rosseinsky (University of Exeter), P.D. Beer (University
of Oxford), and J.R. Reynolds (University of Florida) is acknowledged. P.M.S. Monk (erstwhile
Senior Lecturer, Manchester Metropolitan University) is thanked for his earlier extensive litera-
ture reviews and our collaboration (with D.R. Rosseinsky) in the preparation of the key research
monographs cited as References 1 and 2.

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MR41CH10-Mortimer ARI 27 May 2011 14:1

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Annual Review of
Materials Research

Contents Volume 41, 2011


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Materials Science of Biological Systems


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Advances in Drug Delivery


Brian P. Timko, Kathryn Whitehead, Weiwei Gao, Daniel S. Kohane,
Omid Farokhzad, Daniel Anderson, and Robert Langer p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 1
Crystallization Pathways in Biomineralization
Steve Weiner and Lia Addadi p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p21
Deformation and Fracture Mechanisms of Bone and Nacre
Rizhi Wang and Himadri S. Gupta p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p41
Linear and Nonlinear Rheology of Living Cells
Philip Kollmannsberger and Ben Fabry p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p75
Mussel-Inspired Adhesives and Coatings
Bruce P. Lee, P.B. Messersmith, J.N. Israelachvili, and J.H. Waite p p p p p p p p p p p p p p p p p p p p p p99
Nanomechanics of the Cartilage Extracellular Matrix
Lin Han, Alan J. Grodzinsky, and Christine Ortiz p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 133
Plant Stems: Functional Design and Mechanics
Thomas Speck and Ingo Burgert p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 169

Current Interest
Elastic and Mechanical Properties of the MAX Phases
Michel W. Barsoum and Miladin Radovic p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 195
Electrocaloric Materials
J.F. Scott p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 229
Electrochromic Materials
Roger J. Mortimer p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 241
Nanowire Solar Cells
Erik C. Garnett, Mark L. Brongersma, Yi Cui, and Michael D. McGehee p p p p p p p p p p p p 269
Nonconventional (Non-Silicon-Based) Photovoltaic Materials
T. Unold and H.W. Schock p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 297

v
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On the Future Availability of the Energy Metals


T.E. Graedel p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 323
Oxide Electronics Utilizing Ultrafast Metal-Insulator Transitions
Zheng Yang, Changhyun Ko, and Shriram Ramanathan p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 337
Point Defects in Oxides: Tailoring Materials Through
Defect Engineering
Harry L. Tuller and Sean R. Bishop p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 369
Recent Developments in Semiconductor Thermoelectric Physics
and Materials
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Ali Shakouri p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 399


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Thermoelectric Phenomena, Materials, and Applications


Terry M. Tritt p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p p 433

Index

Cumulative Index of Contributing Authors, Volumes 3741 p p p p p p p p p p p p p p p p p p p p p p p p p p p 449

Errata

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vi Contents