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A Vertically Integrated Solar-Powered Electrochromic

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Window for Energy Efficient Buildings
Aubrey L. Dyer, Rayford H. Bulloch, Yinhua Zhou, Bernard Kippelen, John R. Reynolds,*
and Fengling Zhang*

It is well recognized that the most abundant source for renew- windows.[4] However, while ECWs can offer the ability to lower
able energy is solar radiation, and with continued improve- cooling needs, these windows still require an external power
ments in research and development, efforts in adopting source, offsetting some of the energy savings.
photovoltaic (PV) technologies are at an all-time high. However, To address this last point, there have been efforts towards
while solar radiation provides renewable sources for electricity, integration of electrochromics with photovoltaic devices,
it is also one of the main causes for energy consumption in res- resulting in so-called self-powered, or photoelectrochromic,
idential and commercial buildings through increased cooling devices.[5–11] Many device types incorporate the PV component
demands in warm months and increased interior lighting externally, or at the periphery of the ECW,[6,7,11] while others
needs to counteract added shading used to cut daytime glare.[1] incorporate it vertically, as part of the device stack.[8–10] This
One report estimates that 41% of the energy consumed in latter device type requires the PV to be highly transparent and
the U.S. in 2009 was in the buildings sector (commercial and is typically based on low-gap a-Si or dye-sensitized solar cells as
residential) which is an increase of 48% from 1980.[1] Of this, the power-generating component and metal oxides (e.g., WO3)
19% can be attributed to space cooling and lighting combined as the active electrochrome.[8–10] While these are early proof-of-
(37% is attributed to space heating and the remainder to water principle demonstrations of the vertical self-powered window
heating and consumer electronics/appliances).[1] A technology concept, inherent drawbacks remain as these examples require
that holds much promise for decreasing both lighting and sputter-deposited layers, and/or an external power source to
cooling energy use through modulation of transmitted light switch the device back to the bleached state.
and solar heat is variable transmission electrochromic windows Here, we demonstrate a self-powered, solution processable
(ECWs).[2,3] The ECWs offer tunable shading, allowing lighting and vertically integrated, polymeric variable transmission elec-
energy use savings of 48-67%, while decreasing annual peak trochromic/photovoltaic (EC/PV) device, where the EC and PV
cooling loads up to 19–26% when compared to efficient low-e components share common transparent conducting polymer
electrodes. Solution processability offers the advantage of pro-
cessing under ambient conditions and the promise of high
Dr. A. L. Dyer, R. H. Bulloch, Prof. J. R. Reynolds
throughput roll-to-roll processing of fully flexible devices for
School of Chemistry and Biochemistry retrofit integration. This EC/PV concept is shown in Figure 1
Center for Organic Photonics and Electronics with device schematics and photographs. The device consists of
Georgia Institute of Technology two inverted PV cells in tandem with an ECD, which shares two
Atlanta, GA 30332, USA transparent electrodes with the PV cells, as shown in Figure 1a.
E-mail: [email protected]
The PV cells (PV1 and PV2 in the schematic) are based on
Prof. J. R. Reynolds
School of Materials Science and Engineering an inverted geometry with the photoactive layer comprised of a
Center for Organic Photonics and Electronics blend of the low band gap polymer, poly(diketopyrrolopyrrole-
Georgia Institute of Technology terthiophene (PDPP3T), and phenyl-C61-butyric acid methyl
Atlanta, GA 30332, USA ester (PC61BM) as previously reported.[12,13] To produce these
Dr. Y. H. Zhou, Prof. B. Kippelen cells, ITO surfaces were first converted to electron-collecting
School of Electrical and Computer Engineering
Center for Organic Photonics and Electronics
contacts via modification with solution-processed ZnO and
Georgia Institute of Technology poly(ethylenimine ethoxylate) (PEIE) (Electrodes 1 and 4).[14]
Atlanta, GA 30332, USA The use of PEIE on the ZnO allows further reduction of the
Dr. Y. H. Zhou work function of the electron-collecting layer and improves the
Wuhan National Laboratory for Optoelectronics electron collection efficiency, which has previously been con-
Huazhong University of Science and Technology firmed by Kyaw et al.[15] Next, the PDPP3T:PC61BM layer was
Wuhan 430074, China
deposited through spin casting (PV layers). This is followed by
Prof. F. Zhang
Biomolecular and Organic Electronics a layer of high-conductivity poly(3,4-ethylenedioxythiophene):
Department of Physics poly(styrene sulfonate) (PEDOT:PSS) spin cast on top to serve
Chemistry and Biology simultaneously as transparent hole-collecting electrodes for the
Linköping University PV cells and as transparent electrodes for the ECD portion of
58183, Linköping, Sweden
E-mail: [email protected]
the device (labeled as electrodes 2 and 3).
Fabrication of the EC portion was performed by airbrush
DOI: 10.1002/adma.201401400 spraying of two electrochromic layers onto exposed PEDOT:PSS

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coloring electrochrome—switching from highly absorptive

magenta in the neutral state to highly transmissive colorless
in the oxidized state, while MCCP exhibits minimal color in
either redox state—providing only charge balance within the
ECD.[16,17] The repeat unit structures for each of the polymeric
materials used in the PV and EC portions of the device are pro-
vided in Figure S1. An ionically conducting gel electrolyte was
then deposited between the two separate EC layers and the
device laminated to complete the fully integrated EC/PV device
as shown in Figure 1b.
Device operation between colored and bleached states
(Figure 1c and Video 1 in SI) is achieved through connection
of the appropriate PV electrodes to the EC electrodes. The
bleached state is induced (top schematic) by connecting elec-
trode 1 (PV1) to electrode 3 (MCCP-coated electrode). This
causes reduction of the MCCP layer and, to maintain charge
balance, oxidation of the ECP-Magenta layer to result in the
device bleached state as shown in the photograph to the right.
In order to switch the device to the colored state, electrode 4
(PV2) is connected to electrode 2 (ECP-Magenta-coated elec-
trode) to cause ECP-Magenta to reduce and color, while the
MCCP layer oxidizes as shown in the bottom schematic and the
photograph to the left of Figure 1c.
Uniquely, this device provides vertical integration of solu-
tion-processed polymeric materials with common electrodes for
different devices; a single PV cell providing sufficient voltage
to drive the EC layers, and a high degree of visible transpar-
ency from the low bandgap photovoltaic polymer:PCBM layer.
As can be seen in Figure 2a, a single cell has a transmittance
at 550 nm (the peak wavelength of photopic sensitivity) of 76%,
while two stacked cells maintain a high transmittance of 58%.
This can also be seen in the inset photograph of a single cell.
This high level of transparency is attributed both to the low
bandgap and relatively narrow absorption profile of the photo-
active polymer (PDPP3T), which absorbs in the NIR with a
peak at 850 nm (with an optical bandgap of 1.37 eV), and the
highly transparent electrode layers.
As provided in Figure 2b (with values reported in Table 1) a
PV cell, with an active area of 1 cm2, generates 0.70 V open-cir-
cuit voltage (Voc), ∼3 mA short-circuit current (Isc), and 0.8 mW
at the Maximum Power Point (MPP) before application of an
electrochromic layer by spray-casting. The initial modest per-
formance of these cells is not unexpected as the active layer is
thin (∼40 nm) for high transparency and relatively large area
(1 cm2) and use of the less conductive PEDOT:PSS top elec-
Figure 1. Concept and structure of solar-powered electrochromic device. trode (as compared to metal electrodes). After application of
a) Schematic cross section structure of the EC/PV laminated vertical the electrochromic layers (exemplified by ECP-Magenta onto
stack. The device consists of two inverted PV cells (PV1 and PV2) and PV cell 1), the cell performance drops, possibly due to spray-
an EC cell. The electrodes comprising the device are (Electrode 1) the
processing of the EC layers from an organic solvent. It should
electron-collecting electrode of the bottom PV cell, (Electrode 2) the
hole-collecting electrode of the same PV cell/working electrode of the be noted that a decrease in current and voltage for the PV2 cell
ECD, (Electrode 3) the hole-collecting electrode of the top PV cell/counter coated with MCCP was more than that for PV1 (Table 1). We
electrode of the ECD, and (Electrode 4) the electron-collecting electrode attribute this to the low oxidation potential of MCCP resulting
of the top PV cell. b) Schematic of device layer components (numbering in electron exchange at the interface to oxidize the MCCP and
corresponds to electrodes in a). c) Photograph and schematic of EC/PV reduce a thin layer of the PEDOT:PSS, decreasing the conduc-
self-powering concept showing connections required to cause bleaching
tivity of the conducting polymer electrode and resulting in a
(top) or coloring (bottom) of ECD under illumination.
drop in PV cell efficiency.
PV electrodes (EC layers). The EC polymers are PProDOT- It is evident that the desire for transparent PV cells (giving
(CH2OEtHx)2, referred to as ECP-Magenta, and PProDOP- away photon absorption to allow for transparent windows) and
N-C18H37, referred to as MCCP. ECP-Magenta is the actively orthogonal processing of multiple layers are at the expense of

2 wileyonlinelibrary.com © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2014,
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device efficiency.[18,19] This is exemplified in Figure S2 where

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the PV device characteristics while not powering the EC device
are illustrated. On the other hand, while the efficiencies are not
targeted to high values, they are sufficient to operate the EC
device in a net positive power mode. When comparing the
current, voltage, and power needs of the electrochromic cell
to that delivered by the photovoltaic cells, it is apparent that
the energy demands for electrochromic operation are far less.
As is shown in Figure S3, the initial current demands of the
electrochromic layers peaks at 2.3–2.9 mA (corresponding to
a power of 3-4 mW) and quickly (within 2 seconds) decays to
a background current of 0.2-0.3 µA (corresponding to a power
of 20-33 µW). This current profile is typical of electrochemical
devices of this type where a majority of the current demands
are instantaneous and compromise of both redox and double-
layer charging currents. As the double-layer is established and
redox process complete, a minimal background current can be
applied to maintain the redox (i.e., color) state of the device.
However, in thin layer electrochromic devices, such as the one
employed here, there is sufficient electrochromic memory (the
color of the device is maintained even with no voltage applied)
that the device can be operated for longer periods of time
with even lower power requirements. This is demonstrated
in Figure S4, where the percent reflectance maintained after
removal of the solar cell connections is monitored over a period
of up to 75 s. The percent drift (the amount by which the reflec-
tance decreases at the end of 75 s relative to when the photo-
voltaic connection is removed indicated by the dotted lines) is
less than 5%, after allowing enough time (≥3 s) for the device to
switch completely.
With the low power demands of the EC cell and the elec-
trochromic memory discussed, power needs for switching
the electrochromic layers from fully colored to fully bleached
Figure 2. Current-Voltage Profile and Transmittance Spectra for Trans- (or reverse) and maintaining those colored states, for even a
parent Tandem Solar Cells used in EC/PV Stack. a) Spectral transmittance short amount of time, can be estimated. For example, to afford
across the visible and near infrared for two PV cells (blue line) and for a
a switch from colored to bleached would require as little as
single PV cell (red line) illustrating high level of transmittance of cells with
inset photograph of a single PV cell. b) Current-Voltage curves for a single 0.4 mW for a 1 cm2 device over a 5 s period of time (or energy
PV cell after coating with ECP-Magenta (triangles) and current-voltage of 2 mJ). This 5 s hold is more than enough time to allow for
curves for PV cells in complete EC/PV stack when connected in parallel the EC device to fully bleach, as is shown in Figure 3a where
(solid circles) and in series (open circles). the transmittance contrast saturates at 2 s of full illumination
(inset). Figure S5a shows the time of illumination required to
reach saturation as 3 s for the coloring process. When consid-
Table 1. Semi-transparent photovoltaic device characteristics. ering the electrochromic memory, a further 70 s of time can
pass (or longer) with less than a 5% decrease in transmittance
PV cells Voc Jsc FF Power before a refresh voltage pulse is required from the solar cell.
[V] [mA cm−2] [mW] During this additional 70 s where the electrochromic cell is not
PV1 (before spray)a) 0.70 3.2 0.38 0.84 powered, the energy generated by the PV devices can be uti-
PV2 (before spray)a) 0.68 2.8 0.41 0.79 lized to power other functions. Further, given that there are two
b)
PV cells in tandem with the EC layers, these cells can be con-
PV1 (after spray) 0.66 3.2 0.28 0.61
nected in either parallel or series to generate additional current
PV2 (after spray)b) 0.42 1.8 0.26 0.20 or voltage as shown in Figure 2b and in Table 1. For example,
PV1/PV2 0.51 3.3 0.30 0.50 when not powering the EC portion of the device, PV1 and PV2
tandem-Parallelc) can be connected in series to generate additional power to
PV1/PV2 1.04 1.4 0.38 0.54 operate peripheral devices (e.g., lighting, fans, consumer elec-
tandem-Seriesd) tronics, etc.), or to charge a battery that would allow for opera-
a)PV device performance prior to addition of EC layer; b)PV device performance
tion of the windows when no lighting is present. This, in effect,
after spray-casting of EC layer; c)tandem PV devices in EC/PV stack connected in
allows the EC/PV windows to operate as net energy positive
parallel as shown schematically in Figure S2a; d)tandem PV devices in EC/PV stack devices as the power generated by the PV cells is in excess of
connected in series as shown schematically in Figure S2b. what is required for EC operation. It should be noted that in the

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a)
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Of course, it is understood that operation of PV windows

55 25
occurs under conditions markedly different than those in
50 typical laboratory settings. In fact, the angle at which the solar
Percent transmittance (% T)

20
radiation hits a building window is not at normal incidence at
45

Δ% T
15 midday, while typical laboratory devices are characterized at
40
10 normal incidence. Add to this the fact that there are very few
35 days that the illumination intensity is consistently 1 sun, which
5
30 0 1 2 3 4 5 6 raises the question as to whether the EC/PV windows would
25 Time (s) operate with full efficiency under these non-ideal conditions.
20 With that in mind, the EC/PV devices were characterized for
contrast and switching speeds under illuminations that are less
15
than 1 sun for 3 s of illumination (i.e., 75%, 50%, and 25% of
10
1 sun, correlating to 75, 50, and 25 mW/cm2 intensity). As is
5 shown in Figures 3b and S5b, there is a difference in contrast
0 achieved under reduced illumination when switching from
400 500 600 700 the colored to bleached (Figure 3b) and bleached to colored
Wavelength (nm) (Figure S5b) states. The maximum contrast (20%) is achieved
with intensities greater than 75 mW/cm2 when switching to
b) 55 the bleached state and full intensity (100 mW/cm2) is needed to
50 20 achieve the maximum contrast when switching to the colored
Percent transmittance (% T)

45 state (Figure S5b inset). Yet there is only a 4% difference in

18
contrast when lower intensities (50 or 75 mW/cm2) are utilized.
Δ% T

40
16 To gain a practical perspective on these intensities, we meas-
35
ured the solar irradiance under non-ideal conditions (i.e., dif-
30 14 ferent times of day in Atlanta during the month of December,
25 50 75 100
25 from different angles) to allow correlation with how these
% Sun
20 devices would be expected to perform in real applications. For
15 example, the measured intensity of solar radiation varied from
0.09 sun (facing East), to 0.20 sun (facing North), 0.40 sun
10
(facing West), and 0.88 sun (facing South).[20] Additionally, we
5
measured the solar irradiation in Southern Sweden (Latitude:
0 +58.41) at 2 pm in early December with a measured value of 0.19
400 500 600 700
sun. To further characterize device performance under these
Wavelength (nm) conditions, we monitored the contrast after different illumina-
tion times under 25 mW/cm2 illumination shown in Figure S6.
Figure 3. Transmittance spectra across the visible region for a fully
assembled EC/PV device during bleaching. a) Full device spectra when Even under this reduced illumination, full device contrast is
illuminated for increasing time periods under AM 1.5 (1 sun) illumina- achieved, albeit with longer illumination times required (6 s for
tion. Filled square = fully colored state at start, open square = 1 s illumi- bleaching and 3 s for coloring). This is not unexpected as the
nation, circle = 2 s, up-triangle = 3 s, down-triangle = 4 s, and diamond PV voltage (what drives EC operation) is less sensitive to illumi-
= 5 s. Inset shows delta percent transmittance (as measured at 550 nm) nation intensity and the PV current (what drives EC operation
for various illumination times illustrating fully contrast achieved for 2 s speed) is linearly dependent on illumination intensity, hence
of illumination under 1 sun. b) Full device spectra when illuminated for
3 s under varying intensities of light. Filled square = fully colored state
the longer illumination times required.[21–23] These results
at start, open square = 25% sun (i.e., 25 mW/cm2), circle = 50% sun show that this device concept is promising for practical solar-
(i.e., 50 mW/cm2), up-triangle = 75% sun (i.e., 75 mW/cm2), and down- powered, net energy positive windows for lighting and solar
triangle = 1 sun (i.e., 100 mW/cm2). Inset shows delta percent transmit- heat control for energy efficient buildings. However, it should
tance (as measured at 550 nm) for various illumination intensities. be noted that while this is the first proof of concept demonstra-
tion of a polymeric, solution processed net energy positive EC/
tandem configuration, there are limitations in obtained power PV device, further work is needed to improve device operation,
in both series and parallel connections. This can be attributed optimize device components, increase device area, and incor-
to the drop in OPV performance after spraying of the organic porate fully solution processed and flexible device layers while
EC layers as the parallel/series measurements provided were understanding limitations on device lifetime and durability.
performed on these altered cells. In a series connection, the Future work will tackle these improvements and challenges.
combined current density is limited by the subcell with the In conclusion, we demonstrate the first solution processed
smaller current (PV2 in this case) while in the parallel configu- polymer EC/PV window type device by vertically integrating a
ration, the overall voltage of the tandem configuration is limited polymer ECD with two inverted transparent organic PV cells
by the subcell with the lower voltage (PV2 again). The result is using EC and PV active materials that are all solution process-
a drop in combined overall power for both configurations. It is able. Selectively connecting two of four electrodes of the EC/PV
expected that as improvements are gained in preparing these device, a self-powered ECD can be reversibly switched between
layered devices, this loss in overall power will be minimized. transparent and colored states driven by two integrated PV cells.

4 wileyonlinelibrary.com © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim Adv. Mater. 2014,
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Considering that the EC/PV operates effectively even under 180 nm (+/− 20 nm) and 250 nm (+/− 30 nm) as measured by stylus
low intensity illumination of 0.25 sun with a switching time of profilometry (Bruker Dektak XT). Strips of VHB (3M) foam acrylic tape
3–6 s demonstrates the feasibility of the EC/PV in window appli- were then used to define the device area. A gel electrolyte (0.5 M LiBTI
in propylene carbonate, 8 wt% PMMA) was pipetted into this area, and
cations under oblique illumination of the Sun. Furthermore, the sealed in with the second transparent PV cell onto the surface of which
two PV cells can be connected in parallel or series to function as the second ECP has been spray cast. Contact to the completed device
a tandem PV cell generating power for other applications. There- was facilitated by the addition of ½ inch copper tape (series 1181, 3M)
fore, the EC/PV cell is a net energy positive device, which gener- at the substrate edges.
ates electricity in addition to modulating incoming light and heat Characterization of ECDs: Photography of films and devices was
through windows. This work may have broad impact as such performed using a Nikon D90 DLSR camera, with a Nikon 18-105 mm
VR lens. UV-Vis-NIR transmittance spectra (Figure 2a and Figure S7a)
EC/PV device concepts can lead to solar powered EC windows
and device switching kinetic data (Figure S8b) were recorded using a
which will decrease the energy demand for space cooling and Cary 5000 spectrophotometer. Colorimetric data (Figure S7b) was
significantly cut the energy consumption of buildings, especially generated using this data. Potential control for device switching in
for skyscrapers and passive houses. Moreover, the EC/PV fully Figure S7 and Figure S8b was facilitated by a Princeton Applied Research
processed from organic solutions is compatible with printing potentiostat/galvanostat (model PAR273A), under CorrWare control.
or roll-to-roll techniques for large-scale production to lower ulti- Visible region transmittance spectra for device switching (Figure 3,
Figure S5, Figure S6) was recorded using an Ocean Optics USB2000+
mate cost. The EC/PV windows may also have a large impact on
fiber optic spectrometer. Reflectance data (Figure S4 and Figure S8a)
the building and glass industries by adding two new functions to was gathered using a multichannel spectroradiometer (Optronix, model
conventional windows to offset electricity consumption of build- OL770-DMS) with a CCD imaging telescope attachment (Optronix,
ings and relieve our dependence on fossil fuels. model OL610). Samples were placed on a PTFE diffuse reflectance
standard (Optronic Laboratories, model OL25RS) in order to reflect
light to the CCD imaging telescope for recording. Illumination for device
switching and reflectance spectroscopy was provided by a Newport lamp
Experimental Section (model 94021A).
Preparation of transparent PV cells: ITO-coated glass substrates
(15 Ω sq−1, Colorado Concept Coatings LLC) were cleaned in sequential
ultrasonic baths of detergent, distilled water, acetone, and isopropanol.
The ZnO precursor was prepared by dissolving zinc acetate dihydrate Supporting Information
(Sigma-Aldrich, 0.5 g) and ethanolamine (Aldrich, 0.14 g) in 5 mL Supporting Information is available from the Wiley Online Library or
2-methoxyethanol (Sigma-Aldrich) and stirred overnight in air. Then the from the author.
solution was spin coated on the plasma-treated ITO substrates at a speed
of 3000 rpm and annealed at 150 °C in air for 1 h. The ZnO film was
30 nm thick. A polymer surface modification layer of polyethylenimine
ethoxylate (Sigma-Aldrich, PEIE) was spin coated on top of the ITO/ Acknowledgements
ZnO samples at a speed of 5000 rpm and annealed at 100 °C in air for
10 min. The film thickness is nominally 10 nm derived from ellipsometry F. Z. greatly appreciates financial support from Swedish Governmental
as previously demonstrated.[14] Then the samples were transferred into Agency for Innovation Systems (VINNOVA) through program VINNMER
a N2-filled glove box to coat the photoactive layer PDPP3T (Solarmer (2008-03422). J.R.R thanks BASF and the Office of Naval Research
Materials Inc.): phenyl-C61-butyric acid methyl ester (PCBM, Nano-C (N00014-11-1-0245) for funding, while Y.Z. and B.K. acknowledge
Inc.). The photoactive layer was prepared by spin coating from the funding from the Office of Naval Research (N00014-14-1-0126).
overnight stirred solution of PDPP3T:PCBM (1:2, weight ratio) in a
mixture of dichlorobenzene:chloroform,1,8-diiodooctane (79:16:5, v/v/v) Received: March 28, 2014
solution with a total concentration of 18 mg ml−1 at a speed of 1000 rpm Revised: April 23, 2014
for 1 min. The photoactive layer was pumped for 10 min and annealed Published online:
for 5 min at 75 °C to remove residual solvent. 5% dimethyl sulfoxide
was added into PH1000 solution and stirred overnight at 300 rpm at
room temperature to increase its conductivity. PH1000 solution was spin
coated on the active layer at 1000 rpm for 15 s and annealed on a hot [1] U.S. Department of Energy, Energy Efficiency and Renewable
plate at 80 °C for 5 min in the glove box. Prior to the spin coating of Energy, 2011 Buildings Energy Data Book, prepared by D&R Interna-
PH1000, the surface of PDPP3T:PCBM was exposed for a short time (1 s) tional, Ltd. March 2012.
to plasma treatment to render the surface hydrophilic. Current-voltage [2] N. L. Sbar, L. Podbelski, H. M. Yang, B. Pease, Int. J. Sustainable
(I-V) characteristics were measured inside a N2-filled glove box by using Built Environ. 2012, 1, 125.
a source meter (Keithley Instruments 2400) controlled by a LabVIEW [3] C. G. Granqvist, Switchable Glazing Technology: Electrochromic Fen-
program. To test the solar cell properties under illumination, an Oriel estration for Energy-Efficient Buildings, in Nearly Zero Energy Building
lamp with an intensity of 100 mW/cm2 was used as the light source.
Refurbishment, Springer, London, UK 2013.
Fabrication of electrochromic devices (ECDs): Synthesis and purification
[4] E. S. Lee, S. E. Selkowitz, R. D. Clear, D. L. DiBartolomeo,
of the electrochromic polymers used in device fabrication, referred to as
J. H. Klems, L. L. Fernandes, G. J. Ward, V. Inkarojrit, M. Yazdanian,
ECP-Magenta (26 kDa, PDI – 1.7) and MCCP (63 kDa, PDI – 1.7), has
been described elsewhere.[8,11] Polymers were dissolved into toluene at a Advancement of Electrochromic Windows, California Energy Commis-
concentration of 2 mg mL−1, and passed through 0.45 µm PTFE syringe sion, PIER. 2006, Publication number CEC-500-2006-052.
filters prior to spray casting. Solutions were then spray cast, using an [5] C. Bechinger, S. Ferrere, A. Zaban, J. Sprague, B. A. Gregg, Nature
Iwata-Eclipse HP-BC airbrush with nitrogen at a pressure of 20 psi, onto 1996, 383, 608.
the outermost PEDOT:PSS layer of the transparent PV cells fabricated as [6] D. K. Benson, H. M. Branz, Sol. Energy. Mater. Sol. Cells 1995, 39,
described. Spray casting was performed under ambient conditions with 203.
the airbrush at an approximate distance of 10 cm from the substrate. [7] S. K. Deb, S.-H. Lee, C. E. Tracy, J. R. Pitts, B. A. Gregg, H. M. Branz,
The film thicknesses of both ECP-Magenta and MCCP were respectively Electrochim. Acta 2001, 46, 2125.

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[8] A. Hauch, A. Georg, S. Baumgärtner, U. O. Krašovec, B. Orel, Elec- [16] B. D. Reeves, C. R. G. Grenier, A. A. Argun, A. Cirpan,
trochim. Acta 2001, 46, 2131. T. D. McCarley, J. R. Reynolds, Macromolecules 2004, 20,
[9] K.-S. Ahn, A. J. Yoo, M.-S. Kang, J.-W. Lee, Y.-E. Sung, J. Power 7559.
Sources 2007, 168, 533. [17] E. P. Knott, M. R. Craig, D. Y. Liu, J. E. Babiarz, A. L. Dyer,
[10] W. Gao, S. H. Lee, J. Bullock, Y. Xu, D. K. Benson, S. Morrison, J. R. Reynolds, J. Mater. Chem. 2012, 22, 4953.
H. M. Branz, Sol. Energy. Mater. Sol. Cells. 1999, 59, 243. [18] C.-C. Chen, C.-C. L. Dou, J. Gao, W.-H. Chang, L. Gang, Y. Yang,
[11] J. Jensen, H. F. Dam, J. R. Reynolds, A. L. Dyer, F. C. Krebs, J. Polym. Energy Environ. Sci. 2013, 6, 2714.
Sci. Part B, Polym. Phys. 2012, 50, 536. [19] Z. Tang, Z. George, Z. Ma, J. Bergqvist, K. Tvingstedt, K. Vandewal,
[12] J. C. Bijleveld, A. P. Zoombelt, J. Mathijssen, M. M. Wienk, E. Wang, L. M. Andersson, M. R. Andersson, F. Zhang, O. Inganäs,
M. Turbiez, D. M. de Leeuw, R. A. Jenssen, J. Amer. Chem. Soc. Adv. Energy Mater. 2012, 12, 1467.
2009, 131, 16616. [20] Between the time of 1:45 to 2:15pm on December 17th, 2013
[13] P. Adhikary, S. Venkatesan, P. P. Maharjan, D. Galipeau, Q. Qiao, in midtown Atlanta as measured with a photodetector outside
IEEE Trans. Electron Devices 2013, 60, 1763. the Molecular Sciences and Engineering Building at Georgia
[14] Y. H. Zhou, C. Fuentes-Hernandez, J. Shim, J. Meyer, A. J. Giordano, Tech.
H. Li, P. Winget, T. Papadopoulos, H. Cheun, J. Kim, M. Fenoll, [21] L. J. A. Koster, V. D. Mihailetchi, R. Ramaker, P. W. M. Blom, Appl.
A. Dindar, W. Haske, E. Najafabadi, T. M. Khan, H. Sojoudi, Phys. Lett. 2005, 86, 123509.
S. Barlow, S. Graham, J. L. Bredas, S. R. Marder, A. Kahn, [22] L. J. A. Koster, V. D. Mihailetchi, H. Xie, P. W. M. Blom, Appl. Phys.
B. Kippelen, Science 2012, 336, 327. Lett. 2005, 87, 203502.
[15] A. K. K. Kyaw, D. H. Wang, V. Gupta, J. Zhang, S. Chand, [23] A. K. K. Kyaw, D. H. Wang, V. Gupta, W. L. Leong, L. Ke, G. C. Bazan,
G. C. Bazan, A. J. Heeger, Adv. Mater. 2013, 25, 2397. A. J. Heeger, ACS Nano 2013, 7, 4569.

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DOI: 10.1002/adma.201401400