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Jpn. 2003, 72, 3041. m) J. W. Lynn, Q. Huang, C. W. Brown, V. L. their neutral form have been reported, the first report of a
Miller, M. L. Foo, R. E. Schaak, C. Y. Jones, E. A. Mackey, R. J.
Cava, Phys. Rev. B 2003, 68, 214 516. n) J. D. Jorgensen, M. Avdeev,
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[6] C. Fouassier, G. Matejka, J.-M. Reau, P. Hagenmuller, J. Solid State
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[7] R. J. Balsys, R. L. Davis, Solid State Ionics 1996, 93, 279.
[8] C. Delmas, C. Fouassier, P. Hagenmuller, Physica 1980, 99B, 81.
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[10] J.-J. Braconnier, C. Delmas, C. Fouassier, P. Hagenmuller, Mater.
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K. Kato, M. Takata, H. Sakurai, E. Takayama-Muromachi, T. Sasaki,
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[14] J.-J. Braconnier, C. Delmas, C. Fouassier, P. Hagenmuller, Mater.
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Chem. B 1999, 103, 10 365.
[16] a) N. Strukan, M. Cindric, B.Kamenar, Acta Crystallogr. C 1999, 55,
291. b) M. S. Wickleder, Z. Anorg. Allg. Chem. 2001, 627, 1439.
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[17] I. D. Brown, D. Altermatt, Acta Crystallogr. B 1985, 41, 244.
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2004, 16, 1693.
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[20] F. Izumi, R. A. Dilanian, in Recent Research Developments in Physics,
Vol. 3, Part II, Transworld Research, Kerala, India 2002, pp. 699±726.
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[22] F. Izumi, S. Kumazawa, T. Ikeda, W. Z. Hu, A. Yamamoto, K. Oika-
wa, Mater. Sci. Forum 2001, 378, 59.
Red, Green, and Blue Colors in
Polymeric Electrochromics**
By Gursel Sonmez,* Hayal B. Sonmez,
Clifton K. F. Shen, and Fred Wudl
Having three additive primary colors (red, green, and blue
(RGB)) constitutes an important step forward for the use of
conducting polymers in polymeric electrochromic devices
(PECDs). Although many red- and blue-colored polymers in
± homogeneous polymer films. These polymer films on the
[*] Prof. G. Sonmez,[+] Dr. H. B. Sonmez,
Dr. C. K. F. Shen, Prof. F. Wudl
Department of Chemistry and Biochemistry
and Exotic Materials Institute
University of California
Los Angeles, CA 90095-1569 (USA)
E-mail: sonmez@sabanciuniv.edu
[+] Permanent address: Sabanci University, Faculty of Engineering and
Natural Sciences, Orhanli 34956 Tuzla, Istanbul, Turkey.
[**] We gratefully acknowledge financial support from the Air Force Of-
fice of Scientific Research through F49620-00-1-0103 and the Army
Research Office through MURI DAAD19-99-1-0316. Instrumentation
for this research was partially funded by NSF grand DGE-0114443.
Adv. Mater. 2004, 16, No. 21, November 4 DOI: 10.1002/adma.200400546
green-colored conjugated polymer has only recently been dis-
closed.[1,2] The main reason for this delay has been the diffi-
culty in obtaining the absorptions required in the visible re-
gion to reflect green light. Since the three components of
color space are completed, all other colors can be obtained ac-
cording to color-mixing theory[3] which states that if two color
stimuli are mixed, the resulting color stimulus will lie some-
where along a straight line connecting two points on the chro-
maticity diagram. The position of the point depends on the ra-
tio of the amounts of the two mixed colors. A ªfine-tuningº of
color is possible by adjusting film thickness. Here we report
three additive primary colors (RGB) based on conjugated
polymers as well as other colors obtained from their mixtures.
Studies on electrochromic devices began with inorganic
compounds such as tungsten trioxide (WO3) and iridium diox-
ide (IrO2).[4] Because of the different colors observed with
these compounds while switching among their different redox
states,[5,6] organic materials (viologens, metallophtalocyanines,
and conducting polymers) have recently received much atten-
tion for electrochromic applications.[7] Conducting polymers
in particular have several advantages over inorganic com-
pounds. These include outstanding coloration efficiency, fast
switching ability,[8] multiple colors with the same material,[9]
and fine-tuning of the bandgap (and the color) through chemi-
cal-structure modification.[10,11] As shown here and elsewhere
almost all colors can be obtained using different conducting
polymers at various oxidation states.[12,13] However, it would
also be possible to get all colors from only three polymers that
reflect RGB colors by mixing them in appropriate propor-
tions.
We have recently discovered a conjugated polymer from
the electrochemical polymerization of 2,3-di(thien-3-yl)-5,7-
di(thien-2-yl)thieno[3,4-b]pyrazine (DDTP) (2) that reflects
green light in the neutral state and is transmissive in the oxi-
dized state.[1] Dioctyl substitution of DDTP produced a more
soluble monomer, 5,7-bis-(3-octyl-thiophen-2-yl)-2,3-di-thio-
phen-3-yl-thieno[3,4-b]pyrazine (2), as well as its polymer and
gave the first soluble green electrochromic conjugated poly-
mer in its neutral form.[2] A combination of green 2 with red
poly(3-alkylthiophene) (1) and blue poly(3,4-ethylenedioxy-
thiophene) (3) completes the RGB additive color-space.
Polymers 1, 2, and 3 were electrochemically polymerized
onto indium tin oxide (ITO)-coated glass slides according to
the procedure explained previously,[1] giving very smooth and
ITO-coated glass slides were used for further characterization
and color mixing. Figure 1 presents the structures and a com-
bined spectroelectrochemistry of 1, 2, and 3 in their neutral
states. Obviously, polymer 1 absorbs in the blue region of the
electromagnetic spectrum's visible region with a maximum
peak at 500 nm and reflects red light. Polymer 3 absorbs in
the red region of visible region with a maximum at 615 nm
and reflects blue light. Since polymer 2 has two chromophores
coming from two different conjugations,[1] it has a blue and
red absorption of the visible with maxima at 380 and 760 nm
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1905
COMMUNICATIONS

a)

I II III IV

b) visible
0.8

0.7

0.6
Absorbance (a.u.)

0.5 P3MeTh
PDDTP
0.4 PEDOT

0.3

0.2
I II III IV
0.1

0.0
300 400 500 600 700 800 900
Wavelength (nm)

Figure 1. a) Structure of the polymers used for additive primary colors

and b) their combined spectroelectrochemistry in the neutral form: 1
(P3MeTh), 2 (PDDTP), and 3 (PEDOT).

and a valley at 550 nm. It is important to note that these ab-

sorption maxima and minima are located exactly at the wave-
lengths which are required in order to reflect green (rarely
found in conjugated polymers). It should also be noted that a
combination of the spectra of these three polymers covers the
whole visible region completely without reflecting any light.
Figure 2 presents colors that can be obtained from 1, 2, and
3 as well as a mixture of colors that can be obtained from
polymers 1, 2, and 3 in two oxidation states (neutral and oxi-
dized). For color mixing experiments, polymer films were pat-
terned on ITO-coated glass slides, followed by face-to-face in-
sertion in a quartz UV-vis cuvette containing 0.1 M
tetrabutylammonium hexafluorophosphate (Bu4NPF6) in ace-
tonitrile (ACN) as electrolyte. In addition, platinum and silver
wire electrodes were used for controlling the potentials to
change the oxidation states of polymers. Neutral polymers 1
and 2 reflect red and green colors, respectively. The mixture
of these two colors produces a very dark brown color
(Fig. 2A-I). As 2 was oxidized, its color changed from green
to transmissive brown and (a mixture of) this color with red
produced a different tone of brown (reddish-brown in color
(Fig. 2A-II)). The oxidized state of 1 gives a sky-blue color
which gives a dark-green color when mixed with neutral 2
(Fig. 2A-III). When the oxidized states of 1 and 2 are mixed,
a grey±brown color is obtained (Fig. 2A-IV). Similarly, differ-
I II III IV
Figure 2. Different colors obtained when A) 1 and 2, B) 1 and 3, and
C) 2 and 3 were mixed at the neutral (n) and oxidized (o) states. A-I: 1
(n) and 2 (n), A-II: 1 (n) and 2 (o), A-III: 1 (o) and 2 (n), A-IV: 1 (o) and 2
(o); B-I: 1 (n) and 3 (n), B-II: 1 (n) and 3 (o), B-III: 1 (o) and 3 (n), B-IV: 1
(o) and 3 (o), C-I: 2 (n) and 3 (n), C-II: 2 (o) and 3 (n), C-III: 2 (n) and 3
(o), C-IV: 2 (o) and 3 (o).
ent colors can be obtained from a combination of 1 and 3, and
2 and 3 (Figs. 2B,C, respectively). It is important to note that,
although the same polymers were used in Figures 2A±C, color
tones vary depending on the color of other polymer present.
When studying a color, its hue will vary depending on its illu-
mination and its surroundings. Illumination changes the hue
because of the color of light. Color is the product of wave-
lengths that are either absorbed or reflected by the surface of
an object being strongly illuminated. The hue appears to alter
according to a color's surroundings as the retina is affected by
these wavelengths and the stimuli are communicated to the
cortex (the part of the brain that enables us to distinguish one
shade from another).

1906  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.advmat.de Adv. Mater. 2004, 16, No. 21, November 4

In addition to the mentioned advantages of conjugated
polymers as electrochromics, there is another very important
point which has not been underlined so far, which is the differ-
ent oxidation states that give different tones of the same color
or sometimes different colors from the same polymer. As
shown in Figure 3a, the oxidation states of a conducting poly-
mer can easily be controlled by an electrical potential which
changes the oxidation state of polymer, depending on the
a)
visible
1.8
+1.0 V
1.6 -0.9 V
Absorbance (a.u.)
COMMUNICATIONS
meric electrochromic device[11] using two different conducting
polymers can produce at least 400 different colors (20 colors
from one polymer times 20 colors from the other). In princi-
ple, based on this product, when conjugated polymers with
the three primary colors (RGB) are used for color mixing, at
least 1200 different colors can be obtained from their mixture.
In conclusion, the additive primary color-space was com-
pleted by the discovery of the first green polymeric electro-
chromic. Mixtures of any two of the three additive primary
colors in various oxidation levels can produce thousands of
colors resulting from possible tones of these polymers that
-0.90 V
-0.80 V can be obtained at different oxidation levels. Some of the col-
-0.70 V
-0.60 V ors that can be obtained from only two redox states of these
-0.50 V
three polymers (fully oxidized and fully reduced) as well as

-0.40 V
1.4 -0.9 V -0.30 V
+1.0 V -0.20 V the three additive primary colors are given in Figure 3b. Com-
-0.15 V
1.2 -0.10 V bining the many advantages of conducting polymers together
-0.05 V
1.0 +0.00 V with recent developments in inkjet printing technologies
+0.05 V
+0.10 V furnishes the possibility of printing them out (at a specific
0.8 +0.15 V
+0.20 V
+0.25 V
resolution) onto flexible substrates.[14] We believe that the
0.6 +0.30 V
+0.35 V
completion of additive primary color-space together with the
0.4
+0.40 V
+0.50 V
discovery of the first green polymeric electrochromic heralds
+0.60 V
+0.70 V
a PECD era.
0.2 +0.80 V
+0.90 V
0.0 +1.00 V

400 600 800 1000 1200 1400 1600

Wavelength (nm)
b)
Figure 3. a) Spectroelectrochemistry of 3 at different oxidation states
with inset pictures of variation in the blue color at different oxidation lev-
els. b) Different colors obtained using mixtures of RGB colors and their
two redox states.
applied potentials. For example, PEDOT (3) can be switched
stepwise from its fully neutral, dark-blue state at ±0.9 V, to a
transparent sky-blue color in its fully oxidized state at +1.0 V
(Fig. 3a). There are at least 20 steps that can easily be con-
trolled by changing the applied potential, resulting in different
intensities of the same polymer's absorption at the same
wavelength in the visible spectrum. Very similar results were
reported for all conducting polymers including 1 and 2. Since
each of these steps produces different color tones, a dual poly-
Experimental
All chemicals were purchased from Aldrich Chemical. Propylene
carbonate (PC) (99.7 %, anhydrous), dichloromethane (DCM), and
acetonitrile (ACN) were distilled over calcium hydride before use.
Electropolymerization was carried out with a BAS 100B/W poten-
tiostat, employing ITO-coated glass slides as working electrode, a
platinum flag or wire as counter electrode, and a silver wire or 0.01 M
Ag/AgNO3 (Ag/Ag+) as reference. The electrolyte used was 0.1 M of
tetrabutylammonium hexafluorophosphate (Bu4NPF6) in DCM,
ACN, or mixture of ACN and DCM. The electrodeposition was per-
formed from a 0.01 M solution of the monomer in the electrolyte po-
tentiodynamically at a scan rate of 20 mV s±1 or potentiostatically at
50 mV above the oxidation potential of monomer.
Spectroelectrochemical data were recorded on a Hewlett Packard
8453 UV-vis spectrophotometer connected to a computer. A three-
electrode cell assembly was used where the working electrode was an
ITO-coated glass slide (7 mm ” 50 mm ” 0.6 mm, Rs £ 10 X/h, Delta
Technologies Inc.), the counter electrode was a platinum wire and a
Ag wire was used as pseudo-reference electrode. The pseudo-refer-
ence was calibrated externally using a 5 mM solution of ferrocene
(Fc/Fc+) in the electrolyte (E1/2(Fc/Fc+) = +0.130 V versus Ag wire
and +0.080 V versus Ag/Ag+ in 0.1 M Bu4NPF6/ACN). The potentials
are reported versus Ag/Ag+. Polymer films for spectroelectrochemis-
try were prepared by potentiodynamic deposition on ITO-coated
glass slides.
For color-mixing experiments in Figure 2, polymer films were first
electrochemically deposited on ITO-coated glass slides, patterned by
careful removal of some parts of polymers. Then a face-to-face inser-
tion of two patterned polymer-coated ITO-slides in a quartz UV-vis
cuvette containing a 0.1 M Bu4NPF6 in ACN as electrolyte was fol-
lowed. Platinum and silver wires were used as counter and reference
electrodes, respectively, to control potentials for changing the oxida-
tion states of polymers.
A Fujifilm (FinePix A303) digital camera was used to take photo-
graphs of the polymers at high resolution.
Received: April 13, 2004
Final version: June 21, 2004

Adv. Mater. 2004, 16, No. 21, November 4 http://www.advmat.de  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 1907
COMMUNICATIONS

± mers used, as well as different blend compositions, provide

[1] G. Sonmez, C. K. F. Shen, Y. Rubin, F. Wudl, Angew. Chem. Int. Ed.
routes towards optimized device efficiencies. It has been dem-
2004, 43, 1498.
[2] G. Sonmez, H. B. Sonmez, C. K. F. Shen, R. Jost, Y. Rubin, F. Wudl,
onstrated that controlling the morphology of the phase-sepa-
Macromolecules 2004, in press. rated structure inside blend devices can be used to enhance
[3] R. D. Overheim, D. L. Wagner, Light and Color, Wiley, New York exciton dissociation and photodiode performance.[4±6] How-
1982. ever, even in the best devices, only a limited amount of light
[4] W. C. Dautremont-Smith, Displays 1982, 3, 3. can escape the device since an estimated 70 % of the light
[5] P. M. S. Monk, R. J. Mortimer, D. R. Rosseinsky, Electrochromism:
generated is trapped in the waveguide mode (Fig. 1a) and is
Fundamentals and Applications, VCH, Weinheim, Germany 1995.
[6] K. Bange, T. Bambke, Adv. Mater. 1990, 2, 10. generally lost through edge emission or re-absorption.[7]
[7] R. J. Mortimer, Electrochimica Acta, 1999, 44, 2971. Several approaches which are based upon the introduction of
[8] A. Kumar, D. M. Welsh, M. C. Morvant, F. Piroux, K. A. Abboud, periodic corrugations such as spincoating on top of a corru-
J. R. Reynolds, Chem. Mater. 1998, 10, 896. gated photoresist layer[8] or by embossing the emissive layer[9]
[9] G. Sonmez, H. Meng, F. Wudl, Chem. Mater. 2004, 16, 574.
have been used to extract successfully the polymer-anode
[10] G. Sonmez, I. Schwandemann, P. Schottland, K. Zong, J. R. Rey-
nolds, Macromolecules 2003, 36, 639.
waveguide mode, but all rely on additional lithographic tech-
[11] I. Schwendeman, R. Hickman, G. Sonmez, P. Schottland, K. Zong, niques. In this communication, we report on the inclusion of
D. M. Welsh, J. R. Reynolds, Chem. Mater. 2002, 14, 3118. self-organized, two-dimensional (2D) photonic structures with
[12] S. A. Sapp, G. A. Sotzing, J. R. Reynolds, Chem. Mater. 1998, 10,
2101.
[13] B. C. Thompson, P. Schottland, K. Zong, J. R. Reynolds, Chem. Ma-
ter. 2000, 12, 1563.
[14] Special issue on ªInkjet Printing of Functional Materialsº, MRS
Bull. 2003, 28, 802.

Self-Organized Photonic Structures in

(a) (b)
Polymer Light-Emitting Diodes**
By Guillaume Fichet, Nick Corcoran, Peter K. H. Ho,
Ana C. Arias, J. Devin MacKenzie,
Wilhelm T. S. Huck, and Richard H. Friend*

Phase separation in polymer blends is strongly dependent

upon substrate surface energy.[1] By locally varying this sur-
face energy, it is possible to induce periodic structures in a
polymer blend film,[2] since one component of the blend will
preferentially migrate away from regions of higher surface
energy if the difference in surface energy between the two
regions is sufficient.[3] Blends of conjugated polymers have
been used extensively in the fabrication of polymer light-emit-
ting devices (PLEDS). Structural modifications in the poly- (c)

±
[*] Prof. R. H. Friend, Dr. N. Corcoran, Prof. P. K. H. Ho,[+] * * *

Dr. A. C. Arias, Dr. J. D. MacKenzie

Cavendish Laboratory, Department of Physics N N
n n
University of Cambridge C8H17 C8H17 C8H17 C8H17 S

Madingley Road, Cambridge CB3 0HE (UK)

E-mail: rhf10@cam.ac.uk PFO F8BT

G. Fichet, Dr. W. T. S. Huck (d)

Melville Laboratory for Polymer Synthesis, Department of Chemistry
University of Cambridge
Lensfield Road, Cambridge CB2 1EW (UK)
[+] Present Address: Faculty of Science, National University of Singapore,
Lower Kent Ridge Road, S117543, Singapore.
[**] We acknowledge the EPSRC (G. F.), the Cambridge European Trust
and Robert Gardiner Fellowship (N. C.), Cambridge Display Tech-
nology (G.F.), St John's College (P. K. H. H.), ICI and the Isaac
Newton Trust (W. T. S. H.) for financial support.
Figure 1. a) Light-emission modes of a typical polymer LED showing the
surface emission and ITO/polymer waveguide mode. b) Light-emission
modes of a periodically patterned polymer blend LED showing the
surface emission and recovered ITO/polymer waveguide mode.
c) 20 ” 20 lm AFM phase image of 7-octenyltrichlorosilane SAM printed
on O2-plasma treated PEDOT:PSS with the SAM chemical structure
shown in the inset. The axes shown in (c) define the primary x and y mea-
surement directions. d) Chemical structures of F8BT and PFO.

1908  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim DOI: 10.1002/adma.200400316 Adv. Mater. 2004, 16, No. 21, November 4