Synthetic Metals 110 Ž2000.

133–140
www.elsevier.comrlocatersynmet

Photovoltaic cells with a conjugated polyelectrolyte

L. Ding a , M. Jonforsen b, L.S. Roman a , M.R. Andersson b, O. Inganas
¨ a,)

a
¨
Laboratory of Applied Physics, IFM, Linkoping ¨
UniÕersity, S-58183 Linkoping, Sweden
b
¨
Department of Polymer Technology, Chalmers UniÕersity of Technology, S-41296 Goteborg, Sweden

Received 21 October 1999; accepted 22 October 1999

Abstract

We describe photovoltaic cells made from a novel conjugated polyelectrolyte, the lithium salt of polyŽthiophene-3-acetic acid.
ŽPTAA-Li.. The aqueous solubility of this polyelectrolyte allows formation of blend electrodes with a dispersion of the metallic polymer
PolyŽEthylene DiOxyThiophene. ŽPEDOT.. The incident monochromatic photon to current conversion efficiency ŽIPCE. of the cells were
improved up to 19% by blending PTAA-Li with PEDOT to modify the ITO electrode, in combination with the low bandgap polymer
polyŽ3-Ž4-octylphenyl.thiophene. ŽPOPT., and C 60 as electron acceptor. We attribute the increase of efficiency to the improved contact
area between the conjugated polyelectrolyte and PEDOT. q 2000 Elsevier Science S.A. All rights reserved.

Keywords: Photovoltaic cells; Conjugated polyelectrolyte; Polythiophene; Polymer blend

1. Introduction sion efficiencies based on a dye-sensitized heterojunction

of TiO 2 with a amorphous organic hole-transport material
Organic and polymeric photovoltaic cells are currently
¨
were described by Gratzel’s group w4,5x as a improvement
intensively investigated with the aim to convert solar
on their old devices w3x.
energy to electricity efficiently. The configurations for all
Up to now, most of the polymerrmolecule devices are
devices are based on the mechanism of photoinduced
based on modified polyŽphenylene vinylene.s or polythio-
electron transfer across the internal or external donor–
phenes. The vast majority of these polymers are soluble in
acceptor ŽDrA. heterojunctions w1x. Notable examples
organics only. Introduction of water-soluble conjugated
include organicrorganic w2x, organicrinorganic w3–5x,
polymers could render the processing of these materials Žif
polymerrcarbon w6–12x, polymerrpolymer w1,13–16x,
ever produced and used on the large scale. more eco-
polymerrorganic w17–19x, and polymerrinorganic w20,21x
friendly. Use of supramolecular assembly techniques for
systems. Photovoltaic cells based on conjugated polymers
the DrA networks is of great interest, and the use of
have been studied for several years since the discovery of
interactions in aqueous systems should widen the scope of
photoinduced electron transfer from a conducting polymer
assembly techniques to include hydrogen bonding and
to buckminsterfullerene in 1992 w22,23x. These devices
coulombic interactions. It is also of great importance that
attract interest due to the potential for producing low-cost,
the transport properties of the conjugated polymers are
large-area and flexible ‘‘plastic’’ solar cells w12x. Great
optimised, to allow photocurrent harvesting in solar cells;
efforts were made to design new devices with enhanced
therefore, the packing of polymer chains and the means of
efficiency by using novel materials or novel configura-
controlling that packing via transferring from solution
tions. Friend’s group reported a two-layer polymeric pho-
could be of importance. As an increasingly important
tovoltaic cell fabricated by a new lamination technique
element of these devices, we find a polymer buffer layer of
followed by controlled annealing w14x. Another promising
a metallic conjugated polymer, polyaniline or PolyŽEthyl-
solid-state solar cells with high photon-to-electron conver-
ene DiOxyThiophene. ŽPEDOT., which help in stabilizing
the interface to a transparent indium tin oxide electrode
)
Corresponding author. Tel.: q46-13-281-231; fax: q46-13-288-969; ŽITO.; it also reduces barriers to hole injection and collec-
e-mail: ois@ifm.liu.se tion in polymer diodes. PEDOTrPSS ŽFig. 1. is an air-sta-

0379-6779r00r$ - see front matter q 2000 Elsevier Science S.A. All rights reserved.
PII: S 0 3 7 9 - 6 7 7 9 Ž 9 9 . 0 0 2 8 4 - 2
134 L. Ding et al.r Synthetic Metals 110 (2000) 133–140

Fig. 1. The chemical structures for PTAA-Li, PEDOTrPSS and POPT.

ble conducting polymer material with good photostability,
electrical stability and narrow band gap of 1.6 eV which
can give transparent smooth spin-coating films w24–26x
and was often used in the fabrication of light emitting
diodes w27,28x and photodiodes w7,10,14x. As PEDOT
comes from an aqueous dispersion, manipulation of the
interface between the semiconducting photon absorbing
layer and the hole collecting electrode may be enabled by
compatibility of the two polymers in a common aqueous
solution.
In this paper, we report photovoltaic cells based on a
novel conjugated polythiophene in polyelectrolyte format.
PTAA-Li is a water-soluble polyelectrolyte material with
the polythiophene backbone; its chemical structure is pre-
sented in Fig. 1. Excellent golden bright thin films can be
obtained by spin-coating PTAA-Li solution with a special
formulation. It is therefore possible to use this material in
photodiodes. The solubility of conjugated polymer in aque-
ous solvent also enables some novel processing steps. We
have used the aqueous dispersion of PEDOT to combine
both the semiconducting polymer and a polymer electrode
into the same layer. This reduces the problem of combin-
ing a polyelectrolyte on top of PEDOTrITO, where the
water-soluble PEDOT may dissolve upon exposure to the
 L. Ding et al.r Synthetic Metals 110 (2000) 133–140
aquoeus polyelectrolyte solution. We use this novel com-
posite layer as a contact to yet another semiconducting
polythiophene, now designed for optical absorption at
lower energies than that already covered by absorption in
PTAA-Li, and soluble in organics only. The photoinduced
charge separation now occurs at the interface between
polymer and C 60 , which was deposited by evaporation on
the semiconducting polymer layers.
2. Experimental
PolyŽthiophene-3-acetic acid. ŽPTAA. was prepared at
room temperature from thiophene-3-acetic acid Ž2.0 g.
with FeCl 3 Ž9.15 g. in chloroform Ž280 ml. w29x. After 20
h, the reaction was stopped and the polymer precipitated in
methanol. The polymer was purified further by being
dissolved in 3 M NaOH Žaq., neutralised with concentrated
HCl and washed with methanol. After drying, 0.7 g of the
polymer was obtained. The lithium salt was made by
mixing the polymer with lithium hydroxide monohydrate
in methanol Žmolar ratio 1:1.. After a few hours, every-
thing had dissolved and the solution could be evaporated
to obtain the salt. Similar salts have been prepared earlier
w30x.
PTAA-Li was dissolved in methanol with small amount
of water Ž11.6 vol.%. or pure water to form homogeneous
solutions. The blend solutions were prepared by adding
PTAA-Li solution to PEDOTrPSS dispersion and then
using sonication to promote mixing. At first, we blended
PTAA-Lirmethanol solution with PEDOTrPSS disper-
sion with PTAA-Li:PEDOT monomer molar ratio of 1:1;
these blends did not make smooth films, however; and
particles were visible to the naked eyes. Then we tried
pure water as solvent for blends with PTAA-Li:PEDOT
monomer molar ratio of 1:1 and 2:1, respectively. These
Fig. 2. Absorption spectra for PTAA-Li, PEDOTrPSS, W-blend, POPT Ža., annealed POPT Žb. and C 60 .
135
blends are coded W-blend. We observe that the 2:1 solu-
tion is comparable to the PEDOTrPSS dispersion, while
the 1:1 solution shows orange particles precipitating in the
solution; these might be due to the formation of insoluble
particles. The 2:1 W-blend solution gives excellent thin
films, so we choose it as the ITO electrode modification
layer. The PTAA-Li or W-blend layers were spincoated
onto ITO coated glass substrates. The substrates were
treated at 1008C for 10 min to remove solvents, especially
water. Then, in some devices, we coated the POPT layer
by spincoating the 4 mgrml POPTrchloroform solution
with a speed of 800 rpm. The POPT devices are heated at
1008C for 10 min. After further evacuation of the samples
inside the vacuum chamber Ž10y6 Torr. for 2–3 h, we
deposited 30 nm C 60 layer by evaporation, to form a
heterojunction. The Al cathode was deposited on top of the
devices by vacuum evaporation Ž10y6 Torr. and patterned
with a shadow mask to define active areas of 2 = 3 mm2 .
The thickness of the layer in devices was measured by a
Sloan Dektak 3030 surface profilometer. Absorption spec-
tra were taken with a Perkin Elmer l9 spectrophotometer.
The photocurrent was measured with Oriel series instru-
ments and a Keithley Picoammeter by using a self-made
Projeto program. I–V measurements were carried out with
a Keithley 617 Programmable Electrometer by using a
Labview program. Scanning force microscopy measure-
ments were obtained with a Digital Instruments Nanoscope
III running in tapping mode. The samples analyzed by
SFM were prepared by spin coating the polymers from
solutions onto ITO coated glass substrates.
3. Results and discussion
The absorption spectra for PTAA-Li, PEDOTrPSS,
W-blend, POPT and C 60 are shown in Fig. 2. PTAA-Li
136 L. Ding et al.r Synthetic Metals 110 (2000) 133–140

has its maximum absorbance at 441 nm, while PEDOT has
high transmission in the visible spectrum. For W-blend
film, the peak wavelength of absorption moves to 409 nm.
By spin coating POPT film from chloroform solution, a
metastable conformation is obtained. After the film is
heated, the colour changes irreversibly from red to purple,
the absorption redshifts from 496 to 510 nm and the
polymer is transformed to a more ordered conformation
w31,32x. This redshift is useful to further broaden the
absorption of the devices.
The morphology of the spincoated films of PTAA-Li
and the W-blend onto ITO substrate is presented in the
SFM pictures in Fig. 3. Looking to the range in the vertical
gray scales it is possible to notice the change in the film
roughness when mixing PEDOTrPSS into PTAA-Li,
where one polymer forms agglomerates with average size
of hundred nanometers.
The incident monochromatic photon to current conver-
sion efficiency ŽIPCE. determines the action spectra for
the devices. It is obtained by measuring the short circuit

Fig. 3. Scanning force microscopy images taken of PTAA-Li Ža. and W-blend Žb. films spincoated onto ITOrglass substrate.
 L. Ding et al.r Synthetic Metals 110 (2000) 133–140 137

photocurrent of the device while the device is illuminated
by monochromatic light at different wavelengths and using
Eq. Ž1. w7,10x, where Isc is the short-circuit current
ŽmArcm2 ., l is the wavelength Žnm., and Pin is the
incident light intensity ŽWrm2 .:
IPCE%s 1240 = Ž Isc rl Pin . .
The IPCE vs. wavelength plots for the four devices Ža.
IT O r P T A A -L ir C 6 0 r A l, Ž b . IT O r P T A A -
LirPOPTrC 60 rAl, Žc. ITOrW-blendrC 60rAl, and Žd.
ITOrW-blendrPOPTrC 60 rAl, are shown in Fig. 4. The
peaks at 335Ž340. nm and the two small shoulders at 610
and 680 nm originate from C 60 . Comparing a and b, c and
d, we see that after POPT coating, the IPCE of the devices
increase significantly between 450 to 550 nm, and there
are obvious red shifts Ž25, 15 nm. for the second biggest
peaks which are determined mainly by the active polymer
layers. When W-blend is used as the first layer to modify
ITO rather than pure PTAA-Li, for devices without or with
POPT, the second maximum IPCE increases 5.5 and 4.3
times, respectively. The best device, device d, gives us
maximum IPCE of 19% and 16% for the two peaks, which
is five and seven times higher than that of device a.
If we inspect the action spectra in more detail, we find
that the enhancement of device c compared to a suggests
that absorption in the PTAA-Li polymer is more effec-
tively utilised in the blend electrode. The shift of maxi-
mum IPCE Žin the visible range. from 475 to 425 nm
verifies that absorption in the PTAA-Li layer is contribut-
ing to the photocurrent. Adding the POPT layer on top
does not increase the IPCE much, but the maximum is now
shifted to lower energies, which is expected if some ab-
sorption in the POPT phase is contributing to photocurrent.
The major changes in devices a, b, c, d are due to the
introduction of a polymer blend electrode; smaller modifi-
cations are due to the inclusion of a low bandgap polythio-
phene.
Current vs. voltage characteristics for the four devices
Ž 1. in the dark and upon illumination with intensity of 3.125
= 10y4 , 3.504 = 10y4 , 2.848 = 10y4 and 3.125 = 10y4
Wrcm2 at maximum photocurrent wavelength of 495,
519, 480 and 495 nm, respectively, are shown in Fig. 5.
The rectification ratio is defined as the ratio of the current
in positive bias to the current measured at negative bias
with ITO being held positive relative to the low-work-
function Al contact. From the I–V measurements, one can
notice that adding the POPT layer decreases the rectifica-
tion ratio greatly; double-layer devices have good diode
characteristics. Using PEDOT to modify the ITOrPTAA-
Li interface would give better diode performance. For
devices a and b, the open-circuit voltage Ž Voc . is 0.45 V
which conforms well with the work function difference
between the two electrodes, ITO Ž4.7–4.8 eV. w33–36x and
Al Ž4.28 eV.. For devices c and d, Voc is 0.35 V. From the
IV curves upon illumination, we obtained short-circuit
current of 2.30 = 10y6 , 4.15 = 10y6 , 1.09 = 10y5 and
1.74 = 10y5 Arcm2 , respectively. According to the defini-
tion of fill factor:
FF s Ž IV . maxrIsc Voc Ž 2.
From the I–V characteristics under monochromatic illumi-
nation ŽFig. 5., we obtained FF of 44.1%, 23.0%, 54.0%
and 40.9%, respectively. There is improvement of the FF
when including the PTAA-Liq PEDOT blend electrode,

Fig. 4. IPCE curves of the devices: Ža. ITOrPTAA-LirC 60 rAl, Žb. ITOrPTAA-LirPOPTrC 60rAl, Žc. ITOrW-blendrC 60rAl, and Žd. ITOrW-
blendrPOPTrC 60 rAl.
138 L. Ding et al.r Synthetic Metals 110 (2000) 133–140

correlating to the increased interface area between PEDOT Although the quantum efficiency for photoinduced
and PTAA-Li, improving the hole collection. charge separation is near unity for a DrA pair, the overall

Fig. 5. The current–voltage characteristics of photovoltaic cells in the dark and under illumination. Ža. ITOrPTAA-LirC 60 rAl, Žb. ITOrPTAA-
LirPOPTrC 60 rAl, Žc. ITOrW-blendrC 60rAl, and Žd. ITOrW-blendrPOPTrC 60rAl.
 L. Ding et al.r Synthetic Metals 110 (2000) 133–140 139

Fig. 5 Žcontinued..

device efficiency is limited by the molecular nature of the enhancing the photon to electron conversion efficiency of
charge separation process and the collection efficiency w1x. organic photodiodes. We suggest that a major cause of this
Interpenetrating network ŽIPN. w15x formed from a phase- enhancement is the enlarged interface area between the
segregated blend of two semiconducting polymers or ‘‘bulk photoactive polyelectrolyte and PEDOT in the buffer layer.
DrA heterojunction material’’ w1,12x provides both the
spatially distributed interfaces necessary for efficient charge
photogeneration and the means for separately collecting
the electrons and holes. Devices made with such materials Acknowledgements
yield promising photovoltaic conversion with high energy
conversion efficiency w1,10,12,15x. In this work, four de- ¨
This work was supported by the Goran Gustafsson
vices were fabricated with double-layer or triple-layer foundation.
structures, with ITO as the hole collection electrode and Al
as the electron collection electrode. It has been shown that
the injectionrcollection properties of the ITOrPEDOT
References
electrode are better than that of ITO electrode w7x. So the
first layer in devices c and d using PTAA-LirPEDOT-PSS
blend not only absorbs blue-violet light to provide exci- w1x G. Yu, A.J. Heeger, J. Appl. Phys. 78 Ž1995. 4510.
w2x C.W. Tang, Appl. Phys. Lett. 48 Ž1986. 183.
tons, but also modifies the ITO electrode to improve the w3x ¨
B. O’Regan, M. Gratzel, Nature 353 Ž1991. 737.
performance. In PEDOTrPSS aqueous dispersion, there w4x W.C. Sinke, M.M. Wienk, Nature 395 Ž1998. 544.
are already strong interaction between PEDOT and the w5x ¨
U. Bach, D. Lupo, P. Comte, J.E. Moser, F. Weissortel, J. Salbeck,
doping PSS molecules, so PTAA-Li as a polyelectrolyte ¨
H. Spreitzer, M. Gratzel, Nature 395 Ž1998. 583.
w6x N.S. Sariciftci, D. Braun, C. Zhang, V.I. Srdanov, A.J. Heeger, G.
material blending with PEDOTrPSS would produce a new
Stucky, F. Wudl, Appl. Phys. Lett. 62 Ž1993. 585.
self-assembling system with abundant interfaces between w7x L.S. Roman, W. Mammo, L.A. Pettersson, M.R. Andersson, O.
PEDOT and PTAA-Li. In other words, this molecular ¨ Adv. Mater. 10 Ž1998. 774.
Inganas,
assembly provides more interface area between photoac- w8x J.J.M. Halls, K. Pichler, R.H. Friend, S.C. Moratti, A.B. Holmes,
tive polymer PTAA-Li and the PEDOT modified ITO Appl. Phys. Lett. 68 Ž1996. 3120.
w9x D.B. Romero, M. Carrard, W. de Heer, L. Zuppiroli, Adv. Mater. 8
electrode. Thus, the great increase of the photocurrent
Ž1996. 899.
occurring upon the PEDOT electrode modification is sug- w10x L.S. Roman, M.R. Andersson, T. Yohannes, O. Inganas, ¨ Adv.
gested to be due to the enhanced surface area of the Mater. 9 Ž1997. 1164.
electrode contact which would finally improve the hole w11x K. Yoshino, X.H. Yin, K. Muro, S. Kiyomatsu, S. Morita, A.A.
collection efficiency. Zakhidov, T. Noguchi, T. Ohnishi, Jpn. J. Appl. Phys. 32 Ž1993.
L357.
w12x G. Yu, J. Gao, J.C. Hummelen, F. Wudl, A.J. Heeger, Science 270
Ž1995. 1789.
4. Conclusions w13x K. Tada, M. Onoda, A.A. Zakhidov, K. Yoshino, Jpn. J. Appl. Phys.
36 Ž1997. L306.
In summary, we have shown that the processability of w14x ¨ K. Petritsch, A.C. Arias, A. Lux, M.R. Andersson,
M. Granstrom,
semiconducting polymers in aqueous solution may help in R.H. Friend, Nature 395 Ž1998. 257.
140 L. Ding et al.r Synthetic Metals 110 (2000) 133–140
w15x J.J.M. Halls, C.A. Walsh, N.C. Greenham, E.A. Marseglia, R.H.
Friend, S.C. Moratti, A.B. Holmes, Nature 376 Ž1995. 498.
w16x J. Gao, G. Yu, A.J. Heeger, Adv. Mater. 10 Ž1998. 692.
w17x J.J.M. Halls, R.H. Friend, Synth. Met. 85 Ž1997. 1307.
w18x K. Takahashi, Solar Energy Mater. Solar Cells 45 Ž1997. 127.
w19x J.Y. Park, S.B. Lee, Y.S. Park, Y.W. Park, C.H. Lee, J.I. Lee, H.K.
Shim, Appl. Phys. Lett. 72 Ž1998. 2871.
w20x N.C. Greenham, X. Peng, A.P. Alivisatos, Synth. Met. 84 Ž1997.
545.
w21x J.S. Salafsky, W.H. Lubberhuizen, R.E.I. Schropp, Chem. Phys.
Lett. 290 Ž1998. 297.
w22x N.S. Sariciftci, L. Smilowitz, A.J. Heeger, F. Wudl, Science 258
Ž1992. 1474.
w23x S. Morita, A.A. Zakhidov, K. Yoshino, Solid State Commun. 82
Ž1992. 249.
w24x A.G. Bayer, Product Information for Baytron P, 1997.
¨ Polymer 35 Ž1994.
w25x Q. Pei, G. Zuccarello, M. Ahlskog, O. Inganas,
1347.
w26x M. Dietrich, J. Heinze, G. Heywang, F. Jonas, J. Electroanal. Chem.
369 Ž1994. 87.
w27x M. Granstrom,
¨ O. Inganas,¨ Adv. Mater. 7 Ž1995. 1012.
w28x M. Granstrom,
¨ M. Berggren, O. Inganas, ¨ Science 267 Ž1995. 1479.
w29x R. Sugimoto, S. Takeda, H.B. Gu, K. Yoshino, Chem. Express 1
Ž1986. 635.
w30x R.D. McCullough, P.C. Ewbank, R.S. Loewe, J. Am. Chem. Soc.
119 Ž1997. 633.
w31x M.R. Andersson, M. Berggren, O. Inganas, ¨ G. Gustafsson, J.C.
Gustafsson-Carlberg, D. Selse, T. Hjertberg, O. Wennerstrom, ¨
Macromolecules 28 Ž1995. 7525.
w32x M. Berggren, G. Gustafsson, O. Inganas, ¨ M.R. Andersson, O.
¨ T. Hjertberg, Appl. Phys. Lett. 65 Ž1994. 1489.
Wennerstrom,
w33x I.D. Parker, J. Appl. Phys. 75 Ž1994. 1656.
w34x Y. Yang, Q. Pei, A.J. Heeger, Synth. Met. 78 Ž1996. 263.
w35x F. Cacialli, R.H. Friend, N. Haylett, R. Daik, W.J. Feast, D.A. dos
Santos, J.L. Bredas, Synth. Met. 84 Ž1997. 643.
w36x J. Morgado, J. Gruner, S.P. Walcott, T.M. Yong, R. Cervini, S.C.
Moratti, A.B. Holmes, R.H. Friend, Synth. Met. 95 Ž1998. 113.