Solar Energy 81 (2007) 947–957

www.elsevier.com/locate/solener

A self-rechargeable and flexible polymer solar battery

G. Dennler a,*, S. Bereznev b, D. Fichou c,1, K. Holl d, D. Ilic d, R. Koeppe a,
M. Krebs d, A. Labouret e, C. Lungenschmied a, A. Marchenko c, D. Meissner a,
E. Mellikov b, J. Méot e, A. Meyer f, T. Meyer f, H. Neugebauer a, A. Öpik b,
N.S. Sariciftci a, S. Taillemite c, T. Wöhrle d
a
Linz Institute for Organic Solar Cells, Johannes Kepler University, Linz, Austria
b
Tallinn University of Technology, Tallinn, Estonia
c
LRC Semi-Conducteurs Organiques, CEA SACLAY, France
d
VARTA Microbattery GmbH, Ellwangen, Germany
e
SOLEMS S.A., Palaiseau, France
f
SOLARONIX S.A., Aubonne, Switzerland

Received 23 December 2005; received in revised form 23 December 2006; accepted 8 February 2007
Available online 26 March 2007

Communicated by: Associate Editor Aaron Sanchez-Juarez

Abstract

As an answer to the increasing energy demand of mobile battery-powered electronic devices, we propose a new approach offering an
autonomous power source. Comprising a thin film organic or hybrid solar cell connected to a Lithium-polymer (Li-polymer) battery, the
so-called EURO-PSB device possesses attractive characteristics like low weight (<10 g), small thickness (<1 mm) and mechanical flexi-
bility. Thanks to a smart interconnection between the two units, the battery is always charged with optimized voltage, independent of the
illumination conditions. Such a product, compatible with roll-to-roll production processes, might open a new way for producing and
storing energy for small consumption electronic devices.
 2007 Elsevier Ltd. All rights reserved.

Keywords: Organic solar cells; Li-polymer battery; Flexible device

1. Introduction
During the last decade, an impressive development of
novel battery-powered autonomous devices has been
observed. The market for products like mobile phones,
CD and MP3 players, digital cameras, laptops, pocket
games and medical health care assistants have grown stea-
*
Corresponding author. Present address: Konarka GmbH, Altenberg-
erstrasse 69, A-4040 Linz, Austria. Tel.: +43 732 2468 5113; fax: +43 732
2468 5119.
E-mail addresses: gdennler@konarka.com (G. Dennler), denis.fi-
chou@cea.fr (D. Fichou).
1
EURO-PSB Project coordinator.
dily all over the world. Wireless connected computer key-
boards, headsets for mobile phones, PDAs, electronic
tags or smart cards are now part of our daily life. In order
to reduce energy consumption and improve their mobility,
these electronic devices have to constantly reduce their size.
The integration of a self-rechargeable battery into small
planar and mobile objects (cellular phones, smart cards,
remote controls, tags, etc.) could revolutionize their use.
This could be achieved by coupling batteries to small inde-
pendent electrical energy sources like solar cells.
The main objective of the work presented herein (Euro-
pean Polymer Solar Battery: EURO-PSB project (Euro-
PSB, 2002)) is to develop a thin (<1 mm), lightweight
(<10 g) and flexible photovoltaic (PV) solar battery module

0038-092X/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.solener.2007.02.008
948 G. Dennler et al. / Solar Energy 81 (2007) 947–957
Fig. 1. Potential application of EURO-PSB polymer solar batteries: a TV
remote control.
by coupling on top of each other or side-by-side a thin film
solar cell (Brabec et al., 2001) and a lithium-polymer bat-
tery (Ilic et al., 2004). Such a device, able to create electric-
ity and store it, offers energy autonomy without cost in
terms of space, weight or flexibility (Fig. 1).
Here, we report our recent efforts in building the three
separate components of the EURO-PSB device: (i) the
polymer or hybrid organic–inorganic solar cell, (ii) the
Li-polymer battery and (iii) the electrical interconnection.
Our typical solar cell is an all-solid device based on a poly-
mer–fullerene blend deposited on an ITO-coated flexible
substrate. Despite their relative sensitivity in regard to air
exposure, this type of solar cell can achieve extended life-
time when properly encapsulated. Moreover, the solar cells
offer the possibility to be patternable by Nd:YAG laser
etching and therefore allow easy module design. Besides
polymer–fullerene blends, we consider as well other thin
film PV approaches that might offer other advantages, as
presented below. On the battery side, we use an ultra-slim
Li-polymer batteries recently developed by Varta-Micro-
battery, a new technology called PolyflexTM. Such planar
and flexible batteries are based on PVDF or rubber and
contain no free liquid electrolyte. Providing a nominal volt-
age of 3.8 V and a nominal capacity in the 100 mA h range,
these batteries possess valuable characteristics like flexibil-
ity, low weight, long life time and very small thickness.
Finally, we developed a plastic substrate terminal with elec-
trical interconnections between the solar cell and the bat-
tery. This device is meant to ensure that the battery is
always charged with the optimum voltage, independently
of the light intensity seen by the solar cell.
After presenting the potential market applications of the
EURO-PSB device, we will address and describe each sep-
arate part that it comprises.
2. Market considerations
The most striking characteristic of the EURO-PSB
device is that it is rather thin, which makes it interesting
for slim products. Some devices like credit cards or tags
are so flat (<1-mm thick) that there is not enough volume
to use a traditional storage system. A thin battery is a
definitive advantage in this case.
The EURO-PSB device is also a light and compact
device, ideal for mobile products. Flexibility is a very posi-
tive feature here, yet more difficult to obtain. If the solar
cell and the battery are put on top of each other, the flex-
ibility will be only moderate, but even partial flexibility,
with a high radius of curvature, can be interesting to fit
on curved or equally bendable products. Curvature has
another advantage: The solar cell receives light from differ-
ent directions. It can be an advantage when the application
is not always facing south.
The use of polymer-based materials also offers some
advantages. Glass substrates are not compatible with some
products, for instance toys. The EURO-PSB device should
be better accepted from this point of view. Polymers are
generally easy to cut, or to produce in special shapes, while
glass substrates are more easily cut in straight lines. There-
fore most solar cells on glass are rectangular since round
cutting of glass is rather complicated and expensive.
Finally, it should be possible for this technology to be
compatible, at least for a part of the manufacturing pro-
cess, with a roll-to-roll production. This might allow low
cost, high volume solar cell production.
These technical innovative features can be definitive
advantages for some specific niches of the PV market. Since
the goal of the EUROPSB project is to build a ‘‘self-
rechargeable microstorage’’ battery, the products have to
be rather small with low rated powers. Given the present
flat rechargeable battery systems being of a typical size of
60 · 80 mm, we consider solar cells of similar size. This
allows the overall product to be smaller than 50 cm2 and
2 mm thickness. A solar cell of 50 cm2 with 3% efficiency
produces 150 mW under 1000 W/m2 irradiance (bright
sun) and 750 lW under 500 lux (indoor light). This is
why small power electronic devices have to be considered,
with an electrical consumption in the lW/mW range.
This low power PV market, that may require photovol-
taic components, can be divided into two parts: the con-
sumer and the professional market. The consumer market
concerns the cordless products that we use in our everyday
life such as watches, radios, calculators, PDAs, mobiles
phones, TV remote controls, PC keyboards and mice, etc.
This market has specific commercial issues like high pro-
duction volumes, low prices, strong competition, and also
important technical issues, like the small areas available
for a solar cell, the competition with primary batteries,
the mobility of the products, leading to an irregular light
exposure, often under indoor light. In contrast, the profes-
sional market is not as big in terms of turnover but requires
other features: It is more sensitive to reliability and quality
 G. Dennler et al. / Solar Energy 81 (2007) 947–957 949

Table 1
Performances and characteristics of various consumer cordless devices
[1] [2] [3] [4] [5] [6] [7] [8]
Power Product description Voltage Running Typical use/ Energy consumption/ Storage Conditions of light
range current day day needed exposure
lW h/day Basic calculator 1.4 V 10 lA 0.5 h 7 lW h (NO) Indoor/drawer
Kitchen weighting scale 3V 20 lA 10 min 10 lW h NO Indoor/cupboard
Simple wrist-watch 1.5 V 0.4 lA 24 h 15 lW h YES Indoor/outdoor
TV remote control 3V 10 mA 1 min 500 lW h YES Indoor/drawer
Alarm clock 1.5 V Clock + ringing 24 h 800 lW h YES Indoor
mW h/day PC keyboard (low power) 3V 4 mA 1h 12 mW h YES Indoor
PC mouse (low power) 3V 8 mA 2h 48 mW h YES Indoor/under the hand!
PDA 3V 15–75 mA 20 min 15–75 mW h YES Indoor/pocket
Small radio 1.2 V 15–150 mA 1h 20–180 mW h YES Indoor/outdoor
LEDs torch 3.6 V 20–100 mA 1h 72–360 mW h YES Any
Mobile phone 3.6 V 200 mA 0.5 h 360 mW h YES Indoor /pocket
W h/day Mobile phone 3.6 V 200 mA 3h 2160 mW h YES Indoor/pocket
Laptop (personnal 12 V 3A 1h 36 W h YES Indoor
computer)
Energy pack 3/6/ Personnal ultralight charger YES Outdoor
12 V

of service, but less price dependent, yet the competition
with primary batteries is also imminent. In this segment,
one can find many small products that require low electri-
cal power: measurement devices, LCD displays, price tags,
sensors, alarms, remote access controls, etc.
The energy consumption and conditions for use of
devices to be powered have to be clearly identified. The
working durations are as important as the power itself
and the light exposure conditions are essential to figure
out how much power can be obtained.
For each potential application, the important issues are:
• operational voltage and current
• typical working duration per day or per week
• energy storage needed
• light exposure conditions (depending one the usage of
the product)
Technical and market studies have shown that several
individual electronic devices (computer mice and key-
boards, PDAs, laptops) are not accessible to the EURO-
PSB device because of their high energy consumption.
But there is a potential usability of the EURO-PSB device
in the watch industry, the toy industry and some small elec-
tronics like active tags, smart cards, calculators, radios and
LCD displays (see Table 1).
3. Flexible solar cells
3.1. Conjugated polymer based solar cells
Conjugated polymer solar cells have been the object of
increasing interest during the last decade (Brabec et al.,
2001; Yu et al., 1995). Recently, efficiencies of up to 5%
have been reported (Konarka, 2004). Considering their
intrinsic physical properties like light weight, mechanical
flexibility and semi-transparency, these devices might open
up new opportunities for PV. With soluble conjugated
polymers (Wudl et al., 1991), low cost production of poly-
mer solar cells can be envisaged by applying common
printing techniques (Shaheen et al., 2001a,b), hence allow-
ing large scale and roll-to-roll processing onto flexible sub-
strates, compatible with the polymer-Li battery building
process. These reasons explain our primary choice for the
conjugated polymer photovoltaic approach.
The so-called conjugated polymer solar cells are actually
based on a mixture of conjugated polymers with fullerene
materials. Indeed, it has been observed that if an exciton
created in a conjugated polymer can diffuse to an interface
formed with a C60 based material, it will be split into an
electron and a hole (Sariciftci et al., 1992). While the hole
remains in the highest occupied molecular orbital (HOMO)
of the polymer, the electron is transferred to the lowest
unoccupied molecular orbital (LUMO) of the fullerene.
This charge transfer is known to be ultrafast (45 fs) and
highly efficient (close to 100%) (Brabec et al., 2001). Once
the charges have been created, they drift because of the
electric field present in the device, until they reach their
respective electrode, where they are finally collected.
We have performed the first level of development of
EURO-PSB with the well known (2-methoxy-5-(3 0 ,7 0 -dime-
thyloctyloxy)-1,4-phenylene-vinylene) (MDMO-PPV):1-(3-
methoxycarbonyl) propyl-1-phenyl[6,6]C61 (PCBM) ‘‘bulk
heterojunction’’ approach. This system has been reported
to reach solar energy conversion efficiencies of up to
2.5% (Shaheen et al., 2001a,b). The cells are produced
according to a technologically simple process that can be
easily scaled up and is compatible with roll-to-roll produc-
tion. First, indium tin oxide (ITO) coated poly(ethylene
terephtalate) (PET) is coated with a thin (90 nm)
950 G. Dennler et al. / Solar Energy 81 (2007) 947–957

polyethylene dioxythiophene–polystyrene sulfonate 10000

(PEDOT:PSS Baytron, Bayer AG) layer deposited by 600
doctor blading. On the top, a solution of MDMO-PPV
(Covion GmbH):PCBM (Nano-C Inc.) in a weight ratio 500 1000

Current (μA.cm-2)
1:4 is deposited by the same technique, resulting in a

200 nm thick active layer. Finally, an aluminum electrode
is thermally evaporated through a shadow mask.
Fig. 2 shows a picture of a 65 · 41 mm2 polymer solar
cell processed on a 175 lm thick ITO coated PET sub-
strate. It can be observed that the device is flexible and
semi-transparent with an orange-reddish color. Here the
solar cell comprises 12 individual and independent areas,
each with an active dimension of 3 · 24 mm. Under
100 mW of AM 1.5 illumination (110.000 lux of white
light), one pad of this PET/ITO/PEDOT:PSS/MDMO-
PPV:PCBM/Al structure shows a voltage at open circuit
(VOC) of about 650 mV, a short circuit current (ISC) of
1.25 mA (1.75 mA cm2) and a fill factor (FF) of 0.38.
The quite low ISC and FF result both from a non-optimized
electrode design and quite high RS due to the low conduc-
tivity of ITO deposited on a PET substrate (60 X/sq).
Not only usable under natural solar light, conjugated
polymer based photovoltaic devices can be as well consid-
ered for indoor applications with different illumination
properties. For example, common fluorescent lamps pro-
vide light consisting of six main spectral lines. Four of them
(545, 485, 435, and 405 nm) can participate to light-to-elec-
tricity conversion in the bulk heterojunction solar cells
described above. Fig. 3 illustrates the evolution of VOC,
the voltage at maximum power point (Vmpp), ISC, and the
Voltage (mV)
400
100
300
200 10
100
1
0
100 1000 10000
Illuminance (lux)
Fig. 3. VOC (j), Vmpp ( ), ISC ( ) and Impp (s) of a flexible PET/ITO/
PEDOT:PSS(90 nm)/MDMO-PPV:PCBM(1:4150 nm)/Al(100 nm) solar
cell for various fluorescent lamp illuminances.
current at maximum power point (Impp) for various stan-
dard fluorescent lamp illuminances. In spite of the logarith-
mic decrease of VOC with decreasing light intensity, Vmpp is
almost constant. This phenomenon has its origin in the
increase of the fill factor with decreasing illuminance
induced by a lower contribution of RS. Flexible polymer
solar cells can still easily deliver a VOC of about 500 mV
at an usual indoor fluorescent light intensity (1000 lux).
Moreover, the current intensity that follows a perfect linear
evolution with illuminance still shows decent values at 1000
lux: ISC is about 4.7 lA cm2. It appears that even with

Fig. 2. (a) Picture of a 65 · 41 mm2 polymer solar cell processed on a 175 lm thick ITO coated PET substrate; (b) Pictures of the same cell, but combined
with a Polyflex battery.
 G. Dennler et al. / Solar Energy 81 (2007) 947–957 951

rather low illuminance (500–2000 lux), flexible conjugated 1.0

polymer solar cells provide a useful power output under

Norm. ISC
0.8
indoor artificial light: At 1000 lux (fluorescent lamp), the 0.6
maximum power point is located at about Vmpp = 375 mV 0.4
and Impp = 3.5 lA cm2. Thus these photovoltaic cells are 0.2
suitable to charge batteries of low energy consumption
0.0
devices like remote controls, watches, small displays, and 1.0
back-up security systems.

However, to be viable on the market, such a product
should possess a long lifetime (Brabec, 2004). Conjugated
polymers like poly (para phenylenevinylene) (PPV) are
known to be rather unstable in air environment (Morgado
et al., 2000), being particularly damaged by photodegrada-
tion induced by oxygen and moisture (Sutherland et al.,
1996). In spite of the fact that the degradation effect is sig-
nificantly decreased when conjugated polymers are mixed
with fullerenes (Neugebauer et al., 2001), PPV based solar
cells do not last more than few hours in air (Padinger et al.,
2001). Therefore, accurate encapsulation is absolutely
mandatory for this type of devices.
The simplest and most obvious encapsulation consists of
superimposing two glass plates and sealing them with low
permeation glue. However, the mechanical flexibility is sac-
rificed in this case. Commercially available polymer foils
like PET possess oxygen and moisture permeation rates
that are 6–8 orders of magnitude too high to properly pro-
tect conjugated polymer based devices (Lewis and Weaver,
2004). Moreover, the deposition of one single layer of an
impermeable material like ITO or SiOx on the polymer
substrate decreases these permeation value by a factor of
500 only (da Silva Sobrinho et al., 2000). Smart solutions
based on alternatively stacked layers of inorganic barrier
(Al2O3, SiOx, etc.) and organic buffer materials deposited
on thin (175 lm) polyester substrates can drastically
decrease the diffusion of oxidative gases, and even show
in certain cases permeabilities as low as those of glass
(Czeremuskin et al., 2002).
Fig. 4 displays the shelf lifetime (normalized current at
short circuit condition (ISC) and efficiency g) of polymer
solar cells encapsulated in simple 175 lm thick PET foils
and in a special flexible and transparent material showing
especially low permeation towards moisture and oxygen
(Fig. 5). In the case of PET encapsulation, ISC and g
decrease by 50% in 10 and 6 h, respectively. The difference
between their decay rate arises from the fact that g sums up
the decrease from VOC, FF and ISC. When the cells are
encapsulated in the flexible barrier material, their lifetime
is considerably increased: After 3000 h, ISC and g are at
67% and 54% of their primary value, respectively. This per-
formance is comparable to lifetimes reported for the same
type of cells encapsulated between glass plates (Neugebauer
et al., 2001). This result indicates that the degradation may
not be due to limited performances of the flexible gas bar-
rier, but more to the intrinsic instability of the device.
The 3000 h (above 4 months) achieved in this study are
not enough to ensure viability of this type of solar cells on
the market, yet they represent a critical first step of the real-
Norm. eff.
0.8
0.6
0.4
0.2
0.0
0 500 1000 1500 2000 2500 3000 3500
Time (Hours)
Fig. 4. Normalized ISC and efficiency of the solar cells encapsulated in
simple PET (j) and in flexible gas barrier (w) versus storage time in dark
under ambient air.
Fig. 5. Picture of a bended polymer solar cell encapsulated with flexible
high gas barrier material.
ization of long lived flexible plastic solar cells. MDMO-
PPV is known to be especially unstable and sensitive to
aging. However, new materials much less sensitive to mois-
ture and oxygen and allowing even better photovoltaic con-
version are available today (Schuller et al., 2004). The
combination of these materials with a flexible gas barrier
encapsulation might give rise to very promising devices.
Finally, the MDMO-PPV:PCBM approach has been
proven to be compatible with state-of-the art solar cell laser
patterning technology. The process is based on selective
etching using two different wavelengths of a Nd:YAG laser
(Akimasa and Susumu, 2001), namely the 532 and 1064 nm
lines. Since the latter is absorbed by ITO but not but the
active material, and vice versa for the former, patterning
like described in Fig. 6 is achievable. Laser patterning
allows a large freedom of design strategies to build up mod-
ules which minimize the limitations due to the quite low
conductivity of the ITO.
3.2. Synthesis of functionalized C60 derivatives
As mentioned above, blends of functionalized fullerenes
mixed together with conjugated polymers such as PPV
952 G. Dennler et al. / Solar Energy 81 (2007) 947–957
Fig. 6. Description of the successive steps of selective Nd:YAG laser patterning used to design conjugated polymer solar cells.
allow to building photovoltaic cells with high conversion
efficiencies (Yu et al., 1995; Peumans and Forrest, 2001).
Nevertheless, other systems like donor-linked [60] fulle-
renes have been prepared in view of developing solid state
photovoltaic systems (Loi et al., 2003; van Hal et al., 2002;
Peeters et al., 2000; Maggini et al., 2002). A number of
polycyclic aromatic hydrocarbons (PAHs) have also been
covalently linked as donor moieties to C60. (Martin et al.,
2003; Martini et al., 2000). However, with the exception
of perylene (Eox = 0.85 V vs SCE in MeCN), they all exhi-
bit energy transfer (instead of charge transfer) under pho-
toexcitation due to a too high oxidation potential
(Eox > 1.09 V vs SCE).
Surprisingly, higher acenes such as tetracene and penta-
cene possess electrochemical and photophysical properties
which are in good agreement with the required donor prop-
erties for photoinduced charge transfer. In particular, in
contrast to other PAHs, they possess low oxidation poten-
tials (Eox < 0.77 V vs SCE), low singlet excited state ener-
gies (1 * E < 2.6 eV) and a strong absorption in the
visible. But, they probably have never been used as donors
in C60-donor dyads since they undergo [4+2] cycloaddi-
tions with the [6,6] bonds of C60 (Mack and Miller, 1997;
Murata et al., 1999; Herranz and Echegoyen, 2004; Miller
et al., 2000). Since crystalline tetracene and pentacene pos-
sess excellent hole-transport properties and are currently
studied as organic semiconductors in devices such as
field-effect transistors (Nelson et al., 1998; Schoonveld
et al., 2000), it is interesting to develop synthetic strategies
to obtain functionalized acenes.
We synthetized the newly designed tetracene-[60]fuller-
ene dyad 1 (Fig. 7), the 3,5-bis(dodecyloxy) benzylic group
being introduced to insure its solubility in organic solvents.
Our strategy for the synthesis of the tetracene moiety is
based upon the [2+2+2] cycloaddition of propargylic alco-
hol with a 1,7-diyne (Taillemite and Fichou, 2004). Then,
the reaction of C60 with the soluble tetracene moiety under
O O
1
C12H25O
O O 2
3
4 5
C12H25O
1
Fig. 7. Chemical structure of the Tetracene-[60]fullerene dyad 1.
 G. Dennler et al. / Solar Energy 81 (2007) 947–957 953

Bingel conditions (Bingel, 1993; Nierengarten et al., 1996)
affords the target dyad 1 in 27% yield. The Bingel reaction
allows to proceeding at room temperature thus avoiding
the undesirable Diels-Alder side-reaction. After purifica-
tion by flash chromatography, 1 is isolated as a black pow-
der. The molecular structure of 1 is unambiguously
confirmed by 1H NMR, 13C NMR and MALDI-TOF
MS measurements (m/z = 1520.4).
The 1H NMR spectra of 1 show a substantial low-field
shift by d = 0.2–0.5 ppm of all tetracene protons. This
can be explained by a p-stacking conformation where the
acene and the C60 moieties achieve spatial proximity due
to Van der Waals attraction. p-stacking in dyad 1 is also
supported by its structureless UV–visible absorption spec-
trum and the strong fluorescence quenching of the tetra-
cene moiety (Fig. 8). A solution of 1 in toluene has a
purple-red color and its absorption spectrum consists in a
monotonous broad band extending over the 440–600 nm
range. Besides, under UV irradiation, the typical vibronic
feature of tetracene fluorescence in the 400–500 nm region
disappears. This indicates that a charge or energy transfer
(intra or intermolecular) takes place in solution. However,
since no emission band is observed on the 650–900 nm
zone, it cannot be concluded that charge transfer takes
place in solution. If charge transfer effectively occurs, p-
stacking would yield excited states having short lifetimes,
which would be redhibitory for further charge separation
and efficient photovoltaic effect in the solid state. But,
recent studies show that the charge separation lifetime of
a phthalocyanine-[60]fullerene dyad may be considerably
longer in the solid state than in solution (Loi et al.,
2003). We are currently investigating the photophysical
properties of 1.
3.3. Hybrid flexible PV structures based on Cu-tape
In the field of research and development of low-cost
solar energy converters, organic–inorganic PV junctions
in an all thin-film configuration deserve in depth investiga-
tions (Chartier et al., 1998; Sebastian et al., 1998). In the
present study, a new approach to prepare hybrid solar cells
8 Tetracene 11
7 Dyad 1
6 on the surface of the PEDOT-PSS and ZnPc films.
Emission (a. u.)
using organic buffer layers of Zn-phthalocyanine (ZnPc)
and poly(3,4-ethylenedioxythiophene) (PEDOT) doped
with polystyrenesulfonate (PSS) was investigated. In this
approach, the organic layer is considered as an alternative
for the traditional buffer and window layer in the conven-
tional cell structure (Bereznev et al., 2003). The well-known
conductive polymer PEDOT-PSS and the organic pho-
toabsorber ZnPc are in the focus of this work. The wide
range of associated electrical and optical properties, cou-
pled with a good stability, makes these organic compounds
potentially attractive for application as an active material
for PV and other devices.
The chalcopyrite I–III–VI2 semiconductors are well
established as effective light absorbers in thin film PV cells.
The copper–indium chalcogenide materials e.g. CuInSe2
(CISe), Cu(InGa)Se2 (CIGSe), CuInS2 (CIS) and
CuIn(SSe)2 (CISSe) have been extensively studied because
they allow tailoring of the energy band gap and other mate-
rial properties to enhance device performance (Sterner
et al., 2000; Kessler et al., 2000; Dullwenberg et al.,
2001). In terms of stability, these photoabsorbers do not
show light-induced degradation.
For our investigations, the Cu/CIS structures were
received from the Institut für Solartechnologien (Frankfurt
(Oder), Germany). The so-called CISCuT deposition
method (Penndorf et al., 1998) was used to form a poly-
crystalline CIS absorber layer on a copper tape. The idea
of the CISCuT method is a fast roll-to-roll sulfurization
in Sx+N2 gas atmosphere at 500–600 C of an indium pre-
cursor electrodeposited onto the copper tape substrate.
Five milliliters of an 1.3 wt.% aqueous dispersion of the
conductive polymer PEDOT-PSS in aqueous dispersion
was mixed with 120 ll glycerin, 250 ll N-methyl-2-pyrroli-
done (NMP) and 6.25 ml isopropanol for the preparation
of high conductive stable coatings of PEDOT-PSS. The
mixture was spin-coated on Cu/CIS substrates and dried
at 40 C in vacuum for 3 h. The average thickness of the
PEDOT-PSS films was about 50 nm. Thin films of ZnPc
with a thickness of 20 nm were evaporated in vacuum on
the Cu/CIS substrates.
All investigated photovoltaic structures were fabricated
in a sandwich configuration Cu/CIS/ZnPc/Cr/Au or Cu/
CIS/PEDOT-PSS/Cr/Au as shown in Fig. 9. For the prepa-
ration of the semitransparent chromium–gold contact-win-
dow layers, chromium and gold were thermally evaporated

5 White light with a simulated AM1.5 spectrum and an

4 intensity of 100 mW/cm2 was used for irradiation. The
3 active area of was 2 cm2.
2 According to our approach, a PV p–i–n structure can be
1 formed between the n-type intermediate buried layer of In-
0 rich CIS, low-doped i-CIS at the surface of the absorber
-1 and the p-type PEDOT-PSS or ZnPc buffer layer (Fig. 9).
400 450 500 550
The resulting thickness and morphology of the PED-
Wavelength (nm) OT:PSS buffer depends on dilution, composition of the
Fig. 8. Fluorescence emission spectra of tetracene and dyad 1 in precursor mixture and spin coating rotation speed. The
dichloromethane. (kex = 300 nm; [c] = 9.5 · 106 M). best result was obtained by spin-coating of PEDOT-PSS
954 G. Dennler et al. / Solar Energy 81 (2007) 947–957

Top contact-window layer: Cr(1-2nm)/Au (20nm)

+ Au strip (thickness 200 nm, width2 mm)
PEDOT-PSS (50 nm)or ZnPc(20 nm)buffer layer p
i-CIS ~ 200 nm i
In-rich n-CIS ~ 1300 nm n
Cu-In alloy ~ 300 nm

Copper tape ~0.1 mm

Fig. 9. Schematic drawing and photograph of Cu/CIS/PEDOT-PSS/Cr/Au and Cu/CIS/ZnPc/Cr/Au PV structures.

aqueous dispersion mixed with glycerin, NMP and isopro- Cu / CIS / ZnPc / Cr / Au / Au_strip
100 2
panol as described above. The additives play a very impor- Isc = 15.6 mA (7.8 mA/cm ) Voc = 480 mV FF = 0.492
2
Max. Power output = 3.7 mW Sact = 2 cm Eff. = 1.85 %
tant role in PEDOT-PSS thin-film processing. In 80
particular, an enhancement of the electrical conductivity
of deposited PEDOT-PSS films by the addition of polar 60 Cu / CIS / Pedot-PSS / Cr / Au / Au_strip
Current (mA)
2

Isc = 16.9 mA (8.45 mA/cm) Voc = 440 mV FF = 0.489

solvents e.g. NMP was explained by a screening effect
2
between the dopant and the polymer main chain due to 40 MPoweroutput = 3.6 mW Sact = 2 cm Eff. = 1.8 %

the polar solvent (Kim et al., 2002). Isopropanol, a

quick-drying solvent, was used as wetting agent to improve
the adhesion between the polymer film and the substrate.
The use of lower precursor concentrations yields a thinner
buffer layer that makes formation of pin holes more prob-
able and thus lowers the quality and reproducibility of the
PEDOT-PSS films. On the other hand too thick buffer lay-
ers raise the serial resistance of the structure, increase the
parasitic absorption of light in the PEDOT-PSS film and
reduce the photovoltage/photocurrent. In our devices, the
optimal thickness of PEDOT-PSS was about 50 nm. In
the case of ZnPc buffer layers, high quality uniform films
with a thickness of 20 nm were obtained by evaporation
of ZnPc in vacuum.
It was found that an intermediate chromium layer
improves the PV properties for the structures with a
PEDOT-PSS buffer layer. This phenomenon is probably
related to the limitation of gold penetration into the buffer
layer due to the chromium intermediate layer. It should be
noted, that the active area of prepared PV structures could
be increased from 10–20 mm2 (Bereznev et al., 2003) to
2 cm2 without significant losses.
The photovoltage and photocurrent of the fabricated
PV structures have been studied under simulated AM1.5
white light illumination with an intensity of 100 mW/cm2.
Fig. 10 shows I–V characteristics for the best structures
with PEDOT-PSS and ZnPc buffer layers.
In the case of Cu/CIS/ZnPc/Cr/Au structures, the inci-
dent light produced a short-circuit photocurrent density
ISC = 7.8 mA/cm2 and an open-circuit voltage VOC =
480 mV. The best hybrid PV structure Cu/CIS/ZnPc/Cr/
Au reached a energy conversion efficiency of 1.85%.
Good photovoltaic properties of cells with the PEDOT-
PSS and ZnPc thin film buffer layers are obtained, although
there is still a large room for improvement of the fill-factor.
20
0
-20
-40
-1.0 -0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8
Voltage (V)
Fig. 10. I–V characteristic of Cu/CIS/PEDOT-PSS(50 nm)/Cr(2 nm)/
Au(20 nm)/Au stripe (200 nm) and Cu/CIS/ZnPc(20 nm)/Cr(1 nm)/
Au(20 nm)/Au stripe(200 nm) PV structures.
This might be due to the relatively low conductivity of the
semitransparent Cr/Au contacts. Currently, studies to pro-
vide a more transparent and higher conductive electrode on
the organic buffer layers are on the way. The possibility of
roll-to-roll production, good photovoltaic properties and
the flexibility of the copper foil substrate make this kind
of solar cells very promising power sources for the
EURO-PSB device.
4. Flexible polymer battery
VARTA Microbattery GmbH has developed very thin
polymer batteries that perfectly fit the needs of the
EURO-PSB project. Indeed, having an overall thickness
of about 1 mm, the PoLiFlexTM batteries show very light
weight (few grams) and large flexibility, as described earlier
(Ilic et al., 2004).
The smallest unit of VARTA PoLiFlexTM battery is the
so-called bi-cell. This bi-bell has the following sequence:
cathode–separator–anode–separator–cathode. The cathode
(positive electrode) is based on lithium–cobalt–oxide
 G. Dennler et al. / Solar Energy 81 (2007) 947–957 955

Fig. 11. Scheme of the working principle of a Li-polymer-battery (PoLiFlexTM) designed by VARTA Microbattery.

Fig. 12. Detailed structure of a Li-polymer-battery (PoLiFlexTM) designed by VARTA.

(LiCoO2), the anode (negative electrode) is based on inter-

calation graphite (e.g. MCMB6-28). A shut-down-separa-
tor (PP/PE/PP-sequence) is used to isolate electrically the
electrodes, yet allowing Li-ions to move from one electrode
to the other. This is called the ‘rocking-chair’ principle:
When the cell is charged, the Li-ions are moving from
the host-structure of the metal-oxide to the host structure
of the graphite (Fig. 11).
The electrodes are prepared by casting the electrode
slurry with a casting solvent like acetone onto a collector
foil. This current collector is a copper solid foil and alumin-
ium grid, respectively. The electrodes and the separator are
then assembled to the final bi-cell (Fig. 12). Finally, the bi-
cell is welded to the tabs, packaged in aluminium-multi-
layer-foil (two polymer layers with an aluminium foil in
between) and vacuum dried at 80 C. After activation with Fig. 13. Cycle behaviour of a PolyflexTM battery at room temperature and
the electrolyte, the polymer battery is in a discharged con- at 60 C.
dition. In order to provide a ready-made battery, the cell
has to be formatted (charging step followed by a half dis-
charge step to reach the typical shipping voltage of 3.9 V). solar energy it is exposed to elevated environment condi-
Fig. 13 shows the room temperature cycle-behaviour of tions. Usually higher temperatures lead to higher imped-
a 1 · 66 · 35 mm3 battery. This battery possesses a nomi- ance due to disconnection processes between the metallic
nal capacity of 100 mA h and an overall weight of 3.3 g. collectors and the polymer electrodes. VARTA PoLi-
The cycling behaviour after 500 charge/discharge cycles FlexTM is optimized for higher working temperatures with
shows excellent capacity retention of more than 70%. an appropriate collector treatment. Fig. 13 shows the very
When PoLiFlexTM is used as energy storage device for stable 60 C cycle behaviour.
956 G. Dennler et al. / Solar Energy 81 (2007) 947–957
Thus, the PoLiFlexTM battery that allows a flexible
design and shows a very low self-discharge rate looks very
advantageous for applications as energy storage device for
solar energy applications.
5. Smart interconnection
The low-voltage converter ‘‘PowerDot’’ aims to inter-
connect the polymer solar cell and the polymer battery in
an optimized way, so that a maximum of electrical energy
created can be stored. Here are the main characteristics of
such a desired converter:
• starting voltage: 0.45 V, even under load
• output voltage range: 1 V to >20 V
• current range: lA to 10’s of mA
• conversion efficiency: 50% to >80% depending on the
output voltage
• small component number
Following this design requirements, we have fabricated
prototypes of various sized ferrite E-cores from
6 · 2 mm2 to 6 · 5 mm2 using a patented sand-blasting pro-
cess (Fig. 14).
We tested as well a flex-foil process based on wafer-
based micro-fabrication techniques done in clean room
facilities. We obtained pitches down to 5 microns for a
Cu-inductance on polyimide (Fig. 14).
The sizes of the obtained ferrite devices show that inte-
gration within a thickness of less than 1 mm should be fea-
sible. As an example, we fabricated a PowerDot
application for operating an electronic thermometer
(Fig. 15). The thermometer recharges its 1.6 V Li-Nb2O5
battery with a conjugated polymer based organic solar cell
Fig. 14. (a) Array of ferrite cores, microstructured from a ferrite wafer, in
comparison to a match; (b) photograph of three different sizes of coils
together with their respective ferrite E-cores; (c) assembled inductor
compared to a match.
Fig. 15. A PowerDot application example: a conjugated polymer based
organic solar cell driving a thermometer.
working in low light conditions. The PowerDot converter
located in the battery case converts the 0.45 V from the
solar cell to ca. 2 V to charge the battery through a diode.
It appears that simple voltage limiting charge controllers
for Li-ion batteries delivering voltages from 2.7 V to 4.5 V
and comprising only five components should be achievable
at low cost onto flexible substrate.
6. Conclusion
The feasibility of a polymer solar battery has been pro-
ven. Prototypes of conjugated polymer solar cells con-
nected to polymer-Li batteries via smart interconnection
have been realized. These products show low thickness
(<1 mm), mechanical flexibility and light weight (<10 g).
Thanks to high gas barrier encapsulation, extended life-
times for the organic solar cells have been achieved. The
performance could be increased by choosing different pho-
toactive materials as well as controlling the heat transfer
between the separate elements.
Acknowledgement
We gratefully acknowledge the financial support of the
European Commission R&D Programme (EURO-PSB
Project, Contract No. ENK5-CT2002-00687).
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