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Thin Solid Films 516 (2008) 7205 – 7208

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Dithienothiophene based polymer as electron donor in plastic solar cells

S. Millefiorini, E. Kozma, M. Catellani, S. Luzzati ⁎
Istituto per lo Studio delle Macromolecole, C.N.R., 20133 Milano, Italy
Available online 15 December 2007

Abstract

In this work we have tested in bulk heterojunction solar cells a polymer with a high oxidation potential, Poly-(dithieno[3,2-b:2′,3′-d]
thiophene)-3-decylthiophene (P1), as electron donor together with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) as electron acceptor. We
have studied the photovoltaic characteristics of solar cells made with different P1:PCBM blend composition. The incident photon-to-current
efficiency spectra reaches EQEs of 40%, evidencing good charge photogeneration. The best power conversion efficiency, η = 0.83 under AM1.5
illumination, is found for solar cells containing 67% in weight of PCBM.
As expected for polymers with high oxidation potentials, the open circuit voltage Voc attains high values (Voc ≥ 0.8 V), independently from the
photoactive blend composition, but the fill factors FF of the cells are low (FF: 0.3–0.38), evidencing poor charge transport properties. The data
here reported suggest that transport features, probably arising from poor polymer hole mobility, are the main limitation for cell performances.
© 2008 Published by Elsevier B.V.

Keywords: Organic solar cells; Conjugated polymers; Bulk hetero-junctions; Polydithienothiophene

1. Introduction affinity, like fullerene molecules [7,8]. To obtain photon-to-

Organic photovoltaic devices are promising candidates for
the exploitation of solar energy in a cost-effective way.
Intensive research in this field is stimulated by the inherent
advantages of organic materials: high absorption coefficients,
versatility of the chemical tailoring to impart suitable electronic
properties, ease of processing as well as low manufacturing
costs. Conjugated polymers appear to be particularly suitable
for photovoltaic applications and in recent years the develop-
ment of polymer based devices has made significant progress
[1–3]. The performances of thin film polymer solar cells are
now reaching 5% power conversion efficiencies in simulated
solar light [4–6].
The charge photogeneration in conjugated polymers is rather
poor as the absorption of photons results in the formation of
bound electron-hole pairs; these excitons have to diffuse to
dissociation sites where their charges can be separated. The
dissociation can be obtained by means of photoinduced charge
transfer to another organic material with higher electronic
⁎ Corresponding author.
E-mail address: silvia.luzzati@ismac.cnr.it (S. Luzzati).
0040-6090/$ - see front matter © 2008 Published by Elsevier B.V.
doi:10.1016/j.tsf.2007.12.077
charge conversion, the most efficient device architecture is the
so-called “bulk-heterojunction” in which the active layer,
sandwiched between two different electrodes, consists of a
blend of electron donating material, e.g. a p-type conjugated
polymer, and an electron accepting material (n-type), such as
fullerene derivatives [9].
One of the more studied bulk-heterojunction solar cell is
based on regioregular poly(3-hexylthiophene) (P3HT) blended
with [6,6]-phenyl-C61-butyric acid methyl ester (PCBM).
Poly-alkylthiophenes show the tendency to self organize into
smectic and microcrystalline ordered structures that are
responsible for good polymer hole mobilities [10]. In P3HT:
PCBM solar cells, this peculiarity has been successfully used to
optimize the blend morphology by thermal or solvent
treatments [4–6,11–20], obtaining unprecedented power con-
version efficiencies up to 5% [4–6]. P3HT:PCBM devices have
been taken as a reference to explore the potentialities of
polymer solar cells to further improvements in the conversion
efficiency [21–23]. The photovoltaic parameters of the
optimised P3HT:PCBM solar cells are typically 0.6–0.65 for
the Fill Factor (FF) and for the Open-Circuit Voltage (Voc),
while the photon-to-current conversion efficiency (EQE)
reaches values of 60–70%.
7206 S. Millefiorini et al. / Thin Solid Films 516 (2008) 7205–7208
Scheme 1.
One of the proposed guidelines to improve the conversion
efficiency is to design new materials where the electronic levels
of the photoactive components are optimized in order to
minimize the energetic losses of the photoinduced charge
transfer process, while preserving efficient charge transfer [21–
23]. It is commonly accepted that the Voc strongly depends and
is limited by the difference between the HOMO level of the p-
type polymer to the LUMO level of the n-type fullerene [24].
The extreme versatility in tailoring the band gap and energy
levels of conjugated polymers can be an useful tool to face these
issues. Recently a simple relation between the Voc and the
polymer oxidation potential has been obtained for several donor
polymers in bulk heterojunction with PCBM molecules [22],
showing that it is possible to enhance the Voc parameter
increasing the polymer oxidation potential. [25].
In polythiophenes the structure modification at molecular
level leads to materials whose electronic properties, such as
absorption, energy gap and electron affinities, can be finely
tuned. The insertion of dithieno[3,2-b:2′,3′-d]thiophene units in
a polyalkylthiophene backbone yields to a class of materials
with lower HOMO energy levels respect to polyalkylthiophene.
We have prepared a poly[5,5′-bis(3-alkyl-2-thienyl)-dithieno
[3,2-b:2′,3′-d]thiophene] (P1) (see Scheme 1) showing HOMO
and LUMO energy levels of − 5.84 eV and − 3.84 eV
respectively [26]. In this paper we have tested polymer P1,
blended with different amounts of PCBM, as active material in
bulk heterojunction solar cells. To our knowledge, this is the
first study so far reported on the use of dithienothiophene based
polymers in photovoltaic devices.
2. Experimental
The synthesis of Poly-(dithieno[3,2-b:2′,3′-d]thiophene)-3-
decylthiophene, P1 (Scheme 1) was reported elsewhere [26]. P1
has Mw = 36000 g mol− 1 and a polydispersity Mw/Mn = 2.9 (by
size exclusion chromatography measurements in THF using
polystyrene as a standard); the oxidation potential onset of the
P1 film was found at 1.15 V vs. SCE. PCBM was purchased by
Solenne B.V.
Photovoltaic cells were made by spin coating mixtures of P1
and PCBM at different weight ratios, on patterned ITO glass
covered by PEDOT:PSS, and completed by evaporating
through a mask the back electrode made of 1.5 nm LiF and
100 nm Al; the device area were typically 6 mm2. Photoactive
layers were spin-coated at 1500 rpm from chlorobenzene
solutions, obtaining film thicknesses between 70 and 200 nm,
depending on the solution concentration. Polymer amount in the
solutions was typically 8 mg/cc and PCBM content in the
blends varies from 50 to 80%. Solutions were stirred overnight
at 40 °C before deposition. The device assembling and a thermal
annealing treatment, at 70 °C for 4 min, were done into a N2
atmosphere glove box.
The current density–voltage (J–V) measurements were
performed directly in the glove box, with a Keithley 2600
source meter, using a tungsten-halogen lamp equipped with a
Schott filter KG1 and Balzer filter TL60, to simulate solar
radiation. Light power (approx. 100 mW/cm2) was measured
using a calibrated InGaP solar cell as reference. EQE spectral
responses were recorded by dispersing a Xe lamp through a
monochromator; using a Si solar cell with known spectral
response to measure the incident light power intensity at each
wavelength. The devices were taken outside the glove box for
the EQE measurements, after mounting them on a sealed cell to
avoid moisture and oxygen exposure.
3. Results and discussion
The photo-induced charge transfer process from Poly-
(dithieno[3,2-b:2′,3′-d]thiophene)-3-decylthiophene P1 to
PCBM has been evidenced by photoluminescence and photo-
induced absorption spectroscopy as elsewhere reported [27].
In order to investigate the potentialities of the dithienothio-
phene-based polymer as photoactive donor material, we have
prepared bulk heterojunction solar cells based on P1 and
PCBM, and we have determined their photovoltaic character-
istics. The variation of the devices performances as a function of
the donor/acceptor weight ratio in the photoactive blend was
investigated.
In Fig. 1 are shown the UV–Vis absorption spectra of the
active layer blends with 50%, 67% and 80% in weight of
PCBM. The absorption band peaked at 460 nm is related to the
π–π⁎ transition of the polymer backbone, while the band at
335 nm is ascribable to PCBM (see the inset of Fig. 1).
Photovoltaic cells have been assembled with the conven-
tional geometry ITO/PEDOT/P1:PCBM/LiF/Al starting from
Fig. 1. UV-Vis absorption spectra of P1:PCBM thin films at different PCBM
contents: 50% (circles); 67%: (triangles), 80% (squares). The films are deposited
on quartz substrates by spin coating from chlorobenzene solutions (8 mg/ml of
P1) at 1500 rpm. Pristine P1 (continuous line) and PCBM (dotted line) film
spectra are shown in the inset.
 S. Millefiorini et al. / Thin Solid Films 516 (2008) 7205–7208
Fig. 2. External Quantum Efficiency spectra for different compositions of the
active layer (PCBM in weight % in the legend).
blend solutions containing different amount of fullerene. The
devices have been characterized before and after a thermal
treatment, at 70 °C for 4 min, performed to increase the film
homogeneity and to reduce the contact resistance.
The EQE spectral responses reported in Fig. 2 show good
charge photo-generation properties, arising from the photo-
induced charge transfer process between P1 and PCBM. The
EQE spectral changes follow the blend composition and match
the thin film UV–Vis absorption spectra reported in Fig. 1.
The best photon-to-current efficiency values, with a max-
imum EQE of 40% at 450 nm, are obtained for the blend
containing 67% of PCBM. The device made with 80% of PCBM
displays a decrease of EQE, combined with a blue shift of the
spectral response. We expect from this behaviour, a reduction of
the short circuit current, which is indeed confirmed by the
measurements under white light illumination (see Table 1).
Like for the EQE spectral response, the blends containing
67% of PCBM, have the better J–V characteristics under white
light illumination (see Fig. 3).
In Table 1 are summarised the photovoltaic properties
obtained under white light illumination, for P1:PCBM devices
prepared with different blend compositions. In our experimental
set-up, we measure the cell parameters with an halogen lamp +
filter to simulate the solar radiation. Jsc may differ from the
values that could be obtained from solar radiation standards.
The estimated Jsc values, at 1 sun AM1.5G illumination, cal-
culated from the convolution of the EQE spectra to the standard
AM1.5G spectral radiance are also listed in Table 1. The power
conversion efficiencies, η, have been obtained combining the
Table 1
Photovoltaic characteristics a of P1:PCBM solar cells under white illumination
(97 mW/ cm2)
PCBM% Voc (V) Jsc (mA/cm2) FF Jscb (mA/cm2)
50 0.832 2.16 0.33 2.34
67 0.799 2.56 0.36 2.81
80 0.796 1.53 0.35 1.86
a
Averaged values on 12 devices.
b
Estimated for 1 sun AM1.5G standard solar radiation.
7207
Fig. 3. J–V characteristics of the best 67% PCBM device, under dark (dotted
line) and 97 mW/cm2 white light illumination (continuous line). Voc: 0.854, Jsc:
2.29 mA/cm2, FF: 0.38. Power conversion efficiency under AM1.5 illumina-
tion: 0.83%.
estimated Jsc to the measured Voc and FF parameters. Table 1
shows that Voc is about 0.8 V and does not depend on the P1:
PCBM blend composition.
Therefore the photovoltaic characterisation of P1:PCBM solar
cells confirms that P1 leads to Voc higher than P3HT, as expected
for a donor polymer with a lower HOMO energy level. However
the open circuit voltage improvement for P1 devices is less than
expected and a possible explanation of this feature may be in bad
charge transport properties. The Fill Factor parameter is an useful
tool to probe the transport properties of the photogenerated
charges to the electrodes. We have found relatively low FF on thin
active layer devices, the thickness of the films being about 70 nm
for 50% and 67%, and 140 nm for the 80% PCBM. This is
indicative of unbalanced charge transport of the holes and
electrons [28], that may arise from poor polymer hole mobility. In
order to compare the FF behaviour of devices with similar
thicknesses, we have also prepared a thinner device containing
80% of PCBM (70 nm instead of 140 nm), finding in this case a
η b (%)
0.64
0.81
Fig. 4. J–V characteristics of a 50% PCBM device, under 97 mW/cm2 white
0.51
light illumination, before and after thermal annealing at 70 °C. Prior to annealing
(dotted line) Voc: 0.94, Jsc: 2.39 mA/cm2, FF: 0.31); after annealing: 0,883 V,
Jsc: 2.43 mA/cm2, FF: 0.33.
7208 S. Millefiorini et al. / Thin Solid Films 516 (2008) 7205–7208
FF of 0.38 [27]. Thus in P1:PCBM bulk heterojunctions there is
some enhancement of the FF with PCBM content. This behaviour
is quite common in bulk heterojunctions where the polymeric
component has not too good hole mobilities and the charge
transport is mainly assisted by the PCBM phase. However, with
other polymers, the enhancement of the FF with PCBM can be
much more pronounced than in P1 devices. For example, in
MDMO-PPV devices the FF is doubled passing from 0.3 to 0.6,
when the PCBM content is increased from 50% to 80% [29].
Quite likely in P1:PCBM devices, even at high PCBM loading,
the charge transport within the PCBM component is hindered due
to low phase segregation, arising from the quite good compat-
ibility of P1 and PCBM. Preliminary estimation of the film
morphologies by AFM and luminescence spectroscopy seem to
support this interpretation [27].
Fig. 4 displays the current density-voltage characteristics
under white light illumination of the device containing 50% of
PCBM, before and after a mild thermal treatment at 70 °C. It can
be seen that the annealing of P1:PCBM induces only moderate
improvement of the photovoltaic parameters. Unlike in P3HT:
PCBM bulk heterojunctions, the changes upon thermal
annealing do not reveal an improvement of charge photo-
generation and transport. To conclude, in P1 blends, the thermal
annealing is fruitless in imparting the semicrystalline polymeric
order which is so important for the ordering/demixing of the
photoactive film and that has a crucial role in determining the
charge transport properties of polymeric solar cells.
4. Conclusions
We have prepared bulk-heterojunctions using as donor a
dithienothiophene-based polymer P1 having a lower HOMO
energy level respect P3HT, and PCBM as acceptor. We have
verified that the lowering of the HOMO level in the polymer is
indeed improving the Voc parameter of the solar cell respect
P3HT:PCBM devices. The incident photon-to electron efficien-
cies indicate good charge photogeneration in P1:PCBM blends.
The best power conversion efficiency, η = 0.83, was found for P1:
PCBM blends containing 67% in weight of PCBM.
While the open circuit voltage Voc is improved in P1 devices,
independently from the photoactive blend composition, the fill
factors FF of the cells are relatively low and indicate poor
charge transport properties. The polymer exhibits a quite
remarkable miscibility with PCBM, even in blends with high
content of PCBM, and the thermal annealing is not affecting the
device charge transport properties. These features suggest that
the P1 hole mobility is poor and that, even at high PCBM
loading, the charge transport within the PCBM component is
hindered due to low phase segregation.
P1:PCBM solar cells show an enhancement of open-circuit
voltage, respect to P3HT:PCBM devices, due to the low HOMO
energy level of the polymer, but poor charge transport features
are limiting the device performances. A strategy to enhance the
charge transport properties of the blends is to improve the
polymer three dimensional order, and possibly the P1 hole
mobility; this can be achieved by a lowering of the polymer
steric hindrance via chemical tailoring of the conjugated chain.
Acknowledgements
The financial support of Fondazione Cariplo, “PROTEO”
project, MIUR-FIRB RBNE03S7XZ ‘Sinergy', E.U. RTN-CT-
2007 035533 “SolarNTtype” and of U.E. c. nr. 038889 Co-
ordination Action project “OrgaPVnet” is kindly acknowledged.
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