Appl. Phys.
A 79, 21–25 (2004)
DOI: 10.1007/s00339-003-2496-7
v. dyakonov Mechanisms controlling the efficiency
of polymer solar cells∗
Energy and Semiconductor Research Laboratory, Institute of Physics,
University of Oldenburg, Carl-von-Ossietzky Str. 9–11, 26129 Oldenburg, Germany
Received: 4 August 2003/Accepted: 9 December 2003
Published online: 5 March 2004 • © Springer-Verlag 2004
ABSTRACT To improve the efficiency of polymer solar cells, it
is vital to understand which mechanisms control the current–
voltage characteristics of a given device. Temperature and light
intensity dependence of the main solar cell parameters are very
informative for analyzing losses. We report on the current–
voltage characteristics and the external photogeneration quan-
tum yield of ITO/PEDOT:PSS/OC1C10-PPV:PCBM/Al as
well as of ITO/PEDOT:PSS/P3HT:PCBM/Al devices investi-
gated in the broad temperature range 120–325 K under variable
illumination, between 0.02 and 100 mW/cm2. We discuss the
recombination on traps and the low mobility of charge carriers
caused by poor morphology of active layers as possible mech-
anisms limiting the efficiency of these devices.
PACS 73.50.P; 73.61.P; 72.80.R
1 Introduction
In recent years, the development of thin film plas-
tic solar cells, using polymer-fullerene bulk heterojunctions
as an absorber, has made significant progress [1]. Efficiencies
between 2.5% and 3.5% for laboratory cells under AM1.5 il-
lumination conditions have been reported [2–4]. The typical
structure of these devices consists of a composite of two ma-
terials with donor and acceptor properties, respectively, sand-
wiched between two electrodes having different work func-
tions. The most investigated combination to date is the conju-
gated polymer poly (2-methoxy-5-(3-,7-dimethyl-octyloxy)-
1,4-phenylene vinylene (OC1C10-PPV) and the soluble ful-
lerene derivative [6,6]-phenyl-C61-butyric acid methyl ester
(PCBM; a methanofullerene). One advantage of this type of
devices is the easy processability of the absorber layer as
well as of the optional interface layer(s). They all are solution
processed by using spin-casting or doctor blade techniques.
A significant breakthrough has been achieved by realizing that
the morphology of the composites plays an important role for
the device performance. In the case of OC1C10-PPV:PCBM
solar cells, the improved morphology has been achieved by
using chlorobenzene as solvent [2]. However, a direct trans-
u Fax: +49-441/7983-326, E-mail: dyakonov@uni-oldenburg.de
∗ This work is supported by European Commission (Project HPRN-CT-
2000-00127) and BMBF (Project 01SF0026)
Applied Physics A
Materials Science & Processing
fer of this finding to other systems is not straightforward;
therefore, a morphology optimization, in which the choice of
solvent is only one parameter, should be performed for any
combination of materials.
The internal quantum yield of photogenerated charge car-
riers in these composites is expected to be as high as 100%
in contrast to a very low photogeneration yield in pure con-
jugated polymers. This is due to ultrafast photoinduced elec-
tron transfer between donor and acceptor [5]. The charge
transfer occurs within 40 – 50 fs [6], and the separated state
is metastable [7]. Therefore, a much higher development po-
tential can be anticipated taking the high quantum yield of
charge carrier generation in these composites into account.
In spite of significant advances in the understanding of the
qualitative behavior of polymer solar cells, a fully quantita-
tive description of charge injection at the electrodes, charge
transport in the bulk under solar cell operation conditions, and
electron-hole recombination has yet to be done. To optimize
the efficiency, the electronic processes limiting the device
performance should be identified. Studies of current density–
voltage ( J –V ) characteristics of the polymer solar cells as
a function of the temperature and the illumination intensity as
well as of the external quantum yield may provide valuable
information on the charge transport properties, the injection
mechanisms, and the presence of defects both in the bulk and
at the interface.
2 Experimental
We studied the current density–voltage ( J –V ) be-
havior of the ITO/PEDOT:PSS/OC1C10-PPV: PCBM/Al.
For this, a 1 : 4 (weight) blend of poly [2-methoxy-
5-(3 , 7 -dimethyl-octyloxy-)1,4-phenylene-vinylene] (OC1
C10-PPV) [8], as an electron donor, and [6,6]-phenyl C61 -
butyric acid methyl ester (PCBM), as the electron accepting
moiety, was prepared in chlorobenzene. A 100 nm active
layer of OC1C10-PPV:PCBM was spin cast from solution
under inert atmosphere in the glove-box. As a back elec-
trode, we used aluminum, which was thermally evaporated
in a high vacuum. As a hole extracting electrode, the 80 nm
layer of poly-[ethylene dioxy-thiophene] doped with poly-
styrene sulfonate (PEDOT: PSS), (BAYTRON P, Bayer AG,
Germany) was spin coated onto the substrate. Another set of
devices consisted of poly(3-hexylthiophene-2,5-diyl (P3HT)
purchased at Rieke Met. Inc. in the absorber blend. The active
22 Applied Physics A – Materials Science & Processing

layer was made by casting a 1 : 2 toluene-chloroform solution is observed at higher bias. The dark J –V can be fitted with
of regioregular P3HT and PCBM onto dried PEDOT:PSS. Shockley equation with ideality factor n = 2:
The P3HT based devices were annealed in a manner de-
  
scribed in [4]. The novel fullerene acceptor, the diphenyl- q(V − JRS ) V − JRS
J = J0 exp −1 + , (1)
methanofullerene, DPM-12, was used instead of PCBM in nkB T RP
blends with OC1C10-PPV and P3HT.
Monochromatic external quantum efficiency (EQE) spec- where RS , RP denote series and parallel resistances, respec-
tra were measured using a home made lock-in-based set-up tively, V the applied voltage, n the ideality factor, kB the Boltz-
equipped with a calibrated Si/Ge photodiode, as reference. mann’s constant, T the absolute temperature, J0 the saturation
The light from the halogen and Xenon lamps was spectrally current
dispersed using a monochromator with a set of gratings to  
Eg 1
cover the range of wavelength from 250 to 1000 nm. The J0 = NV NC µkB T exp − , (2)
current–voltage profiling was automatically carried out with kB T L NA
a source-meter unit (Avantest TR-6143) in a variable tem- where NV , NC are the effective densities of states in valence
perature cryostat equipped with a liquid nitrogen supply and and conduction bands, respectively, µ is mobility, E g the band
a temperature controller (Lakeshore 330). The devices were gap, L the mean-free path, NA the acceptor density. In a first
illuminated through a sapphire window by white light from approximation, we treat the absorber composite as a semi-
a Xenon arc lamp whose intensity is controlled by a set of neu- conductor with an effective band gap E g = 1.1 – 1.2 eV (see
tral density filters with transmission coefficients from 10−4 discussion below).
to 1. The maximum intensity was calibrated to 100 mW/cm2 The situation changes significantly, when the device is il-
inside the cryostat. luminated. Deviations of the fit (solid line) from experimental
data (open squares) in the fourth quadrant are clearly seen, as
3 Results and discussion shown in the inset to Fig. 1. The illuminated p-n solar cell is
3.1 Polyphenylenevinylene-based solar cells described by the following equation:

  
3.1.1 Current–voltage characteristics. Figure 1 shows the q(V − JRS )
dark current density–voltage characteristic of a ITO/PEDOT: J = J0 exp − 1 − JL , (3)
nkB T
PSS/OC1C10-PPV:PCBM/Al device at room temperature in
a semi-logarithmic representation. A good diode rectification where JL is photogenerated current density, J = JL ≈ JSC at
behavior can be seen. The J –V curve can be separated into V = 0 V, J0 is saturation current density. The fit curve was
three regions: i) at reverse bias and at forward bias up to the generated with the parameters derived from the dark J –V an-
voltages of approximately of 0.7 V, the characteristic is nearly alysis and JL = JSC .
symmetrical and is governed by a “leakage” current through The illuminated device has a lower fill factor (FF) than was
the parallel resistance; ii) at bias corresponding to flat-band expected. The FF depends of both RS and RP in a complex
conditions, the injection starts and the exponential region can way. Both of them may vary with the light intensity. We found
be distinguished; iii) the saturation due to the series resistance that most dramatic is the variation of RP with light intensity, as
shown in Fig. 2. The RP , which is in the order of 100 kOhm ×
cm2 at a light intensity of 0.02 mW/cm2 , decreases by nearly
three orders of magnitude at 100 mW/cm2 . In contrast, the
RS (not shown) varies very little from 1.2 Ohm × cm2 at

FIGURE 1 Dark J–V for a ITO/PEDOT:PSS/OC1C10-PPV:PCBM/Al

diode. T = 293 K. The solid line represents the fit with the Shockley equa-
tion (Eq. (1)) with the ideality factor n = 2. The inset shows the same cell
under white light illumination P = 100 mW/cm2 . The solid line represents
the expected J–V behavior under illumination with the “dark” fit parame-
ters. The deviations in the fill factor and the open circuit voltage are mostly FIGURE 2 Parallel resistance RP as a function of light intensity in log–log
pronounced scale at temperatures between 120 K and 325 K
DYAKONOV Mechanisms controlling the efficiency of polymer solar cells
ILight = 0.02 mW/cm2 to 1.01 Ohm × cm2 at 100 mW/cm2 ,
both at T = 325 K. This presents evidence that the efficiency
of this type of solar cell is limited by a light dependent shunt
resistance.
3.1.2 Incident light intensity dependence. The charge carriers
in the solar cells under investigation are efficiently photo-
generated via ultrafast electron transfer between donor and
acceptor counterparts of the composite, usually having a very
low charge carrier concentration in the dark. The fate of
the photogenerated electrons and holes is crucial for the
device efficiency; therefore, the influence of light intensity
on the J –V characteristics is important. The illumination
intensity was varied from 0.7 mW/cm2 to 100 mW/cm2 .
Figure 3 shows the short-circuit current density JSC of
an ITO/PEDOT:PSS/OC1C10-PPV:PCBM/ Al device as
a function of incident light intensity at several temperatures
from 120 K to 325 K. The short-circuit current density in-
creases with the illumination intensity ILight . The behavior is
close to linear, but not exactly a linear, i.e., JSC ∝ ILight
0.92
at
T = 325 K. The power exponent decreases further at lower
temperatures ( JSC ∝ ILight
0.85
at T = 120 K). The nearly lin-
ear current density–light intensity relationship indicates that
charge carrier losses in the absorber bulk are dominated by the
monomolecular recombination on defects or impurities. This
implies that some part of charge carriers is trapped on defects
and further recombines with the charges of the opposite sign.
The bimolecular e–h recombination is not significant even at
the highest illumination intensity. This is in agreement with
the picture of photogeneration and transport of charge carri-
ers in a donor-acceptor bulk heterojunction: an ultrafast e–h
separation is followed by the transport of negatively and pos-
itively charged carriers within spatially separated networks:
electrons along percolated fullerenes travel towards the Al
contact, holes within the polymer matrix travel towards the
PEDOT:PSS contact. As both contacts may be considered
ohmic for the respective charge carriers (i.e., the potential
barriers are below 0.5 eV), no space charge limited condi-
tions under short circuit conditions, even at highest generation
rates, exist. A deviation from the linear current density–light
FIGURE 3 Short circuit current density as a function of light intensity for
different temperatures. The scaling exponents (slopes) between 0.85 and 0.92
are obtained for T = 120 K and T = 325 K, respectively
23
intensity dependence at low temperatures is attributed to an
increased bimolecular recombination at lower mobility.
3.1.3 Temperature dependence. The dependence of the de-
vice characteristics on temperature in the range from 120 K
to 325 K was measured. Figure 4 shows the short-circuit cur-
rent density as a function of temperature. JSC grows for all
illumination intensities used. Such a strong temperature de-
pendence of the photocurrent is not typical for inorganic solar
cells. In these devices, the main contribution to a positive
temperature coefficient of the JSC is due to thermally ex-
cited intrinsic charge carriers along with the narrowing of
the semiconductor’s band gap with increasing temperature,
resulting in a red shift in the optical absorption. The strong
temperature effect we observed is not understood in detail to
date, but definitely due to electronic transport properties of
organic absorber materials. Charge carrier transport in dis-
ordered conjugated polymers and methanofullerenes is the
hopping type and, therefore, thermally assisted [9, 10]. (The
dotted lines in Fig. 4 illustrate a thermally activated behav-
ior.) Furthermore, it is negatively influenced by the capture
of charge carriers by traps. In both cases, one expects that an
increase in temperature will promote the current through the
device. A detailed discussion on the quantitative analysis of
the temperature-dependent short-circuit current density can
be found elsewhere [11, 12].
The origin of the open-circuit voltage in bulk-heterojunc-
tion solar cells is a controversial issue. It was found to cor-
relate directly with the acceptor strength (LUMO), i.e., it is
determined by the HOMO–LUMO energy gap of donor and
acceptor, respectively, being nearly independent of electrode
materials in the investigated range of work functions [13].
If both electrodes form Ohmic contacts, the HOMO–LUMO
gap indeed gives an upper limit for the VOC [17]. In a metal-
insulator-metal (MIM) picture [16], the VOC is limited by the
work function difference between electrodes, i.e., is equal to
the built-in voltage. In [18, 19], the VOC is expected to be de-
termined by the electrochemical potential gradient across the
absorber layer. An increase of the open-circuit voltage from
FIGURE 4 Short circuit current density JSC as a function of temperature at
light intensities indicated in the legend
24 Applied Physics A – Materials Science & Processing

850 mV to 940 mV is observed when cooling down the de-

vice from room temperature to 100 K, as described in [14, 15].
Qualitatively, such behavior is indeed expected, and is typical
for inorganic solar cells [20]. The temperature dependence of
VOC can be easily derived from the Shockley equation describ-
ing the illuminated solar cell:
   
kT Jph E g nkB T NV NC µkB T
VOC = ln +1 ≈ − ln .
q J0 q q JSC L NA
(4)
The overall behavior expected is such that VOC will in-
crease at lower temperatures and, in the limit T → 0 K, will
reach the value E G /q . In our heterojunctions, E g is not the en-
ergy gap of the donor or acceptor materials in the blend, but
rather the energy gap between the LUMO of the acceptor (the
fullerene derivative) and the HOMO of the donor (conjugated
polymer). The blend is treated as a semiconductor with an ef- FIGURE 5 J–V for a ITO/PEDOT:PSS/P3HT:PCBM/Al diode in dark
fective energy gap, which is approximately 1.1 – 1.2 eV. This (closed squares) and under white light illumination (100 mW/cm2 ) (open
squares). The cell parameters are: JSC = 8.2 mA/cm2 , VOC = 0.55 V,
means that the open-circuit voltage of 0.9 eV is close to the FF = 50%, η = 2.24
thermodynamic limit given by absorber material’s redox po-
tentials. In contrast, the difference in the work function of the
electrode materials, expected to be in the range of 0.7 – 0.8 eV
for PEDOT:PSS and Al, would give somewhat smaller open
circuit voltage.

3.2 Polythiophene-based solar cells

The poly(3-hexylthiophene-2,5-diyl) (P3HT) rep-
resents at the moment one of the most promising donor mate-
rials for polymer photovoltaics. Compared to OC1C10-PPV,
following features are advantageous: i) red-shifted optical ab-
sorption; ii) higher charge carriers mobility; iii) thermal sta-
bility; iv) large scale commercial availability.

3.2.1 Current–voltage characteristics. Figure 5 shows the

current density–voltage characteristic for a ITO/PEDOT:
PSS/P3HT:PCBM/Al device under white light illumination
at room temperature in a linear representation. Two features
are to be mentioned. The JSC of 8.2 mA/cm2 represents a rea-
sonably high value for the short-circuit current. Note: no
additional interface layer were deposited between absorber
and the top contact. In contrast, the open-circuit voltage of
0.55 V is much lower than in OC1C10-PPV devices. This
value fits neither the HOMO–LUMO gap picture, nor the con-
tact potential difference of electrodes, as a limit for VOC in
bulk-heterojunction solar cells. This issue needs to be fur-
ther investigated. The device shown in Fig. 5 has the power
conversion efficiency of 2.2%.
3.2.2 External quantum efficiency. Efficient charge carrier
generation with a quantum efficiency close to unity is ex-
pected in our devices. Figure 6 shows spectra of the exter-
nal quantum efficiency (EQE) in ITO/PEDOT:PSS/P3HT:
PCBM/Al device: as fabricated (open squares) and ther-
mally treated after deposition of the Al electrode (closed
squares). The EQE spectrum of ITO/PEDOT:PSS/OC1C10-
PPV:PCBM/Al device is shown as reference (open circles).
This figure demonstrates an important feature of the P3HT-
based solar cells, namely, the broadening of the optical ab-
sorption towards low energy part of the visible spectrum with
FIGURE 6 External quantum efficiency spectra for the ITO/PEDOT:PSS/
P3HT:PCBM/Al device: as fabricated (open squares) and annealed for 3 min
at 353 K) (closed squares). The EQE spectrum for a ITO/PEDOT:PSS/
OC1C10-PPV:PCBM/Al diode is shown for comparison (open circles).
T = 293 K
the better match to the solar AM1.5 spectrum. The influence
of the annealing on the polythiophene based light-emitting
diodes and solar cells was reported recently in [4, 21, 22].
However, the detailed mechanisms behind the treatment is not
clear. Modification of the morphology improving the mobil-
ity of charge carriers, and/or the improvement of injection
properties of polymer/Al contact are under discussion. The
broadening of the photocurrent action spectrum is noticeable
in the heat-treated devices only, and is due to the change of
polymer absorption.
3.2.3 Increasing the open circuit-voltage. Alternative accep-
tor materials are possible candidates to improve the optical
absorption and/or the open-circuit voltage of the polymer-
fullerene solar cells. (Note: the photoinduced hole transfer
takes place in blends, too, but it’s contribution to the photocur-
rent is weak due to poor absorption of PCBM in the visible
part of spectrum.)
DYAKONOV Mechanisms controlling the efficiency of polymer solar cells
FIGURE 7 Open circuit voltage VOC for a ITO/PEDOT:PSS/OC1C10-
PPV:DPM-12/Al diode as a function of temperature under different illumi-
nation intensities (white light) as indicated in the legend in units of mW/cm2
We studied a novel fullerene acceptor, DPM-12, in blends
with both OC1C10-PPV and P3HT. Though DPM-12 has the
identical redox potential as PCBM, surprisingly high open-
circuit voltages in the range VOC = 0.94 V at room tempera-
ture and nearly 1 V at T = 220 K were measured for OC1C10-
PPV:DPM-12 based devices. Figure 7 shows the temperature
dependence of the open-circuit voltage VOC for a OC1C10-
PPV:DPM -based diode as a function of temperature under
different illumination intensities (white light). The VOC is well
above the difference in the work functions of the electrodes al-
ready at room temperature. However, the efficiency of these
devices is limited by a low photocurrent and high series resis-
tance, which arises from poor absorber morphology and low
electron mobility within the fullerene subnetwork.
A straightforward suggestion is to blend the DPM-12 with
P3HT to benefit from the better electrical transport proper-
ties of the latter. Significantly higher JSC (4.4 mA/cm2) was
obtained for annealed ITO/PEDOT:PSS/P3HT:DPM-12/Al
devices [23]. However, the open circuit voltage was found to
be much lower, being in the range of 0.6 V, i.e., similar to de-
vices based on the PCBM acceptor. The P3HT:DPM-12 based
devices are, therefore, controlled by the hole transport through
the polymer network.
4 Conclusions
We have examined the electrical transport prop-
erties of novel polymer-fullerene solar cells by means of
current–voltage characteristics in the temperature range
120– 325 K and the monochromatic external quantum ef-
ficiency technique. The short circuit current density in
OC1C10-PPV based devices grows monotonically with tem-
perature until 320 K. This is indicative for a thermally acti-
vated transport of photogenerated charge carriers, influenced
by recombination on shallow traps. We present evidence that
the efficiency of this type of solar cell is limited by a light
dependent shunt resistance. Hence, the electronic transport
properties of the absorber materials, e.g., low effective charge
25
carrier mobility with a strong temperature dependence, limit
the photogenerated current due to a high series resistance.
Therefore, the active layer thickness must be kept low, which
results in low absorption for this particular composite ab-
sorber. High monochromatic external quantum yield in the
range of 60% (at absorption maximum) was measured in all
investigated devices. These values were not corrected for the
transmission and reflexion and are, therefore, in accord with
expected internal quantum efficiency close to 100%. Ther-
mal post-treatment significantly improves the parameters of
P3HT-based cells; however, the microscopic mechanisms for
this remain unclear. The overall solar cell power efficiencies
of the devices investigated in this work were in the range of
1.8% and 2.2% under white light illumination.
ACKNOWLEDGEMENTS Author thanks I. Ridel, E. von Hauff,
D. Chirvase, M. Pientka, Z. Chiguvare, V. Mertens and J. Parisi (U. of Old-
enburg, Germany), C.J. Brabec, P. Schilinsky, Ch. Waldauf (Siemens AG,
Germany), J.C. Hummelen (U. of Groningen, The Netherlands), D. Van-
derzande, L. Lutsen (L.U. C, Diepenbeek, Belgium), N. Martin, F. Giacalone
(UCM, Madrid, Spain) for stimulating ideas, material supply, experimental
support and fruitful discussions.
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