Recombination and loss analysis in polythiophene based bulk

heterojunction photodetectors
Pavel Schilinsky, Christoph Waldauf, and Christoph J. Brabec

Citation: Appl. Phys. Lett. 81, 3885 (2002); doi: 10.1063/1.1521244

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APPLIED PHYSICS LETTERS VOLUME 81, NUMBER 20 11 NOVEMBER 2002

Recombination and loss analysis in polythiophene based bulk

heterojunction photodetectors
Pavel Schilinskya) and Christoph Waldauf
Department of Energy and Semiconductor Research, University of Oldenburg, 26129, Oldenburg, Germany
and SIEMENS AG, CT MM1, Innovative Polymers, Paul Gossenstrasse 100, D-91052 Erlangen, Germany
Christoph J. Brabec
SIEMENS AG, CT MM1, Innovative Polymers, Paul Gossenstrasse 100, D-91052 Erlangen, Germany
共Received 11 April 2002; accepted 19 September 2002兲
The monochromatic external quantum efficiency of a bulk heterojunction photodetector based on a
blend of poly-3共hexylthiophene兲 with a methanofullerene is reported to be as high as 76% at the
peak maximum at 25 °C. Analysis of the temperature dependence, the illumination intensity
dependence together with absorption measurements in reflection geometry, allow calculation of the
internal quantum efficiency of the device close to 100% at the peak maximum. Recombination of
photoinduced carriers is negligible or even absent in these photodetectors when operated in the
photovoltaic mode. Optical losses in these bulk heterojunction devices are analyzed. © 2002
American Institute of Physics. 关DOI: 10.1063/1.1521244兴

A bulk heterojunction is by definition a homogeneous
blend of a p-type with a n-type semiconductor 共donor/
acceptor兲. Photodetectors and photovoltaic devices based on
blends of conjugated polymers with fullerences, forming in-
terpenetrating donor/acceptor networks1,2 are a prototype ap-
plication for the bulk heterojunction geometry. Recent
progress on these solar cells reported a power conversion
efficiency of ⬎2.5% under air mass 共AM兲 1.5 illumination
and an external quantum efficiency 共EQE兲 of 60%.3,4
Due to the outstanding fast kinetics of the photoinduced
charge transfer between polymers and fullerenes 共⬍40 fs兲,5
this process has a quantum efficiency of 1. In this geometry,
a photon absorbed anywhere within the bulk of the photoac-
tive layer produces a photoinduced excited state that is sepa-
rated into a free hole and electron immediately. Conse-
quently, interpenetrating phase separated p-type/n-type
共donor/acceptor or D/A兲 network composites; that is, ‘‘bulk
heterojunctions’’ appear to be ideal photovoltaic composites.
However, photodetector or photovoltaic operation demands
more than an efficient charge carrier generation. The trans-
port of the single charges to the proper electrodes has to
occur on a time scale faster than the inverse recombination
rate of the carriers. Therefore, the question arises as to
whether the high efficiency for charge generation in the com-
posite can be transferred into an equally high external quan-
tum efficiency for photon to electron conversion in a device.
The EQE of a photodetector in the photovoltaic mode de-
pends primarily on the wavelength ␭ and on the transport
properties determined by the mobility–lifetime 共␮␶兲 product:
EQE共 ␭ 兲 ⫽A 共 ␭ 兲 ␩ G 共 ␭ 兲 Q 共 ␮␶ 兲 .
Here A(␭) is the absorption spectrum of the photoactive
layer, ␩ G (␭) is the photogeneration efficiency, and Q( ␮␶ ) is
the charge collection efficiency. Please note that the product
of ␩ G (␭)Q( ␮␶ ) is also called the internal quantum effi-
a兲
Electronic mail: pavel.schilinsky.ext@erls.siemens.de
ciency 关IQE共␭兲兴, taking into account only absorbed photons.
While ␩ G (␭) is known to be close to 1, electrical losses,
such as recombination, lead to the situation that Q( ␮␶ ) is
usually considerably smaller than 1. In this work we analyze
a detector with high A(␭), and point out that identical high
values for ␩ G (␭) and Q( ␮␶ ) can be realized.
The high mobility,6 the good solubility, and the film giv-
ing properties as well as the rather low bandgap of 共poly共3-
hexylthiophene兲兲 共P3HT兲 would dedicate this polymer to the
prototype candidate for photodetector and photovoltaic ap-
plications. However, photophysical studies find a strong bi-
molecular recombination in composites of P3HT and
fullerenes7 and up to now, the performance of photovoltaic
operated devices from polyalkylthiophenes8 has been found
to be rather low.
Devices were fabricated on glass/ITO substrates. After
cleaning of the ITO, a conducting polymer poly共ethylene di-
oxythiophene兲 doped with polystyrene sulphonic acid 共PE-
DOT:PSS, Bayer AG兲 was spin-coated to a layer with a
thickness of 60 nm. The active layer consisting of P3HT
blended with the methanofullerene 关6,6兴-phenyl C 61 butyric
acid methyl ester 共PCBM兲 共1:3 by wt. for the 350 nm device
and 1:2 by wt. for the 70 nm device兲 was cast to give an
active area of 4 mm2 . The metal electrode 共Ca/Ag兲 was ther-
mally deposited with a thickness exceeding 100 nm.
Figure 1 shows the EQE of P3HT/PCBM bulk hetero-
junction solar cells with different thicknesses of the active
layer. A peak value of 76% is observed at the maximum at
550 nm for the 350-nm-thick device, one of the highest re-
ported values for polymer based photodetectors. The peak
共1兲 value of the thinner device with lower fullerene concentra-
tion is slightly shifted to 520 nm with a maximum of 70%,
but is considerably broader than in the case of the 350 nm
device. The difference in the spectral behavior of the two
devices will be qualitatively discussed later; in the following
the discussion is focused on the 350-nm-thick device. The
EQE has a full width at half maximum of almost 200 nm.
This EQE should correspond to a short circuit current I sc of

0003-6951/2002/81(20)/3885/3/$19.00 3885 © 2002 American Institute of Physics

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3886 Appl. Phys. Lett., Vol. 81, No. 20, 11 November 2002 Schilinsky, Waldauf, and Brabec

FIG. 1. EQE of P3HT/PCBM bulk heterojunction devices with active layer

thicknesses of 350 nm 共䊐兲 and of 70 nm 共䊉兲. The measured photocurrent
has been converted to the EQE according to: EQE关 % 兴
⫽1240* I sc关 ␮ A/cm2 兴 /␭ 关 nm兴 I 关 W/m2 兴 . The inset shows the dark and illumi-
nated I/V curve. Under AM 1.5 spectral conditions with 100 mW/cm2 an I sc
of 8.7 mA/cm2 , a V oc of 580 mV, and a FF of 0.55 is measured. This yields
a power conversion efficiency of ⬃2.8%. R s is 1.4 ohm/cm2 and R p is 1200
ohm/cm2 , I 0 共determined ⫺10 mV兲 is 100 pA/mm2 .

⬎8 mA/cm2 at 25 °C, as calculated by integrating the EQE

folded with the AM 1.5 solar spectrum. Measurements under
AM 1.5 共100 mW/cm2 ) simulated illumination conditions of
the same device yielded an I sc of 8.7 mA/cm2 at 25 °C. The
origin of the difference between these two values is attrib-
uted to the small spectral mismatch of the solar simulator’s
spectrum with the AM 1.5 spectrum.
Bimolecular recombination can be a serious problem for
bulk heterojunction devices due to the intimate mixing of
p-type and n-type semiconductors. In order to analyze losses
due to bimolecular recombination, temperature and intensity
dependent photocurrent measurements have been performed.
The intensity dependent measurements have been performed
under white light from the solar simulator, thus probing the
rate for 共bimolecular兲 recombination within the full spec-
trum. Figure 2共a兲 shows the illumination intensity depen-
dence of I sc at 25 °C. The best fit for the data is obtained by
a straight line with slope ⬃1. Thus, bimolecular recombina-
tion within the bulk of the device 共i.e., in the regimes where
the concentration of p-type and n-type carriers is compa-
rable兲 can be neglected. The typical temperature dependence FIG. 2. 共a兲 Illumination intensity dependence of a P3HT:PCBM diode at
of the I sc of a P3HT:PCBM diode under high illumination 25 °C. The data were fitted by a line according to I sc⬃(I light) ␣ with ␣⬃1.0.
intensity is plotted in Fig. 2共b兲. A linear increase of the I sc 共b兲 Temperature dependence of I sc under AM 1.5 simulated illumination
with 65 mW/cm2 . After each temperature change, devices were stabilized
with temperature is observed up to 70 °C. Figure 2共c兲 sum-
for more than 10 min on a Peltier controlled temperature unit before taking
marizes the illumination and temperature dependence of the measurement. 共c兲 Illumination intensity dependence of I sc at various tem-
I sc in P3HT:PCBM bulk heterojunction solar cells. Between peratures between 0 and 70 °C. At each temperature, the illumination depen-
0 and 70 °C the short circuit current I sc scales linearly with dence was measured over more than two decades in intensity and data were
fitted according to I sc⬃(I light) ␣ . Excellent fits were obtained at each tem-
the illumination intensity with a slope ␣⬃关0.99–1兴. perature.
An increase in the illumination intensity coefficient from
␣⬃0.99 to ⬃1 can result in an increase of the short current at
100 mW/cm2 of ⬃5% (1001 /1000.99), that is, close to the safe side, since the intensity dependence measurements 共see
increase in I sc when going from 0 to 70 °C. Such a small Fig. 2兲 of the I sc , yielding an increase of ⬃4% upon increas-
change of ␣ is certainly within the precision of the measure- ing the temperature from 25 to 70 °C have been performed
ments 关Fig. 2共c兲兴 and might explain the positive T coeffi- under white light. While an EQE of 80% at 70 °C certainly is
cient, which was recently also discussed for bulk heterojunc- an impressively high value, it is even more interesting to
tion solar cells in terms of temperature dependent mobility analyze whether optical losses can explain the residual loss
enhancement. of 20%. The optical loss in the substrate of the bulk hetero-
Combining the results from Figs. 1 and 2, the EQE at junction device is analyzed by absorption measurements in
70 °C is as high as 80%. This calculation is certainly on the transmission geometry. Figure 3共a兲 shows the absorption of a
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Appl. Phys. Lett., Vol. 81, No. 20, 11 November 2002
FIG. 3. 共a兲 Absorption in transmission geometry of a glass/ITO/PEDOT
substrate. 共b兲 Absorption of the bulk heterojunction device 共glass/ITO/
PEDOT/P3HT:PCBM/Ca–Ag兲 measured in reflection geometry using an in-
tegrating sphere. 共c兲 IQE of the devices with active layer thicknesses of 350
nm 共䊐兲 and 70 nm 共䊉兲, as calculated from the ratio of EQE/absorbed
photons.
glass ITO/PEDOT substrate as used for the devices in this
study. At 550 nm, the absorption loss in this substrate is 13%.
It has to be noted that absorption measurements of the sub-
strate in transmission geometry can not observe losses occur-
ring in the device due to thin film phenomena like reflection
or scattering at the substrate/semiconductor interface. Conse-
quently, the optical loss in the real device due to the substrate
might differ slightly from these 13% at 550 nm. Since Fig. 2
proves that I sc scales linearly with the illumination intensity,
it is safe to conclude that the bulk heterojunction device from
P3HT:PCBM presented in this work has the potential to
reach an EQE of ⬃90% or higher if reflection and absorption
losses in the substrate can be minimized.
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Schilinsky, Waldauf, and Brabec 3887
In order to determine the internal quantum efficiency,
absorption measurements in reflection geometry, utilizing an
integrating sphere, have been performed for the bulk hetero-
junction devices. The use of an integrating sphere turned out
to be necessary because of the small active area of the de-
vices. Spectra were corrected for light scattered at the front
glass under normal incidence 共⬃10%兲 and are plotted in Fig.
3共b兲. At 800 nm ⬃30% of the incident light is lost in the
substrate, which is passed twice, at incidence and after re-
flection, at the back electrode. At 550 nm, nearly 90% of the
incident photons are absorbed by the device 关high A(␭)].
The IQE, calculated as the fraction of electrons versus ab-
sorbed photons, is plotted in Fig. 3共c兲 for the 70 and the 350
nm devices. It is interesting to note that the IQE 共as well as
the EQE, see Fig. 1兲 of the 70 nm device is spectrally
broader than of the 350 nm device. From comparison of
EQE, absorption, and IQE measurements, the thick device
共1:3 wt. ratio PCBM兲 has a relatively higher absorption in
the blue as compared to the thin device 共1:2 wt. ratio兲 which
is caused dominantly by fullerene absorption. As recently
shown by correlation studies between morphology and per-
formance of bulk heterojunction solar cells,4 large fullerene
domains do not contribute so efficiently to the generation of
free carriers as when highly dispersed into the polymer.
Therefore, the higher fullerene concentration of the 1:3 de-
vice leads to a dilution of charge generation centers for blue
light. Thus, the 70 nm device with a 1:2 PCBM ratio has a
more pronounced response in the blue and significant spec-
trally broader IQE. Nevertheless, in the red spectral region, a
peak maximum of 94% at 530 nm is observed for the 350 nm
device at 25 °C. Taking into account the positive temperature
coefficient, the IQE at 70 °C is expected to be ⬃98%. From
this we conclude that ␩ G (␭) and Q( ␮␶ ) are both close to
100% at the peak wavelength.
In summary, P3HT:PCBM bulk heterojunction devices
with an EQE of 76% at room temperature have been dem-
onstrated. The analysis of the loss mechanisms in these de-
vices allows the conclusion that an external quantum effi-
ciency of up to 90% is realistic given that optical losses in
the substrate can be minimized. The internal quantum effi-
ciency is shown to be close to 100%, confirming, that
P3HT:PCBM bulk heterojunction devices can be designed
nearly free of electrical losses over a broad wavelength re-
gion.
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