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Oxygen doping of P3HT:PCBM blends: Influence on trap states, charge carrier

mobility and solar cell performance


Julia Schafferhans 1 ,∗ Andreas Baumann 1 , Alexander Wagenpfahl 1 , Carsten Deibel 1 , and Vladimir Dyakonov 1,2†
1
Experimental Physics VI, Faculty of Physics and Astronomy,
Julius-Maximilians-University of Würzburg, Am Hubland, 97074 Würzburg, Germany and
2
Bavarian Center of Applied Energy Research e.V. (ZAE Bayern), Am Hubland, 97074 Würzburg, Germany

We investigated the influence of oxygen on the performance of P3HT:PCBM (poly(3-


arXiv:1008.4230v1 [cond-mat.mtrl-sci] 25 Aug 2010

hexylthiophene):[6,6]-phenyl C61 butyric acid methyl ester) solar cells by current–voltage, thermally
stimulated current (TSC) and charge extraction by linearly increasing voltage (CELIV) measure-
ment techniques. The exposure to oxygen leads to an enhanced charge carrier concentration and
a decreased charge carrier mobility. Further, an enhanced formation of deeper traps was observed,
although the overall density of traps was found to be unaffected upon oxygen exposure. With the
aid of macroscopic simulations, based on solving the differential equation system of Poisson, con-
tinuity and drift-diffusion equations in one dimension, we demonstrate the influence of a reduced
charge carrier mobility and an increased charge carrier density on the main solar cell parameters,
consistent with experimental findings.

1. INTRODUCTION 2. EXPERIMENTAL

Power conversion efficiencies of almost 8% for organic The investigated bulk heterojunction solar cells
solar cells have already been achieved, with growing ten- were prepared by spin coating P3HT:PCBM (ra-
dency [1]. A critical issue yet to be addressed are the tio 1:0.8) blends made from solutions of 30 mg/ml
factors influencing the device lifetime. To gain a detailed in chlorobenzene on poly(3,4-ethylenedioxythiophene)
understanding of the device stability, as well as the un- poly(styrenesulfonate) (Pedot:PSS) covered indium tin
derlying degradation mechanisms and their impact on oxide/glass substrates. The active layer was about 240
the solar cell performance is an important prerequisite nm thick. After an annealing step of 10 min at 130 ◦ C, Ca
for lifetime enhancements. (1.5nm)/Al (60nm) contacts were evaporated thermally
(base pressure during evaporation < 7 · 10−7 mbar). The
Organic solar cells undergo many degradation path-
effective areas of the solar cells were 3 mm2 and 9 mm2 .
ways during their lifetime. Efficiency losses due to light
[2], oxygen [3, 4] and water [5] are reported. The details PEDOT:PSS was purchased by H.C.Starck (CLEVIOS
of the degradation processes, however, are still not com- P VP Al 4083). P3HT was delivered by BASF (Sepiolid
pletely understood. Other studies, on the contrary, are P200), PCBM (purity 99,5 %) by Solenne. All materials
only focused on the degradation of a single active mate- were used without further purification. All preparation
rial instead of the blend. For example for P3HT oxygen steps were performed in a nitrogen glovebox and an at-
is known to form a charge transfer complex [6] resulting tached thermal vacuum evaporation chamber.
in p-doping of P3HT [7, 8], which is also investigated Initial current–voltage (IV) characteristics of the solar
theoretically by band-structure calculations [9]. Further- cells were measured in the nitrogen glovebox. For the
more, oxygen induced degradation of P3HT is reported to illumination of the cells we used an Oriel 81160 AM1.5G
result in decreased mobilities [6, 10] and increased trap solar simulator. The power conversion efficiencies of the
densities [10]. In the case of C60, oxygen also causes investigated samples were 3% – 3.5%.
decreased electron mobilities [11, 12] and increased trap Degradation studies of the unprotected solar cells were
densities [13], as demonstrated by investigations of C60 performed in a closed cycle cryostat. During the ther-
based field effect transistors. mally stimulated current (TSC), charge carrier extrac-
This paper addresses the oxygen induced degradation tion by linearly increasing voltage (CELIV) [14, 15] and
of poly(3-hexylthiophene):[6,6]-phenyl C61 butyric acid IV–measurements the cryostat was filled with helium as
methyl ester solar cells in the dark, as well as under si- contact gas. To investigate the influence of oxygen on
multaneous illumination. Detailed investigations includ- the solar cells, the helium was replaced with synthetic
ing charge carrier mobility, charge carrier density and air (80% N2 , 20% O2 , < 1ppm H2 O) for different degra-
defect spectroscopic measurements are performed to get dation times. Thus, the effect of humidity was excluded.
an insight of the degradation mechanism due to oxygen This exposure was always done at a constant tempera-
in P3HT:PCBM solar cells. ture of 300 K. Two different degradation conditions were
investigated: in synthetic air either in the dark or under
illumination. For the latter we used a 10 W high power
white light emitting diode (Seoul). The light intensity
∗ Electronic mail: julia.schafferhans@physik.uni-wuerzburg.de was adjusted to match the short circuit current of the
† Electronic mail: dyakonov@physik.uni-wuerzburg.de non degraded cells obtained under the solar simulator.
2

The LED was also used for the illuminated IV-curves in 0 h and 120 h in synthetic air in the dark are shown in
the cryostat. Fig. 1a. The obtained values for the power conversion ef-
For TSC measurements the trap filling was achieved by ficiency (PCE), fill factor (FF), open circuit voltage (Voc )
illumination of the samples at 18 K for five minutes using and short circuit current (Jsc ), normalized to the initial
the 10 W LED. After a dwell time of five minutes the tem- values are presented in Fig. 1b The observed efficiency
perature was increased with a constant heating rate of 7 loss with dark degradation time is only due to Jsc , which
K/min up to 300 K. The TSC signals were detected by decreases about 60% within 120 h, whereas Voc and FF
a Sub-Femtoamp Remote Source Meter (Keithley 6430) remain almost constant. Since the exposure of the sam-
without applying an external field, implying that the de- ples to synthetic air in the dark results only in a loss in
trapped charge carriers were extracted from the samples Jsc , a degradation of the electrodes being the origin of
only due to the built-in voltage. Further details of the these findings can be excluded. Degradation (oxidation)
TSC measurements are described elsewhere [10]. of the Ca/Al electrode would result in the occurrence of
CELIV measurements were performed at 300 K. The an s-shaped IV-curve [16], at least in a strong loss in FF
peak voltage of the triangular bias pulse in reverse direc- or Voc . Neither of these effects was observed within the
tion was Va = 2 V applied on the Ca/Al electrode. A timescale of degradation considered here.
voltage pulse width of 50 µs was chosen.
(a)
0 min
60
2 min
0 min

] mc/Am[ ytisned tnerruc


2
6 min
3. RESULTS AND DISCUSSION 20 min

40 60 min

120 min
3.1. Experimental Results 180 min
180
20 min

The IV-curves for different degradation times between


0
180 min
80
0 min

(a) 0h

1h -0.4 0.0 0.4 0.8


3h
] mc/Am[ ytisned tnerruc

60
2

10h voltage [V]

30h

40
120h 1.0
0 h

(b)
normalized parameter

20 0.9
120 h PCE
120 h
FF
0
0.8 Voc
0 h Jsc

-0.4 0.0 0.4 0.8

0.7
voltage [V]

1.0
0 2 6 20 60 120 180
(b)
0.9 degradation time [min]
normalized parameter

0.8
FIG. 2: Illuminated IV-curves of P3HT:PCBM solar cells for
0.7 PCE different degradation times in synthetic air under simultane-
FF
Voc ous illumination (a) and the normalized values of the PCE,
0.6
Jsc fill factor, open circuit voltage and short circuit current (b).
0.5 In contrast to dark degradation in synthetic air all parameters
decrease.
0.4
0 1 3 10 30 120 In contrast to degradation in synthetic air in the dark,
degradation time [h] the efficiency loss due to degradation in synthetic air and
simultaneous illumination (Fig. 2a, b) occurs on a faster
FIG. 1: Illuminated IV-curves of P3HT:PCBM solar cells for time scale—about 30% efficiency loss within 180 min—
different dark degradation times in synthetic air (a) and the and is caused by a decrease of Jsc , as well as FF and
normalized values of the PCE, fill factor, open circuit voltage Voc , which all decrease about 10% within this time scale.
and short circuit current (b). The efficiency loss is due to the Since, in the case of dark degradation, FF and Voc are
decrease of the short circuit current. unaffected, the decrease of both during photodegrada-
3

tion is due to light in the presence of oxygen, indicating 200 meV to 400 meV which are not seen in pure P3HT,
an additional degradation path due to photooxidation in with the center at about 250 meV. We refer to the lat-
addition to doping as found under oxygenation in the ter trap distribution as T3. Therefore we conclude that
dark. the DOOS of the blend consists of three different traps,
To gain a deeper understanding of the underlying with the dominant trap T2 at 105 meV. This interpreta-
degradation mechanisms, we performed TSC measure- tion is also supported by the TSC spectrum of pristine
ments to obtain information about the electronic trap P3HT:PCBM solar cells, where T2 has a lower concen-
states of P3HT:PCBM solar cells for dark as well as pho- tration compared to T1 and T3, so that T1, T2, and T3
todegradation. First of all, the trap distribution of non can be clearly distinguished (data not shown). The trap
degraded P3HT:PCBM solar cells was investigated by density obtained from the TSC measurements of the in-
applying a fractional TSC measurement—the so-called vestigated P3HT:PCBM solar cells is in the range of 6 –
Tstart -Tstop technique [10, 17]—with Tstop varied be- 8 ·1022 m−3 which is considerably higher than the value
tween 25 K and 150 K in steps of 5 K. The resulting obtained for P3HT (1 ·1022 m−3 ) [10].
density of occupied states (DOOS) distribution is shown The TSC spectra of P3HT:PCBM solar cells for dif-
in Fig. 3. The continuous activation energies of the traps ferent dark degradation times in synthetic air are shown
in Fig. 4a. Thermally stimulated current is observed
21
6x10 T2
P3HT
0
T1 (a)
P3HT:PCBM
5
-10
]
3-
m[ ytisned part

4 -20 0h

TSC [pA]
3 T3 -30 100 h

-40 0h
2 100 h
1h
-50 3h
1 10 h
30 h
-60
100 h
0 0h
0.1 0.2 0.3 0.4 -70
40 80 120 160
activation energy [eV] temperature [K]
23
1.0x10
FIG. 3: Comparison of the DOOS distribution of P3HT and (b)
P3HT:PCBM blends, as obtained by TSC-Tstart -Tstop mea-
0.8
surements. The DOOS of P3HT consists of two different traps
trap density [m ]
-3

(T1, T2), which both also contribute to the DOOS of the


blend. Additionally to these two traps the DOOS of the blend 0.6
features a third trap distribution (T3) with higher activation
energy. 0.4

range from 20 meV to 400 meV with the center of distri- 0.2
bution at about 105 meV. For further interpretation of
the DOOS distribution of the blend, we consider the re- 0.0
0 1 3 10 30 100
sults for pure P3HT. For P3HT, the DOOS was related to
degradation time [h]
two different overlapping traps with approximately Gaus-
sian energy distributions [10], with the center of distri-
FIG. 4: TSC spectra of P3HT:PCBM solar cells for different
bution of the dominant trap at about 105 meV (T2) and dark degradation times in synthetic air (a) and the obtained
the other at about 50 meV (T1) (shoulder at the low en- trap densities (b). The trap density remains almost constant.
ergy side of the DOOS distribution) (Fig. 3). Since the The slight decrease of the trap density for 100 h degradation
centers of distribution for the blend as well as the pure time is possibly due to recombination of the detrapped charge
P3HT are at 105 meV, we attribute the dominant trap to carriers.
P3HT, although the distribution of the main trap in the
blend is broadened as compared to the pure P3HT, indi- between 18 K and 160 K. At higher temperatures no ad-
cating a higher disorder in the blend. Furthermore, the ditional TSC peaks can be observed up to 300 K. With
T1 can also be seen in the DOOS distribution of the blend exposure to synthetic air, a shoulder at about 100 K
in the steep onset of the distribution on the low energy appears, which increases with longer degradation times
side, but is less pronounced due to the higher concentra- within the investigated time scale up to 100 h. The ap-
tion of the main trap T2, overlapping T1. Additionally pearance of a shoulder indicates an increase in density
to these two traps, the DOOS distribution of the blend of the deeper traps or even the formation of additional
features further trap states with activation energies of traps. The main peak however decreases slightly. As a
4

result the overall trap density of the blend obtained by almost the same behavior of TSC spectra, but on a faster
the TSC measurements remains almost constant for the timescale than during dark degradation.
different degradation times (Fig. 4b). In this context it To get further information about the influence of oxy-
has to be mentioned that the determined trap density gen on the mobility and also the charge carrier con-
from the TSC spectra is only a lower limit of the actual centration of the blend, we used the CELIV technique,
trap density [18]. One reason is a possible recombination which enables the simultaneous investigation of equilib-
between electrons and holes after one of them got de- rium charge carrier density and mobility by recording
trapped due to thermal activation. For degradation on transient currents . The CELIV measurements for dif-
synthetic air and simultaneous illumination we monitored ferent degradation times in synthetic air in the dark
are shown in Fig. 5a. The CELIV curves exhibit a
high asymmetry, especially for longer degradation times,
2.5 (a) which might result from trapped charge carriers being
extracted as the higher voltages at longer times promote
] mc/Am[ ytisned tnerruc

0 h
2

2.0 120 h 1 h
emission from traps. This is in accordance with the in-
3 h crease of the deeper traps density as revealed by the
10 h
1.5
30 h
TSC measurements. The mobility for different degra-
120 h dation times was calculated from the position of the cur-
1.0 rent peak maximum according to reference [15]. Only
0 h
a slight decrease of the mobility with degradation time
0.5 can be observed (Fig. 5b), resulting in a decrease of
about 50 % after 120 h in synthetic air. The equilibrium
0.0 charge carrier density, extracted by the CELIV measure-
0 10 20 30 40 50
ments, however, increases about a factor of two within
time [ ms] a degradation time of 120 h in the dark (Fig. 5c). We
assign these additional charge carriers to oxygen doping
-7
1.0x10 (b) of P3HT, which was also reported for P3HT diodes [10]
]sV/ m[ ytilibom reirrac egrahc

and P3HT field effect transistors [7, 8]. We note that


2

0.8
the concentration of charges measured by CELIV pro-
vides only a lower limit of the actual charge carrier den-
0.6
sity, since only charge carriers extracted within the time
scale of the experiment (voltage pulse width typically 50
0.4
µs) are observed. Thus, the experimental number in-
0.2
cludes charges from comparably shallow traps which can
be emitted from them and then be extracted; charges in
0.0
deeper traps as well as the ones lost within the sample
0 1 3 10 30 120
(by recombination) are disregarded. The degradation on
exposure time [h] synthetic air and simultaneous illumination shows simi-
lar results for the changes in mobility and charge carrier
21
8x10
concentration, but again the degradation is accelerated
(c)
to a timescale of minutes instead of hours.
]
3-
m[ ytisned reirrac egrahc

3.2. Simulation
4

In order to understand the influence of a decreased


2 mobility as well as charge carrier doping on the solar cell
parameters, we performed macroscopic simulations based
0
on solving the differential equation system of the Poisson,
0 1 3 10 30 120 the continuity and the drift–diffusion equations in one
exposure time [h]
dimension [19, 20]. In the simulation we accounted a bi-
molecular non-geminate recombination rate according to
FIG. 5: CELIV measurements of P3HT:PCBM solar cells for Langevin [21]. The charge carrier generation by light was
different dark degradation times in synthetic air for offset bias assumed to create free polarons, neglecting any influence
of -0.3 V applied at the Ca/Al electrode (a) and the obtained of electric field driven polaron pair dissociation. Further-
mobilities (b) as well as the charge carrier densities (c). The more the charge carrier mobilities of electrons and holes
charge carrier mobility slightly decreases with degradation were set equal in the simulations. The used parameters
time, whereas the charge carrier density shows an increase are listed in Table I. Using this approach we investigated
due to oxygen doping. the effect of charge carrier doping by oxygen on the solar
5

20
1.0
-8 2
(a) µ=3 á10 m /Vs
(b)
-3
15 hole doping [m ]

] mc/Am[ ytisned tnerruc


2

retemarap dezilamron
0 0.8 PCE
21
10 10 FF
22
10 V
oc
23
5 10 0.6 J
sc
24
10

0.4

-5

-10 0.2

21 22 23 24
0.0 0.2 0.4 0.6 0.8 1.0
0 10 10 10 10
-3

voltage [V] hole doping [m ]

20 1.2

(c) (d)

15 2
] mc/Am[ ytisned tnerruc

mobility [m /Vs]
2

retemarap dezilamron
-7 1.0
1á10
10 -8
1á10
-9
1á10
5 0.8

PCE
0 FF

0.6 V
oc

-5 J
sc

0.4
0.0 0.4 0.8 1.2 -7 -8 -9
10 10 10

2
voltage [V]
mobility [m /Vs]

FIG. 6: Simulated IV-curves for different levels of hole doping (a) and the normalized values of the PCE, fill factor, open circuit
voltage and short circuit current (b). An increased doping level results in a decrease of Jsc . A lowered charge carrier mobility
(c) instead leads to a decrease of Jsc and FF (d).

parameter symbol value unit by an increased bimolecular recombination probability.


temperature T 300 K Since doping implies additional charges within the de-
effective band gap Eg 1.30 eV vice, it leads to less band bending and therefore a reduced
relative dielectric constant ǫr 3.6 electrical field within the solar cell. As a consequence the
extraction time for the charge carriers increases leading
active layer thickness L 100 nm
to a higher recombination probability and thus to a lower
effective density of states Nc , Nv 8.0 × 1025 1/m3 short circuit current.
generation rate G 6.0 × 1027 1/m3 s
injection barriers Φa , Φc 0.1 eV
The influence of the mobility on the solar cell perfor-
TABLE I: Parameters used for simulation. mance is shown in Fig. 6 c, d, revealing a loss of Jsc and
FF and a small increase of Voc for decreased mobilities.
A lower mobility leads to a higher extraction time for the
charge carriers and therefore to an enhanced bimolecular
cell parameters. recombination probability, which results in the decreased
The simulated IV-curves for different hole doping lev- FF. At the same time, the charge extraction becomes less
els are shown in Fig. 6 a and the corresponding nor- efficient. The slightly increasing open circuit voltage is
malized solar cell parameters in Fig. 6 b. For the given due to a lower Langevin recombination rate due to de-
parameter set, doping concentration up to 1022 m−3 does creased mobilities. The higher charge carrier densities
not change the PCE, whereas for higher concentrations and their more balanced distribution reduce the inter-
the PCE strongly decreases due to a decrease of Jsc . nal electric field and therefore increase the open circuit
FF and Voc , however, remain almost unaffected. This voltage[22, 23]. If the field dependent polaron pair dis-
behavior is almost independent of the mobility (within sociation was also taken into account, it would mostly
changes of one order of magnitude) used for the simula- influence the FF and Jsc resulting in an even stronger
tions. The decreased Jsc due to doping can be explained decrease with lower mobilities.
6

3.3. Discussion illuminated case occurs on a faster timescale. In contrast,


the loss in FF is only observed for photodegradation. Ad-
The influence of oxygen on P3HT:PCBM solar cells ditionally, we experimentally observed also a decrease of
results in the case of dark degradation in a loss of Jsc , Voc for photodegradation, whereas a decrease in mobil-
whereas photodegradation results in a decrease of all so- ity should result in an increase of Voc as exhibited by the
lar cell parameters. Further, the degradation due to simulation (Fig. 6 d). Therefore, the decreased mobility
oxygen is accelerated by light. A similar behavior was is not the reason for the FF loss.
recently reported for inverted P3HT:PCBM solar cells Another important factor which can negatively influ-
[3], where the efficiency yields almost no change for ence the solar cell performance are electronic trap states,
dark degradation within the investigated timescale of since they lower the mobility, disturb the internal field
1h, whereas a strong loss for photodegradation within distribution and can act as recombination centers. Ex-
120 min is observed. The loss in Jsc can be explained posure of P3HT:PCBM solar cells to oxygen results in
by charge carrier doping, as we demonstrated by using a rise of the density of deeper traps for both dark and
macroscopic simulations. This interpretation is in ac- illuminated degradation. On the other hand, the main
cordance with the CELIV measurements, which show an peak of the TSC slightly decreases due to oxygen expo-
increasing charge carrier concentration with degradation sure, which is in contrast to the observed increase of the
time. We attribute the increased charge carrier concen- main TSC peak of pure P3HT [10]. For comparison, the
tration to oxygen doping of P3HT [7, 8, 10]. The dif- trap density in pure P3HT increases almost by a factor
ference between the doping levels in the simulations and of three within 100 h under oxygen exposure [10]. In this
these determined by CELIV can be explained by the fact context we want to mention again that the determined
that the extracted charge carrier density by CELIV is trap density from the TSC spectra is only a lower limit
only a lower limit of the actual charge carrier concen- of the actual trap density [18].
tration, as mentioned before. The actual charge carrier The appearance of deeper traps due to oxygen expo-
density can be significantly higher. Furthermore, the ac- sure could also be the reason for the observed loss in fill
celerated increase of the charge carrier density in the case factor, since they can disturb the internal field distribu-
of photodegradation compared to the dark degradation tion and act as recombination centers, as mentioned be-
is in good agreement with results of P3HT transistors, fore. Further investigations concerning the influence of
which also showed an expedited oxygen doping with light deep traps on the solar cell performance have to be done,
[7]. like the implementation of deep traps within the macro-
In addition to an increased charge carrier concen- scopic simulation. Other crucial factors concerning FF
tration, CELIV measurements reveal a decrease of the and Voc we want to address, are imbalanced electron–hole
charge carrier mobility for the P3HT:PCBM blends mobilities (resulting in the formation of space charges)
due to oxygen. A decreasing mobility with degrada- and a field dependent photogeneration. These two fac-
tion time is also reported for pure P3HT [10], but tors have not been accounted so far and will be addressed
in contrast to pure P3HT, where the mobility de- in the future to completely clarify the origin of the loss
creases about two orders of magnitude within 100 h of FF and Voc in the case of oxygen induced degradation
[10], only a slight decrease in the blend—by about 50 under simultaneous illumination.
%—can be observed. This difference could be due to
a stabilization effect of PCBM for P3HT in analogy
to findings for MDMO-PPV (poly(2-methoxy-5-(3’,7’- 4. CONCLUSIONS
dimethyloctyloxy)-1,4-phenylene-vinylene)):PCBM solar
cells [4]. The decreased mobility could also result from a We investigated the influence of oxygen on unprotected
degradation of PCBM due to oxygen. Decreased electron P3HT:PCBM solar cells by controlled exposure to syn-
mobilities for C60 based field effect transistors after oxy- thetic air. Two different degradation conditions were
gen exposure have already been reported [11, 12]. Since used: in the dark and under simultaneous illumination.
electron and hole mobilities can not be discriminated by Exposure of the solar cells to synthetic air in the dark
CELIV, it is not possible to resolve which carrier mobility results in a loss of Jsc of about 60 % within 120 h. In
decreases. contrast, simultaneous illumination during oxygen degra-
A lower mobility leads to a decrease of FF and Jsc , dation results in a loss of all solar cell parameters, yield-
as revealed by macroscopic simulations. Although our ing an efficiency loss of about 30 % within only 3 hours.
CELIV measurements show a slight decrease in mobility Thus, the degradation of the P3HT:PCBM solar cells is
with degradation time, there are some facts indicating strongly accelerated by light.
that the decreased mobility is not the origin of the FF CELIV measurements revealed an increased charge
loss in the case of photodegradation. First of all the ex- carrier concentration after oxygen exposure for dark, as
perimentally observed mobility reduction is too limited well as photodegradation. We attributed these additional
to have a strong impact on the FF. Furthermore, the charge carriers to oxygen doping, which is also known for
mobility decreases in the same range for both dark and pure P3HT. With the aid of macroscopic simulations we
illuminated degradation, although the degradation in the have shown that doping of the solar cells is the origin of
7

the loss in Jsc for both degradation conditions. Acknowledgements


Another impact of oxygen exposure on P3HT:PCBM
solar cells is a slight decrease of the charge carrier mobil-
ity, as also revealed by CELIV measurements. Although
a decreased mobility may result in a loss of the fill factor, The current work is supported by the Bundesminis-
as shown by macroscopic simulations, the experimentally terium für Bildung und Forschung in the framework of
observed mobility decrease is too small to be the origin the OPV Stability Project (Contract No. 03SF0334F).
of the FF drop in the case of photodegradation. J.S. thanks the Elitenetzwerk Bayern for funding. A.B.
In addition to an enhanced charge carrier concentra- thanks the Deutsche Bundesstiftung Umwelt for funding.
tion, oxygen induced degradation results in an increase of C.D. gratefully acknowledges the support of the Bavar-
the density of deeper traps, as was revealed by TSC mea- ian Academy of Sciences and Humanities. V.D.’s work
surements. These deep traps could be the origin of the at the ZAE Bayern is financed by the Bavarian Ministry
decreased FF and Voc , although further investigations to of Economic Affairs, Infrastructure, Transport and Tech-
correlate the trap density to the solar cell performance nology. The authors thank Jens Lorrmann for fruitful
are required for a verification. discussion.

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