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1008 4230 PDF
1008 4230 PDF
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
40 60 min
120 min
3.1. Experimental Results 180 min
180
20 min
(a) 0h
60
2
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
0.7
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
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
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
20
1.0
-8 2
(a) µ=3 á10 m /Vs
(b)
-3
15 hole doping [m ]
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
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).
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