Organic Electronics 43 (2017) 142e147

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Organic Electronics
journal homepage: www.elsevier.com/locate/orgel

On the influence of the photo-oxidation of P3HT on the conductivity of

photoactive film of P3HT:PCBM bulk heterojunctions
ret c, Philippe Lecle
Yoshinori Aoyama a, d, Olivier Douhe re b, c, David Moerman b, c,
Junji Mizukado e, Hiroyuki Suda e, Roberto Lazzaroni b, c, Yuji Yoshida a, d, *
a
Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, 4259 Nagatsutatyo, Midori-ku, Yokohama, 226-8503, Japan
b
Laboratory for Chemistry of Novel Materials, Center for Innovation and Research in Materials and Polymers, CIRMAP, University of Mons, UMONS, Place du
Parc 20, B-7000, Mons, Belgium
c
Materia Nova Materials R&D Center, Avenue Nicolas Copernic 1, B-7000, Mons, Belgium
d
Research Center for Photovoltaic Technologies, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki,
305-8565, Japan
e
Research Institute for Innovation in Sustainable Chemistry, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi,
Tsukuba, Ibaraki, 305-8565, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Previously, we reported that the photo-oxidation of P3HT:PCBM was shown to induce an increase of the
Received 26 October 2016 electric resistance at the active layer in the solar cells, resulting in a drop in the device performances.
Received in revised form Meanwhile, fragments resulting from the partial molecular scission of P3HT chains were also detected by
15 January 2017
analyzing the produced materials using MALDI-TOF-MS. However, the way the photo-oxidation of these
Accepted 16 January 2017
Available online 18 January 2017
active materials actually impacts on the electric resistance of the resulting device yet remains to be
investigated. In this work, we perform Conductive-AFM (C-AFM) and Space Charge Limited Current
(SCLC) measurements on the photo-oxidized P3HT based films; the results indicate that the conductivity
Keywords:
Conductive atomic force microscope
of P3HT decreases upon irradiation, mainly due to a decrease of the hole mobility. Even though the
Polymer solar cells number average molecular weight of the P3HT only modestly decreases during the photo-oxidation, UV
Polymer scission evis spectra indicate a significant decrease of the long-range ordering of the P3HT chains. These results
Poly(3-hexylthiophene) inferred that P3HT crystal formation may partially be prevented by the oxidized molecular fragments of
Performance degradation reduced molecular weight, resulting in the decrease of P3HT hole mobility, hence leading to the observed
Photo-induced oxidation resistance increase in these photovoltaic active layers.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction
In the current developments of solar energy devices, polymer
solar cells (PSCs) presents several advantages such as mechanical
flexibility, portability (low weight), and possible low
manufacturing costs [1,2]. Among the semiconducting polymers
building up the device, poly(3-hexylthiophene) (P3HT) is one of the
standard donor type semiconducting materials in the photoactive
layer of the PSC. Recent studies on P3HT-based PSCs report a drastic
improvement in the power conversion efficiency [3e6]. Further-
more, large-scale production of PSCs can be expected imminently
* Corresponding author. Research Center for Photovoltaic Technologies, National
Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi,
Tsukuba, Ibaraki, 305-8565, Japan.
E-mail address: yuji.yoshida@aist.go.jp (Y. Yoshida).
[7]. However, among many other possible degradation factor P3HT-
based PSCs tend to progressively degrade with long-term solar light
irradiation [8e10]. In order to understand and depict the mecha-
nisms ruling such specific degradation and eventually improve on
the poor long-term durability, the photo-degradation of PSCs has
frequently been investigated [11e14].
Seeman et al. reported that device degradation could be either
reversible or irreversible [15]. Reversible degradation is defined as a
drop in the device performances that is recoverable, typically
through thermal annealing. Kawano et al. used thermally stimu-
lated current (TSC) spectroscopy to report that reversible degra-
dation was mainly caused by the accumulation of charge carriers at
trap sites [16]. Schafferhans et al. used TSC and charge extraction
from linearly increasing voltage (CELIV) measurements to show
that the exposure of solar cells to air resulted in degradation while
oxygen doping increases the density of deeper charge traps [15,17].

http://dx.doi.org/10.1016/j.orgel.2017.01.025
1566-1199/© 2017 Elsevier B.V. All rights reserved.
 Y. Aoyama et al. / Organic Electronics 43 (2017) 142e147
Irreversible degradation is however defined as a drop in the
device performances that cannot be restored. Jorgensen et al. pro-
posed that the main cause of irreversible degradation was the
dramatic molecular decomposition of organic materials such as
P3HT and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) upon
photo-oxidation [8]. We previously investigated the effect of
degraded active materials on device performance by employing
slightly photo-oxidized materials, and found that the photo-
oxidation process indeed increases the electric resistance of the
organic films, resulting in a drop in the device performances.
Fragments generated by the partial molecular scission of P3HT
chains were detected after photo-oxidation by MALDI-TOFMS [18].
Though we found that photo-oxidized P3HT:PCBM is responsible
the deterioration of the device performances, the mechanisms
ruling this degradation process remains to be depicted.
In this study, we focus on changes of the conductive and
structural properties of P3HT in photo-oxidized P3HT:PCBM blend
films. Appropriate measurements methods that can selectively and
locally probe changes taking place in P3HT, such as Conductive-
AFM (C-AFM) and Space Charge Limited Current (SCLC) measure-
ments were used for the evaluation of the conductivity and hole
mobility of the blend films, respectively. Ultraviolet visible ab-
sorption spectroscopy (UVevis) and gel permeation chromatog-
raphy (GPC) measurements were used for the analysis of the
structural changes in P3HT. The mechanism of P3HT photo-
oxidation in the blend films and the subsequent deterioration of
the device properties were investigated using those analytical
techniques.
2. Experimental details
2.1. Preparation of the photo-oxidized organic thin films
Poly(3-hexylthiophene) (P3HT) (Merck) (Mw ¼ 18,000 g/mol,
Mw/Mn ¼ 1.60), and [6,6]-phenyl-C61-butyric acid methyl ester
(PCBM) (Solenne) were used as donor like and acceptor like organic
semiconductors, respectively. All materials were used as received.
Anhydrous chlorobenzene (Sigma-Aldrich) solutions of P3HT
(1.8 wt%) and PCBM (1.2 wt%) were prepared in a glovebox and
stirred overnight. The following day, the solutions were transferred
into a transparent air-filled glass bottle. The concentration of oxy-
gen in solution was estimated to be 1.63  106 mol/L using Henry's
law [19]. The bottled solutions were then illuminated with AM1.5G
solar-simulated light irradiation at an intensity of 100 mW cm2 for
0, 20, 40, and 60 min to form four different partially photo-oxidized
organic solutions. No volatilization of the solvent was observed
during the irradiation. Each solution was dropped onto glass sub-
strates, for spin-coating at 2000 rpm for 120 s in the glovebox.
Finally the samples were first annealed at 110  C on a hot plate for
10 min and then at 135  C for 15 min. The thickness of those organic
films was 120 ± 5 nm, as measured by the stylus profilometry
(ULVAC E. S., Inc.).
2.2. Characterization of the photo-oxidized active materials
The organic films were optically characterized using
UVeviseNIR absorption spectroscopy (Shimadzu Co., LTD.). In
addition, gel permeation chromatography (GPC) (Waters, Co.)
measurements were conducted to determine the variations in the
active materials molecular weight in solution and induced by the
irradiation.
2.3. Fabrication and characterization of the devices
For the AFM and C-AFM measurements, samples equivalent to
143
that would be incorporated in devices were fabricated, with the
following architecture: glass/transparent electrode/buffer layer/
P3HT:PCBM organic layer. Indium tin oxide (ITO) and poly(3,4-
ethylenedioxythiophene): poly(styrenesulfonate) (PEDOT:PSS)
(Clevios, PVP. AI 4083) were used as the transparent electrode and
the planarization buffer layer, respectively. Prior to stack deposi-
tion, ITO coated glass substrate (20 mm  26 mm, thickness: 85 nm,
sheet resistance ¼ ~10 U/,, purchased from Naranjo B.V.) were
cleaned using an O2 plasma treatment (Harrick Plasma Inc.) for
30 min. The substrate was then spin-coated at 3000 rpm for 185 s
(thickness of the PEDOT:PSS layer ~30 nm) and dried at 135  C on a
hot plate for 10 min to get rid of water solvent. The substrates were
then transferred into a glovebox (N2, 99.99%; H2O, under 10 ppm;
O2, under 5 ppm). There, each illuminated organic solution was
deposited onto their substrates, and the organic thin films were
fabricated by the same method as described above. C-AFM exper-
iments were carried out using a Dimension Icon microscope
equipped with a Nanoscope V controller (Bruker AXS) [20,21]. A
sketch of the experimental setup and energy level diagram of the
materials are shown in Fig. 1. Soft cantilever-probes (Ref. PPP-
ContPt, Nanosensors GmbH) coated with an additional Pt/Ir layer
on silicon were used to ensure low contact forces and ohmic contact
at low DC sample bias with P3HT in the blend films. This set-up is
expected to provide information on hole transport properties in
P3HT selectively, because the energy barriers for both electron
transport and hole transport at the contact between PCBM and Pt/Ir
probe are far too high (1eV). Consequently PCBM is not contrib-
uting to the charge transport observed in this experimental
configuration. The typical force constant of the cantilever was
about 0.70 N/m, and the radius was below 25 nm. The AFM analysis
was carried out upon air and therefore very rapidly on each im-
aging location to avoid the response deterioration owing to tip
contact induced damage, from any mechanical or electrochemical
degradation mechanisms. The ITO layer was connected to the
conductive chuck of the microscope using Ag paste DC bias was
applied to the sample while the tip was grounded.
To measure the SCLC response, hole-only transport devices
(glass/transparent electrode/buffer layer/P3HT:PCBM organic layer/
gold electrode) were fabricated by thermal sublimation of gold on
the above devices. The active area of the cell was 0.04 cm2. After the
deposition, each device was placed in a sample holder sealed inside
the glove box, and the device characteristics were measured. All
device characterizations were conducted at room temperature. The
current density-voltage (J-V) curves were obtained using a source
meter 2400(Keithley Instruments Inc.)
3. Results and discussion
3.1. Physical properties of the P3HT:PCBM films
The local current measured by C-AFM on the blend films is ex-
pected to originate from either P3HT or PCBM. Firstly, in order to
determine in which material charge transport takes place, local I-V
C-AFM measurements were carried out on reference blends from
non photo-oxidized solutions. A typical I-V curve is shown in Fig. 2.
An asymmetric response (current arises under both negative and
positive bias) was obtained, whose form is similar to those recorded
on pristine P3HT thin films by Desbief et al. [20]. Then, to check
whether PCBM contributes to the C-AFM current, measurements
were conducted for DC sample bias up to þ3 V at PCBM micro-
cluster in samples that were thermally annealed to induce PCBM
aggregation into large domains. Zero current is recorded on those
PCBM crystals (see Figure S1 in the supporting information), in
agreement with the results reported by Alexeev et al. who inves-
tigated the conductivity of photoactive (MDMO-PPV:PCBM) layers
144
Fig. 1. (Left) sample setup for C-AFM and (Right) energy level diagram of the materials used in the present work.
400
200
0 sults suggest that the P3HT current decrease is owing to some
Local current / pA
-200
-400
-600
-800
-1000
-1200
-4 -2 0 2
Applied voltage / V
Fig. 2. Local I-V curve of a ITO/PEDOT:PSS/P3HT:PCBM device derived from C-AFM
measurements. This IeV curve have been obtained by averaging the current values
recorded independently on P3HT:PCBM for different DC sample bias.
by C-AFM using a similar experimental setup [22]. These results
indicate that the local current obtained by C-AFM measurements
only originates from P3HT.
Next, two-dimensional mapping of C-AFM height and currents
signals were simultaneaously recorded with a 2 V DC sample bias
on the photo-oxidized P3HT:PCBM blend films (5.0  5.0 mm2), as
shown in Fig. 3. Fig. 3(a), (b), (c), and (d) displays the height (top)
and current (image) images oft the samples before irradiation, and
after 20 min, 40 min, and 60 min irradiation, respectively. The
height images show that the RMS roughness values are very low
and remain unchanged (around 0.52 nm) upon photo-oxidation.
These values are typical of spincoated P3HT:PCBM blends and are
not dependent on the irradiation time. Thus, no significant differ-
ence of surface morphology was observed in the AFM measure-
ments among the samples prepared from photo-oxidized materials.
It must be noted that no spots with zero current are present in the
C-AFM images, in contrast to the C-AFM report by Alexeev et al.
[22]. They attributed those zero-current spots to PCBM domains
with a size 50 nm in the polymer matrix, the minimum size of
those spots being determined by the tip size. The absence of such
zero-current spots in our images indicate, consistently with
Y. Aoyama et al. / Organic Electronics 43 (2017) 142e147
topographical images, that PCBM domains over 50 nm are not
formed in these samples, and therefore large-scale P3HT:PCBM
phase-separation did not occur upon irradiation. In contrast with
height signal, the current images clearly show that the absolute
current values decrease along with the irradiation time. These re-
changes occurring at the molecular scale inside the film.
To determine the reason for the current decrease, hole-only
devices were fabricated using photo-oxidized blends, and the
hole mobility was extracted from the corresponding I-V curves, as
shown in Fig. 4 [23]. The solid lines correspond to calculated I-V
profiles assuming dominating space charge limited current (SCLC)
regime in the device; these lines show good fitting with the
experimental data. From the fitting, the hole mobility is calculated
by using the Mott-Gurney equation [24,25], as shown in Table 1. It is
found that the hole mobility decreases with the irradiation time.
Furthermore, the relationship between the hole mobility decrease
and the average local conductivity decrease measured by C-AFM is
linear (see Fig. 5). Considering that the conductivity is generally
4
defined by the product of the elementary charge, the carrier den-
sity, and the hole mobility (s ¼ qnm) [25], this relationship indicates
that ms ¼ qn
1 ¼ Const: and therefore the carrier density (n) is constant
before and after irradiation. This tendency is consistent with the
fact that the degree of P3HT:PCBM phase-separation and the
overall optical absorption of P3HT hardly change with irradiation
(see Figure S2). Therefore, it is deduced that the P3HT conductivity
decrease does not originate from a change in the carrier density but
from a decrease of the hole mobility.
3.2. Structural analysis of photo-oxidized active materials
As a first hypothesis, it is assumed that the decrease of the hole
mobility is due to a decrease of the P3HT average molecular length
caused by partial molecular scission during photo-oxidation [18].
To check that hypothesis, GPC measurements of the photo-oxidized
materials were carried out. The GPC curves and the changes of the
number average molecular weight (Mn) and small oxide molecule
number (mol%) estimated from the each Mn values [26] are shown
in Fig. 6 and Table 2, respectively. Those data show an increase in
the relative amount of short polymer chains, consistent with the
occurrence of chain scission upon phot-oxidation. However, the
decrease in the average molecular weight is only about 1000 g/mol,
which is not expected to induce a hole mobility decrease, based on
the work of Kline et al. on the correlation between Mn and field-
effect hole mobility in P3HT [27]. Therefore, the hole mobility
decrease that we observe cannot simply be explained by the
decrease of the P3HT average molecular weight. In the case of regio-
 Y. Aoyama et al. / Organic Electronics 43 (2017) 142e147 145

Fig. 3. C-AFM (Above) height images and (Below) current images obtained simultaneously on photo-oxidized P3HT:PCBM films on Glass/ITO/PEDOT:PSS substrates: (a), (b), (c), and
(d) correspond to no-irradiation, 20 min irradiation, 40 min irradiation, and 60 min irradiation, respectively. The DC sample bias was set to 2 V for every C-AFM captures.

Table 1
Hole mobility of the photo-oxidized P3HT esti-
100 mated by the experimental SCLC in Fig. 4 and Mott-
Gurney equation.

t (min) m (cm2/Vs)
2

0 12.0  106
Current density / mA/cm

20 6.2  106
40 4.4  106
10 60 3.2  106

regular P3HT, it has already been known that the bulk conductivity
increases by forming partial crystal domains (p-stacked lamellar
structures) made from ordered packing of the chains [24,28]. Surin
1 et al. also shows the formation of the fibrillar structure which is
made from p-stacking of the RR-P3HT conjugated backbones and
0 min the interdigitation of the alkyl groups appear to lead to optimal FET
performances [29]. Therefore, the decrease in the conductivity
20 min upon photo-oxidation may originate from the fact that the molec-
40 min ular scission could induce changes in the P3HT crystal domains, in
0.1 60 min other words, the higher-order structure (fiberlike structure) of
P3HT.
Previously, it was demonstrated that it is difficult to estimate a
quantitative crystallinity difference by XRD measurements on
5 6 7 2 3 4 5 67 slightly-photo-oxidized organic films [30]. To probe the degree of
1 10 order of P3HT in the photo-oxidized films, we therefore analyzed in
Applied voltage / V detail the UVevis absorption spectra, as it is well-know that the
vibronic structure present (or not) in those spectra strongly reflects
Fig. 4. Macroscopic I-V curves for (B) 0, ( ) 20, ( ) 40, and ( ) 60 min of the hole- the long-range organization of the chains. . Here we analyze those
only transport devices (ITO/PEDOT:PSS/P3HT:PCBM/Au). The solid lines are fits to UVevis spectra on the basis of the work by Clark et al. which shows
the space-charge-limited current regime, where the current density is given by the
how to estimate the quantitative degree of crystallinity (DOC) in
Mott-Gurney law, JSCLC ¼ 98ε0 εr m VL3 , where ε0 is the vacuum permittivity, εr is dielectric
2

constant of the film (εr ¼ 3 was assumed for P3HT), m is hole mobility, and L is film regioregular P3HT by using a weakly interacting H-aggregate
thickness (120 nm). model [24,31]. In that procedure, the absorbances of P3HT chains
146 Y. Aoyama et al. / Organic Electronics 43 (2017) 142e147

1.0 12x10
-6
0 min 20 min t=0
0.8 40 min 60 min
10

Mobility (cm / Vs)

Pixel count / %

0.6

2
8
0.4
6
0.2
4
0.0 t = 60

-1200 -800 -400 -1200 -800 -400 0

Current / pA <IC-AFM> / pA

Fig. 5. (Left) Statistics of the conductivity for (C) 0, ( ) 20, ( ) 40, and ( ) 60 min obtained from C-AFM current images (measured under 4 V). (Right) Relationship between hole
mobility and average conductivity along with irradiation time. It is found that the relationship between amount of mobility change and amount of average conductivity change is
proportional. In other words, ms ¼ qn1 ¼ Const:. Therefore, the carrier number (n) is constant before and after irradiation.

Table 3
15 Degree of crystallinity (DOC) of photo-oxidized P3HT
0 min (a)
estimated by linear absorption spectroscopy.
20 min t (min) DOC of P3HT (%)
40 min
10 60 min 0 min 44
Intensity (a.u.)

20 min 40
(a) 40 min 36
60 min 32
5 (b)
(b)
crystalline domains, which are made of p-stacked lamellar struc-
tures of P3HT chains, is partially prevented by the presence of the
0 photo-oxidized chains, most probably because the shorter, photo-
oxidized chains co-aggregate with the pristine chains during the
film formation process.
18 20 22 24 26 In this research, the degradation of the polymer compounds was
Retention time / min investigated starting from the initial solution, not on the complete
PSCs. Therefore, the degradation mechanism might not be
Fig. 6. GPC curves for (d) 0, ( ) 20, ( ) 40, and ( ) 60 min of the photo- completely identical to that taking place in the thin film state [9,10].
oxidized P3HT:PCBM organic films. An increase of the small molecule region (a), (b) However, the decrease of the P3HT absorption at the shoulder peak,
along with irradiation time is clearly observed.
which suggests a cristallinity decrease, is also observed in the
photodegradation of an encapsulated thin films [32]. Therefore,
Table 2
also in the organic films used in a complete device, the mixing of
Number average molecular weight (g/mol) and small oxide molecule number (mol%) the small molecular fragments generated by the molecular scission,
 The small
of photo-oxidized P3HT.  oxide molecule number (mol%) is estimated by which impacts on the higher-order structure of P3HT, also probably
using Nlow x ðmol%Þ ¼ M
Mn x  1  100 [26].
n 0
occurs in complete PSC devices. For high durability of PSCs, it is
t (min) Mn (g/mol) Nlow (mol%) important to elucidate the degradation mechanism of PSCs by
connecting the molecular chemistry information that we have
0 min 12,500 0
20 min 12,300 1.6 obtained in this study and the conventional research approach
40 min 11,900 4.8 using the macroscale physical response.
60 min 11,600 7.2

4. Conclusion

from amorphous regions and the organized domains (giving rise to

To understand the effect of the photo-oxidized P3HT:PCBM on
shoulder peaks at long wavelengths) are separated, and the DOC of
the resistance increase of the active layer in the solar cells, we
P3HT is determined by the ratio between those absorbances. The
focused on changes of the physical properties and structure of P3HT
changes of DOC of P3HT in the photo-oxidized organic films are
in photo-oxidized P3HT/PCBM blend films. Conductive-AFM (C-
shown in Table 3 (the UVevis spectral changes and the detailed
AFM) and Space Charge Limited Current (SCLC) measurements
method are described in Figure S2 in the supporting information). It
suggest that the conductivity decrease along with irradiation de-
is found that the DOC of P3HT decreases by about 10% after photo-
rives from a decrease of P3HT hole mobility. Even though the
irradiation. In other words, it is implied that the formation of P3HT
number average molecular weight of the P3HT is slightly decreased
 Y. Aoyama et al. / Organic Electronics 43 (2017) 142e147
by photo-oxidation, the major reason for the decrease of the elec-
trical properties is attributed to a reduction of the crystallinity of
P3HT, compared with that of the non-oxidized polymer, as reflected
in the UVevis spectra. These results indicate that P3HT crystal
formation may partially be prevented by the photo-oxidized frag-
ments with low molecular weight, resulting in the decrease of P3HT
hole mobility and leading to the resistance increase in the organic
films.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.orgel.2017.01.025.
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