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Environmental Science
Cite this: Energy Environ. Sci., 2012, 5, 9662
www.rsc.org/ees PAPER
Highly conductive PEDOT:PSS electrode by simple film treatment with
methanol for ITO-free polymer solar cells
Desalegn Alemu,abc Hung-Yu Wei,d Kuo-Chuan Hod and Chih-Wei Chu*be
Received 19th June 2012, Accepted 17th September 2012
Published on 18 September 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22595F

DOI: 10.1039/c2ee22595f

We proposed a simple yet robust film treatment method with methanol having only one hydroxyl
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group to enhance the conductivity of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)

(PEDOT:PSS) by four orders of magnitude. Different methods of film treatment: immersing
PEDOT:PSS film in the methanol solution; dropping methanol on the film; and a combination of
these are employed and the results are compared. The conductivity of PEDOT:PSS films was
enhanced from 0.3 S cm
1 to 1362 S cm
1 after film treatment with methanol. Other alcohols like
ethanol and propanol were also used to treat the PEDOT:PSS film and showed inferior conductivity
enhancement compared to methanol. The conductivity enhancement was greatly affected by the
hydrophilicity and dielectric constant of the alcohols used. The mechanism of conductivity
enhancement was investigated through various characterization techniques including FTIR, XPS and
AFM. Removal of the insulator PSS from the film, and morphology and conformational changes are
the mechanisms for the conductivity enhancement. The treated films also showed high transmittance
and low sheet resistance desirable for a standalone electrode. ITO-free polymer solar cells were
fabricated using PEDOT:PSS electrodes treated with methanol and showed almost equal performance
to ITO electrodes.

1. Introduction
Polymer solar cells (PSCs) are attractive for next generation
a
Nanoscience and Technology Program, Taiwan International Graduate green energy sources because of their promising potential for
Program, Academia Sinica, Taipei 115, Taiwan roll-to-roll and large area processing, flexibility and cheap cost of
b
Research Center for Applied Sciences, Academia Sinica, Taipei 115,
Taiwan. E-mail: gchu@gate.sinica.edu.tw; Fax: +886-2-27896680; Tel:
manufacture.1–3 The recently reported high power conversion
+886-2-27898000 ext. 70 efficiencies approaching 10% signal that their commercialization
c
Department of Engineering and Systems Science, National Tsing Hua will be soon.4–6 The next challenge is to realize the high speed
University, Hsinchu 30013, Taiwan manufacturing of cells and modules with long lifetimes. The
d
Institute of Polymer Science and Engineering, National Taiwan electrodes are the bottleneck for the roll-to-roll high speed pro-
University, Taipei 10617, Taiwan
e
Department of Photonics, National Chiao Tung University, Hsinchu 300, cessing of PSCs. At least one of the electrodes in solar cells needs
Taiwan to be transparent in order to allow light to be harvested by the

Broader context
Polymer solar cells are considered as next generation renewable energy sources since they can produce low cost electricity owing to
their roll-to-roll processability on flexible substrates. ITO, which is a currently used transparent electrode, is not ideal because of its
high cost due to its limited availability and other technical drawbacks. Poly(3,4-ethylene dioxythiophene) doped with poly(styrene
sulfonate) (PEDOT:PSS) is envisioned as quite promising; however, pristine PEDOT:PSS has a very low conductivity for use as an
electrode. We propose a simple and easy way to scale up the film treatment method with cheap and less environmentally hazardous
methanol to enhance the conductivity of PEDOT:PSS. By employing simple treatment of immersing the PEDOT:PSS film in
methanol, dropping a small amount methanol on the film or a combination of these, we were able to tremendously enhance the
conductivity from 0.3 S cm
1 to 1362 S cm
1. Methanol treated films have sheet resistance as low as 25 U ,
1 while maintaining
85% transmittance. ITO-free polymer solar cells with standalone PEDOT:PSS anodes showed equal performance to their ITO
counterpart. These results indicate that PEDOT:PSS films with high conductivity, transmittance and flexibility are highly promising
to replace ITO for low cost and flexible polymer solar cells.

9662 | Energy Environ. Sci., 2012, 5, 9662–9671 This journal is ª The Royal Society of Chemistry 2012
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active layer. Currently tin doped indium oxide (ITO) coated on both film treatment and additives in the solution show better
rigid glass is used as the standard transparent electrode. conductivity than the additives in the PEDOT:PSS aqueous
However, ITO’s price is skyrocketing due to its limited avail- solution.43,48
ability, in addition it is mechanically brittle and has poor adhe- Earlier reports showed that polar organic additives should
sion on organic and polymeric materials.7,8 This will not only have two or more polar groups to give appreciable conductivity
increase the cost of the solar cells but also affect roll-to-roll improvement.45 Xia and Ouyang used cosolvents like methanol
fabrication on flexible substrates. Additionally, ITO has some and ethanol with water to improve the conductivity by three
inherent problems such as the release of oxygen and indium into orders of magnitude by film treatment while they reported
the organic layer, poor transparency in blue region, and complete that methanol alone didn’t show a great improvement.49 Here
crystallization of ITO films, which requires high temperature we show a simple film treatment of highly conductive PH
processing.9 All these drawbacks of ITO make it a non-ideal 1000 PEDOT:PSS films with cheap and less environmentally
transparent electrode for PSCs and the search for an alternative hazardous methanol giving four orders of magnitude conduc-
transparent electrode is inevitable.10
Published on 18 September 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22595F

tivity enhancement. The PEDOT:PSS films were treated either by

This motivated researchers to investigate different materials immersing in methanol solution or dropping a small amount of
including metal nanowires,11–13 carbon nanotubes,14–18 gra- methanol on the film or a combination the two methods. The
phene19–21 and conducting polymers22–27 as replacements for ITO. high dielectric constant and highly hydrophilic methanol induce
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In particular, the conductive polymer poly(3,4-ethylene dioxy- a screening effect between PEDOT and PSS and hence the
thiophene) (PEDOT) doped with poly(styrene sulfonate) (PSS) is hydrophilic –OH groups of methanol dissolve and remove the
quite promising as a next-generation transparent electrode hydrophilic and insulator PSS from the film and the conductivity
material owing to its enormous advantages over other conduct- was significantly enhanced from 0.3 S cm
1 to 1362 S cm
1 after
ing polymers. PEDOT:PSS films have high transparency in the film treatment. ITO-free PSCs were fabricated with methanol
visible range, high mechanical flexibility, excellent thermal treated PEDOT:PSS films as standalone transparent electrodes
stability and can be fabricated through conventional solution and demonstrate almost equal performance to devices with ITO
processing. However, pristine PEDOT:PSS suffers from a very electrodes.
low conductivity of less than 1 S cm
1 when used as a standalone
electrode. The PSS which is used as the counter ion and charge
compensator and template for polymerization of PEDOT, 2. Experimental
making it easily dispersible in water, is an insulator and the main
2.1. Preparation and characterization of PEDOT:PSS films
reason for the low conductivity of the commercial
PEDOT:PSS.28,29 PEDOT:PSS aqueous solution (Clevios PH1000) was purchased
Increasingly intensive work is going on by several people to from Heraeus with a PEDOT:PSS concentration of 1.3% by
significantly enhance the conductivity of PEDOT:PSS by more weight and the weight ratio of PSS to PEDOT was 2.5. Glass
than three orders of magnitude to replace ITO. Po et. al. have substrates of area 1.5  1.5 cm2 were cleaned with a sonicator
reviewed the work on the conductivity enhancement of successively in detergent water and twice with deionized water
PEDOT:PSS including the methods of treatment and the treat- for 15 min each and then dried in an oven. PEDOT:PSS filtered
ment chemicals used.30 The methods used include vapor phase through a 0.45 mm syringe filter was spin coated at 3000 rpm for
polymerization of PEDOT,31 addition of organic compounds 60 s on glass substrates which were treated with UV/ozone for
such as ethylene glycol (EG), dimethyl sulphoxide (DMSO), 15 min prior to spin coating. The films were annealed on a hot
dimethyl sulphate, sorbitol, mannitol, ionic liquid, anionic plate in the ambient atmosphere at 130  C for 20 min and film
surfactant, etc. in to the PEDOT:PSS aqueous solution27,32–38 and treatment was performed by immersing (hereafter referred as the
treatment of PEDOT:PSS films with polar organic compounds, ‘dip’ method) the annealed films in methanol or other alcohols
salt, acid, zwitterions or cosolvents.39–43 It has been said that the for 10 min. Then the films were again dried at 140  C for 5 min.
origin and mechanism of conductivity improvement differs The other film treatment was done by dropping (hereafter
widely and is considered controversial.25,44,45 It rather is, the referred as the ‘drop’ method) 120 mL of methanol on the film at
mechanism of conductivity enhancement depends on the treat- 130  C before annealing; and annealing continued for 20 min. A
ment chemicals, their properties and the method of treatment combination of the two treatment methods was also done one
employed. Morphology changes with phase separated PEDOT after the other. Thicker PEDOT:PSS films were prepared by
and PSS leading to larger grain sizes and lower intergrain hop- multiple spin coating; and annealing and film treatment were
ing,32,46 screening effects by polar solvents,47 washing away of the conducted after each layer.
excess insulator PSS from the film surface,48 conformational Film thickness was measured using a Veeco Dektak 150 alpha
changes by reorientation of PEDOT:PSS chains leading to better step surface profiler. Conductivities were measured using the van
connection between the conducting PEDOT chains,45,49 and even der Pauw four-point probe technique with Hall effect measure-
some doping effects are among the mechanisms proposed by ment system (Ecopia, HMS 5000). Transmission and absorption
different researchers.36,43 Generally, polar solvents which are spectra of the films were measured using Jacobs V-670 UV-Vis-
secondary dopants added in the PEDOT:PSS aqueous solution NIR spectrophotometer. The values of transmittances reported
bring about morphology changes showing greater grain size and in this paper are at the wavelength of 550 nm and include the
better connected PEDOT chains; whereas film treatments lead to absorption of the glass substrate. X-Ray photoelectron spec-
both morphology change and removal of excess PSS from film troscopy (XPS) was done using a PHI 5000 VersaProbe equipped
surface. That is why mostly methods employing film treatment or with an Al Ka X-ray source (1486.6 eV). The attenuated total

This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 9662–9671 | 9663
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reflectance Fourier transform infrared (ATR-FTIR) measure- for the highly conductive PEDOT:PSS films and they claimed it
ments were conducted with a Vertex-70 (Bruker SN-101050) by may be due to the lesser amount of PSS present in the high
dropping methanol solution collected after film treatment on the conductivity PEDOT:PSS formulation. Motivated by why this is
IR cell. Vecco di Innova was used in the taping mode to take happening, we tried film treatment of highly conductive PH 1000
the atomic force microscopy (AFM) images of polymer films. PEDOT:PSS by immersing in methanol and other alcohols. We
The SEM images were obtained using FEI Noval 200 scanning got a strikingly high conductivity which is among the highest
electron microscope. reported. Fig. 1a shows the conductivities along with the error
bars of pristine PEDOT:PSS and after film treatment with
2.2. Fabrication and characterization of PSCs different alcohols by the dip method for 10 min.
The average conductivity drastically changed from 0.3 S cm
1
PSCs were fabricated using both ITO-free highly conductive for the untreated to 1015 S cm
1 after immersing it in methanol.
PEDOT:PSS films treated with methanol and ITO anodes on This conductivity is far higher than the conductivities obtained
glass. A relatively well studied and stabilized donor:acceptor
Published on 18 September 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22595F

after single treatment using well studied additives like EG and

blend of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61- DMSO reported elsewhere.44,48 The film thickness also decreased
butyric acid methyl ester (PCBM), were used as the active layer. from 60 nm to 50 nm for methanol and to 53–55 nm for ethanol,
The PSC devices were fabricated by a spin coating blend solution
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of P3HT:PCBM, prepared by dissolving 20 mg mL
1 of each

component in 1,2-dichlorobenzene at 70  C for 3 h, at 600 rpm
for 60 s in a nitrogen filled glove box on the PEDOT:PSS
modified with methanol and an ITO surface. Less conductive
PEDOT:PSS (Clevios P VP 4083) was spin coated on an ITO
surface as a buffer layer prior to the active layer deposition. The
active layer was then dried in covered Petri glass dishes, and
subsequently the films were annealed on the top of the hotplate at
130  C for 30 min. The devices were completed by thermal
deposition of 30 and 60 nm thick calcium and aluminum
respectively, at a pressure below 10
6 Torr through a shadow
mask.
The photovoltaic performance of the devices was measured
inside a glove box filled with N2 under simulated AM 1.5G
illumination (100 W cm
2) using a xenon lamp based solar
simulator (Thermal Oriel 1000 W). The light intensity was cali-
brated by a mono-silicon photodiode with KG-5 color filter
(Hamamatsu, Inc.). Devices were illuminated under a mask and
the active area of the device was controlled to be 0.1 cm2. The
external quantum efficiency (EQE) spectra were obtained under
short-circuit conditions. Devices were encapsulated before they
were taken out for EQE measurement. The light source was a
450 W Xe lamp (Oriel Instruments, Model 6123NS). The light
output from the monochromator (Oriel Instruments, Model
74100) was focused on the photovoltaic cell being tested.

3. Results and discussion

3.1. Conductivity and opto-electronics properties of treated
PEDOT:PSS films

Many reports show that adding polyols in the aqueous solution

of PEDOT:PSS or film treatment with them can significantly
enhance its conductivity. Xia and Ouyang49 showed conductivity
enhancement by film treatment with cosolvents, including water
and alcohol, and proposed the mechanism as preferential
solvation of the hydrophilic PSS by the hydrophilic water and
hydrophobic PEDOT by hydrophobic solvents. Cosolvents were
not showing appreciable conductivity enhancement when used to
treat the film as single solvents. Recently, the same authors50
showed conductivity enhancement by three orders of magnitude Fig. 1 Conductivities of PEDOT:PSS films: (a) treated with different
using methanol alone for the less conductive PEDOT:PSS which chemicals by the dip method. (b) Treated with methanol by different
is used as a buffer layer for ITO electrodes. However, they methods of treatment. [10% mix – done by mixing 10% methanol in the
reported that methanol didn’t show a conductivity difference aqueous solution of PEDOT:PSS.]

9664 | Energy Environ. Sci., 2012, 5, 9662–9671 This journal is ª The Royal Society of Chemistry 2012
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isopropyl alcohol (IPA) and i-butanol after film treatment.

Physical properties of treatment chemicals used are presented in
Table 1. As it can be clearly seen from Fig. 1a and Table 1,
conductivity decreased with decreasing dielectric constants and
polarities of the alcohols used. Owing to this, the average
conductivities were 1015, 672, 468 and 286 S cm
1 after film
treatment of PEDOT:PSS with methanol, ethanol, IPA and
i-butanol respectively by the dip method. It is a well established
fact that polar solvents with higher dielectric constants induce a
stronger screening effect between counter ions and charge
carriers, which again reduces the Coulomb interaction between
positively charged PEDOT and negatively charged PSS
dopants.47 It is also worth noting that treatment times 1, 3, 5 and
Published on 18 September 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22595F

10 min gave almost similar conductivities. Methanol treatment

not only enhanced the conductivity by four orders of magnitude,
but also with short treatment times.
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Conductivity values by different methods of treatment with

methanol are shown in Fig. 1b. Dropping 120 mL of methanol on
the PEDOT:PSS film at 130  C prior to annealing gave average
conductivity of 1110 S cm
1. We also observed that the
conductivity of the films treated by the drop method is more
reproducible than those treated by the dip method. When the Fig. 2 SEM images of PEDOT:PSS films: (a) pristine; (b) treated by the
drop treatment is done after annealing, the conductivity is less dip method; (c) and (d) treated by the drop method with methanol.
than the one done before annealing. Before annealing, the
polymer chains are free to segregate as little water is still in the
film and hence methanol can easily penetrate better and dissolve charges required for the necessary morphology change. On the
the hydrophilic PSS facilitated by the heat energy supplied. other hand, when methanol is used for film treatment, it is
Serrated white lines/structures are clearly seen on the film surface available in large quantities and will induce the necessary
by eye, which are similar to the white patches reported by Xia changes in the film before its evaporation.
and Ouyang.41,49 Interestingly, the serrated lines were fully The bulk concentration of PEDOT:PSS films increased from
washed away when the same film was treated by immersing in an order of 17 to the order of 21 after film treatment. The rela-
methanol, again enhancing the conductivity to 1362 S cm
1. tionship between conductivity, mobility and bulk concentration
Fig. 2 shows the SEM images of PEDOT:PSS films before is given by:51
treatment and after treatment by different methods. The darker
lines of the SEM images seen in Fig. 2c and d are segregated PSS s ¼ emN (1)
chains which are easily washed by immersing in methanol. When
the treatment order was immersion followed by the dropping where s is the conductivity, e is elementary charge and N is bulk
methanol on the film (dip + drop), the conductivity is only 1205 S concentration. The bulk concentration for semi metals is in the
cm
1. In the latter case, the excess PSS is already removed from order of 17 to 21 and that of metals is more than order of 22. This
the film surface during immersion, and treatment by dropping indicates that methanol treatment of PEDOT:PSS gave it more
will bring about little impact as methanol can’t fully penetrate the metallic property.
dry film. Mixing even 10% of methanol with an aqueous solution Fig. 3a show the transmittance of ITO and one and three
of PEDOT:PSS hardly improved the conductivity, which is in layers of PEDOT:PSS films on glass treated by dip method with
agreement with the previous reports. The low dielectric constant methanol. Films before and after treatment have same trans-
of methanol, which is present in small amounts in the mittance value, showing that the treatment method didn’t
PEDOT:PSS solution, is unable to bring about a screening effect impair its transmittance. Interestingly, a one layer PEDOT:PSS
compared to the high-boiling-point and high-dielectric-constant film which is about 50 nm thick has more than 90% trans-
solvents like DMSO and EG. Moreover, in the mixing method mittance, and this is a little higher than the transmittance of ITO
methanol will evaporate quickly, due to its low boiling point, especially in the blue and green regions. Fig. 3b gives the vari-
prior to giving the screening effect between PEDOT and PSS ation of sheet resistance and transmittance with film thickness.

Table 1 Physical properties of solvents used for film treatments60

Chemical Boiling pt./ C Dielectric constant Absolute viscosity Polarity (water ¼ 100)

MeOH 64 32.6 0.6 76.2

EtOH 78 22.4 1.08 65.4
IPA 82 18.3 2.0 54.6
i-Butanol 108 17.7 3.96 55.2

This journal is ª The Royal Society of Chemistry 2012 Energy Environ. Sci., 2012, 5, 9662–9671 | 9665
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where T is the transmittance, Rs is the sheet resistance, Z0 ¼ 377

U is the impedance of free space, sop and sdc are the optical and
dc conductivities respectively. T and Rs are controlled by
sdcsop
1 and the minimum industry standard is sdcsop
1 > 35.
All methanol treated films show sdcsop
1 > 58, and even higher
for large thickness films.

3.2. Mechanism of conductivity enhancement

There have been various mechanisms proposed by many
researchers for conductivity enhancement of PEDOT:PSS. We
utilized various chemical and physical characterization methods
Published on 18 September 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22595F

to investigate the mechanism of conductivity enhancement of

PEDOT:PSS by simple film treatment with methanol. The 10 nm
thickness loss after film treatment with methanol (from 60 nm to
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50 nm) gives a clue that PSS is removed from the film surface as
the hydrophobic PEDOT is insoluble in highly hydrophilic
methanol. Fig. 4 shows the UV absorption spectra of the films
before and after methanol treatment. The two absorption bands
originate from the aromatic rings of PSS.24,48 The bands fall well
after methanol treatment and indicate that there is a decrease in
the amount of PSS in the film after methanol treatment.
Further confirmation for the removal of PSS from the film was
conducted using ATR-FTIR. The methanol solution after film
treatment by the dip method was evaporated to increase the
concentration of the washed away PSS; ATR-FTIR measure-
ments were conducted by dropping this methanol solution on the
IR cell. The IR spectra of the methanol solution taken after
methanol evaporation is given in Fig. 5, and represents a char-
acteristic spectra of PSSH.53 The absorbance peaks 1165, 1125,
1035 and 1005 cm
1 correspond to the stretching vibration
of –SO3
group of the PSS. We also compared the PSSH spectra
with the commercial poly(sodium 4-styrenesulfonate) (PSSNa)
taken from the solid pellet, and they have the same spectra. This
confirms that PSS is washed away from the film with methanol
treatment and without any chemical modification too. To the
Fig. 3 (a) Transmittance of ITO and 1-layer (50 nm thick) and 3-layers best of our knowledge, this is the first quantitative confirmation
(150 nm thick) PEDOT:PSS films treated with methanol by the dip using IR for the removal of PSS from the PEDOT:PSS film after
method. (b) Variation of transmittance and sheet resistance with film
thickness for PEDOT:PSS treated with methanol by the dip + drop
method. Inset compares the transmittances of bare glass (1), 1 layer
PEDOT:PSS coated glass (2) and ITO coated glass (3).

The sheet resistance of the single layer films is 197, 164 and 147
U ,
1 after treatment by dip, drop and a combination of both,
respectively. The sheet resistance can go well below 25 U ,
1
with multiple layers while still maintaining more than 78%
(85% without the glass substrate) transmittance. Two layers of
PEDOT:PSS film treated by methanol fulfil the minimum
optical and electrical requirements for transparent electrodes,
which are transmittance higher than 90% and sheet resistance
less than 100 U ,
1, ensuring that PEDOT:PSS films are
promising replacements for ITO electrodes. For transparent
electrodes, the relationship between the transmittance and sheet
resistance is given by:52
 
2
Z0 sop
T ¼ 1þ (2) Fig. 4 UV absorption spectra of PEDOT:PSS films before and after
2Rs sdc methanol treatment by the dip method.

9666 | Energy Environ. Sci., 2012, 5, 9662–9671 This journal is ª The Royal Society of Chemistry 2012
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Published on 18 September 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22595F
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Fig. 5 ATR-FTIR spectra of the methanol solution after PEDOT:PSS

film treatment (PSSH) and commercial poly(sodium 4-styrenesulfonate) Fig. 6 S (2p) XPS spectra of untreated and methanol treated
(PSSNa). (a) 3700–2965 cm
1: stretching vibration of O–H; (b) 2925 cm
1: PEDOT:PSS films.
alkyl C–H stretching vibration; (c) 1640 cm
1: O–H bending vibrations;
(d) 1600, 1495, 1450 and 1410 cm
1: aromatic –C]C– stretching vibra-
tions; (e) 1165 and 1125 cm
1: –SO3
asymmetric stretching vibrations; (f)
PEDOT:PSS, as reported elsewhere,48 and maintained only
1035 and 1005 cm
1: –SO3
symmetric stretching vibrations; (g) 833, 776 about 60% of its conductivity.
and 670 cm
1: ]C–H out of plane deformation vibrations h. 615 cm
1: To gain further information for the mechanism of conductivity
ring in-plane deformation vibrations.53 enhancement and to investigate the possible changes in the
morphology and correlation between morphology and conduc-
tivity, AFM images were taken and are presented in Fig. 8. The
film treatment. Methanol with a reasonably high dielectric phase image shows disconnected PEDOT chains with weak phase
constant induces a screening effect between the positively separation between PEDOT and PSS for the pristine samples,
charged PEDOT chains and negatively charged PSS chains, thus whereas there is a good phase separation between PEDOT and PSS
reducing the Coulombic interaction between them, as is the case chains with more interconnected conductive PEDOT chains after
for high boiling point secondary dopants.47 This will lead to a film treatment. It also suggests that the conformation of PEDOT
phase separation on the nanometer scale characterized by will be changed from a coiled to a linear/extended-coil structure
segregation of the excess PSS. The highly polar hydrophilic owing to the removal of PSS from the film surface. The height image
methanol can also easily dissolve the phase separated hydrophilic shows that both the pristine and treated films are reasonably smooth
PSS and facilitate its removal from the film. with an rms roughness of 0.7 nm and 1.44 nm for the pristine and
The amount of PSS removed from the PEDOT:PSS film was methanol treated films, respectively. PEDOT chains were seen to be
estimated using XPS measurements of the films before and after more aggregated, and increased in size after film treatment.
film treatment with methanol (Fig. 6). The S (2p) peaks observed
at the binding energy of 167.8 eV correspond to the sulfur signal
from PSS and at the 164.2 eV and 163.4 eV correspond to the
sulfur signal from PEDOT both before and after treatment.54
The ratios of PSS to PEDOT were calculated using the integral
area ratio of the peaks assigned to PEDOT and PSS. The ratio of
PSS to PEDOT decreased from 1 : 2.71 before film treatment to
1 : 1.76 after film treatment leading to 35% reduction of PSS
from the film surface. The PSS to PEDOT ratio of 1 : 2.71 for the
pristine film agrees well with the already accepted idea that the
film surface contains more PSS than the bulk.44 The removal of
the insulator hygroscopic PSS from film surface will not only
increase the conductivity of the film but also improve its long
term stability, as PSS is the prime reason for the degradation
of organic solar cells.48 The conductivity stability of the
PEDOT:PSS films was assessed by keeping them in ambient
atmosphere at room temperature and humidity higher than 75%.
As expected, methanol treated films can maintain up to 80% of
the original conductivity while the pristine film maintains only Fig. 7 Conductivity stabilities of PEDOT:PSS films in the ambient atmo-
35% after sixteen days [Fig. 7]. For comparison, another sample sphere treated by different methods with methanol and EG [EG – mixing 6%
was made by mixing 6% EG in the aqueous solution of EG in aqueous solution of PEDOT:PSS].

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Scheme 1 Schematic illustration of the mechanism of conductivity

enhancement of PEDOT:PSS films by film treatment with methanol. The
core–shell structure is changed to a linear/coiled structure. The removal
Published on 18 September 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22595F

of PSS leads to the thickness reduction of the film and also brings about
bigger and better connected PEDOT chains.
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hopping will be lowered and there will be better charge transfer

among the PEDOT chains. The phase separated and re-oriented
PEDOT chains will make the charge hopping easier and even-
tually there will be a tremendously enhanced conductivity.

3.3. ITO-free PSCs using PEDOT:PSS treated with methanol

Fig. 8 AFM images of PEDOT:PSS films before (a and c) and after anodes
film treatment with methanol by the dip method (b and d). (a and b)
are phase images while (c and d) are topography images. All the images PSCs were fabricated using PEDOT:PSS treated with methanol
are 1 mm  1 mm. by different methods as a standalone anode. The chemical
structures of the active layer chemicals (P3HT and PC61BM),
device architecture, the current density (J)–voltage (V) curves
Film conductivity has a direct relation to the PEDOT particle and EQE of the PSCs with single layer (50 nm) PEDOT:PSS
size; as particles grow the total number of particle boundaries in anodes are shown in Fig. 9. PSCs using ITO anodes with a less-
a given volume or area can decrease. An increased particle size conductive PEDOT:PSS (Clevios P VP Al 4083) buffer layer
with decreased particle boundaries leading to few energy barriers were also fabricated as control devices. The power conversion
will bring about conductivity enhancement.46 Moreover, charge efficiency (PCE), short-circuit current density (Jsc), open-circuit
hopping among the polymer chains is believed to be the domi- voltage (Voc), fill factor (FF) and series resistance (RS) and
nant conduction mechanism in conducting polymers.55 The way parallel resistance (RSH) of the PSCs are given in Table 2.
charges are transported among the highly conducting PEDOT- Generally, PEDOT:PSS anodes show an almost equal perfor-
rich grains will decide the overall conductivity of PEDOT:PSS mance to the ITO anode owing to their high conductivity. The
films. Hence, the PEDOT-rich chains with a linear structure, EQE values are in agreement with the J–V values of the devices.
larger grain size and lower intergrain hopping, resulting in PEDOT:PSS anode treated with methanol by the drop method
thinner PSS barriers, can promote charge hopping leading to a showed a Jsc 9.51 mA cm
1, Voc 0.58 V and PCE 3.71% with an
higher conductivity. FF of 67.33%. The PSC with the reference ITO electrode has a
Combining all the above-explained results, we proposed a PCE of 3.77% with little higher FF and lower Jsc. Owing to their
model as in Scheme 1 to fully explain the mechanism of better transmittance, PSCs with the PEDOT:PSS electrodes have
conductivity enhancement by methanol treatment. The current better Jsc than their ITO counterparts. Interestingly, all
suggested model for the morphology of PEDOT:PSS solid films PEDOT:PSS electrodes showed the same Voc value to their ITO
is that it consists of grains with a hydrophobic and highly counterpart, and their FF is higher than 66%. The PEDOT:PSS
conductive PEDOT-rich core and a hydrophilic insulating PSS- electrode treated only by the drop method shows a higher PCE,
rich shell.56 The highly hydrophilic methanol, with a high contributed by its higher Jsc, even though its conductivity is
dielectric constant, will interact with the hydrophilic PSS and lower than the drop + dip method. For the film treated with only
bring about a screening effect between the PEDOT and PSS the drop method, a very thin PSS layer segregated by methanol is
chains. The screening effect and phase separation is dependent still on the film surface and it will act as a functional buffer layer,
on both the dielectric constant and hydrophilicity of the treat- giving an electron blocking function to the device, which results
ment chemicals; that is why ethanol and IPA show lower in higher Jsc value. Additionally, the rough surface after drop
conductivity than methanol. The screening effect will facilitate treatment may serve as a center for the initial crystallization of
the phase separation between the PEDOT and PSS chains and the P3HT polymer which further leads to better alignment of the
hence the PSS will be dissolved by methanol. This intern will P3HT and PCBM domains.57 It is also worth to note that
enable the reorientation of the PEDOT polymer chains from a PEDOT:PSS electrodes showed low RS and high RSH values
coiled to linear or extended-coil structure which allows more comparable to the ITO electrode. Additionally, the preliminary
inter-chain interaction between the conducting polymers. Thus, stability of the devices was considered by keeping the devices in
the energy barrier for inter-chain and inter domain charge an N2 filled glove box. Devices with PEDOT:PSS electrode

9668 | Energy Environ. Sci., 2012, 5, 9662–9671 This journal is ª The Royal Society of Chemistry 2012
 View Article Online

maintained up to 96% of the original efficiency after ten days

while devices with an ITO electrode maintained only 87%. The
highly acidic PSS buffer layer, which corrodes ITO, is the main
reason for the fast degradation of the ITO device.58
The PCE of PSCs with 1 layer PEDOT:PSS decreased across
the lateral distance (shown in the device architecture in Fig. 9b)
due to the decrease in FF; which, in turn, is caused by the high
sheet resistance of the thin layer of PEDOT:PSS electrodes. For
example, the PCE and FF of PEDOT:PSS electrodes treated by
the dip method fell from 3.57% and 66% for the first finger to
3.11% and 51% for the fourth finger, respectively, while the ITO
performance remained almost the same. The power loss due to
Published on 18 September 2012 on http://pubs.rsc.org | doi:10.1039/C2EE22595F

the high sheet resistance of the electrode is dependent on the area

of the cell and is given by:59

ð jlwÞ2 RS w
Ploss ¼ (3)
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3l
where Ploss is the power loss, j is the Jsc, RS is the sheet resistance
of electrode, l and w are the length and width of the area,
respectively, where current is collected at one of the edges with
length l. The power losses of the methanol treated PEDOT:PSS
electrodes across the lateral distance are in agreement with the
above formula.
To circumvent the power loss with lateral distance we used
PEDOT:PSS electrodes with multiple layers treated by the dip
method. Fig. 10 shows the J–V curves of the devices and Table 3
presents the device performance values extracted from the
curves. The lower Jsc value is due to the reduction in the trans-
mittance of the electrodes with increasing thickness. The

Fig. 9 (a) Chemical structures of the active layer chemicals. (b) Device
architecture of the ITO-free PSC. (c) J–V curves of the PSCs with single
layer PEDOT:PSS treated with methanol by different treatment methods
and ITO anode electrodes. (d) EQE of the PSC devices with ITO and
PEDOT:PSS anodes. Fig. 10 J–V curves of different layers of PEDOT:PSS films treated by
the dip method and ITO electrodes.

Table 2 Photovoltaic performances of PSCs with ITO and 1 layer PEDOT:PSS treated with methanol by different methods anodes extracted from the
J–V curves

Anode Jsc/mA cm
2 Voc/V FF (%) PCE (%) RS/U cm2 RSH/U cm2

ITO 9.18 0.58 70.24 3.74 1.75 625

PEDOT:PSS – Dip 9.32 0.58 66.04 3.57 5.11 637
PEDOT:PSS – Drop 9.51 0.58 67.33 3.71 3.51 701
PEDOT:PSS – Drop + Dip 9.41 0.58 66.33 3.62 4.04 1042

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 View Article Online

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