ARTICLE IN PRESS

Solar Energy Materials & Solar Cells 94 (2010) 531–536

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Solar Energy Materials & Solar Cells

journal homepage: www.elsevier.com/locate/solmat

Influence of crystallizable solvent on the morphology and performance of

P3HT:PCBM bulk-heterojunction solar cells
Anusit Keawprajak, Phimwipha Piyakulawat, Annop Klamchuen, Phansak Iamraksa,
Udom Asawapirom n
National Nanotechnology Center, National Science and Technology Development Agency, 130 Thailand Science Park, Phahonyothin Rd., Klong 1 Klong Luang,
Pathumthani 12120, Thailand

a r t i c l e in fo abstract

Article history: In this work, we present the effect of 1,3,5-trichlorobenzene (TCB) on the morphology and performance
Received 18 July 2009 of a 1:1(w/w) rr-P3HT:PCBM polymer/fullerene bulk-heterojunction solar cell. The UV–vis spectra of
Received in revised form the rr-P3HT:PCBM polymer/fullerene formed from a blend with various TCB concentrations (0–28 mg/
17 November 2009
ml) indicate an enhanced absorption within the 500–600 nm wavelength range when formed in the
Accepted 20 November 2009
Available online 16 December 2009
presence of the TCB. By increasing the concentration of TCB in the blend, the resultant spun-cast film
morphology was improved due to grain size reduction, and the polymer film quality can be further
Keywords: improved via an annealing process. Moreover, the device efficiency is also improved due to a good
Crystallizable solvent quality thin film nanostructure. With the optimized TCB quantity and annealing temperature, the
Bulk-heterojunction solar cells
power conversion efficiency (PCE) achieved with the solar cell was up to 20% better than that attained
Morphology
by a similar device without the presence of TCB.
Polythiophene
& 2009 Elsevier B.V. All rights reserved.

1. Introduction polymer solar cells are that of regioregular poly(3-hexylthio-

Organic based composite photovoltaic cells have attracted
increasing attention as a renewable energy resource. Although
inorganic semiconductors are the archetype for the fabrication of
high efficiency solar cells, the cost of the manufacturing processes
of conventional inorganic photovoltaics limits their application in
many areas. The ability to process many organic conjugated
materials in isolation may allow such devices to be made with a
low fabrication cost and ease of manufacture, and as a light
weight product with a large area that is compatible with flexible
substrates [1–3]. The low cost processes also include various
common printing technologies such as ink-jet or doctor blade
screen-printing. Therefore, a new range of electronic devices can
be attached to unexpected elements, such as on paper sheets or
garment products, due to benefit of plastic substrates and
innovative conductive inks [4–6]. Unfortunately, two major
disadvantages of organic solar cells are the low overall power
conversion efficiency (PCE), particularly true for large area devices
and their stability or lifetime compared with conventional
inorganic solar cells, such as silicon solar cells. However, the
PCE and lifespan of organic photovoltaic cells (OPVs) have been
dramatically improved in the past decade [7–9]. One of the most
extensively investigated and promising material combination in
n
Corresponding author. Tel.: + 66 25647100; fax: + 66 25646981.
E-mail address: udom@nanotec.or.th (U. Asawapirom).
phene) (rr-P3HT) with a fullerene derivative ([6,6]-phenyl-C61
butyric acid methyl ester, PCBM) as the donor and acceptor
materials, respectively, in a bulk-heterojunction [10,11]. The
bulk-heterojunction PVCs made from a blend of rr-P3HT and
PCBM have recently been shown to accomplish a PCE up to 3–5%
and more than 6% for tandem cells [2,12–14]. In order to achieve
the high photovoltaic performance, the band gap energy, HOMO/
LUMO levels and carrier mobilities of the heterojunction materials
need to be optimized simultaneously. The types of solvent or
annealing process in the production of the active materials can
also enhance the performance. Therefore, the different device
geometries and interface morphologies need to be evaluated for
the purpose of trapping more light, dissociating excitons more
efficiently, increasing the exciton diffusion length and transport-
ing charges with fewer barriers.
To obtain higher photocurrents, the typical length scale of
phase separation between the donor and the acceptor phases
should be in the order of the exciton diffusion length, which is
around 10 nm for organic semiconductors [15]. The self-align-
ment ability of rr-P3HT facilitates the formation of thin films with
well-ordered lamellae of co-facially stacked planarized main
chains. This assembly ensures a fast charge transport in the layer
of the ordered backbones, result in the achievement of a high
charge carrier mobility. To obtain this condition, apart from
the annealing process, various solvent selections have been used,
such as chlorobenzene, 1,2-dichlorobenzene, 1,2,4 trichloroben-
zene, chloroform and toluene. Among the choice of solvents,

0927-0248/$ - see front matter & 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.solmat.2009.11.018
 ARTICLE IN PRESS
532 A. Keawprajak et al. / Solar Energy Materials & Solar Cells 94 (2010) 531–536
Fig. 1. Schematic of the device structure of a polymer bulk-heterojunction
photovoltaic cell, and the chemical structures of the two main components.
chlorobenzene and its derivatives can produce a good device
performance when compared with toluene [16–18]. Hereby, most
additives in the liquid form with a high boiling point as co-solvent
are applied during the dissolving process to optimize the thin film
morphology, such as a solvent mixing between chlorobenzene
and chloroform or chlorobenzene and alkanedithiols, that can
lead to a small grain boundary and resulting in a high
photocurrent [16,19]. Brinkmann et al. proposed a new method
to obtain thin films of oriented and nanostructured materials,
which are of potential interest for the synthesis of active layers of
solar cells, using the directional epitaxial solidification of rr-P3HT
in crystalline solvent to yield highly oriented and crystalline P3HT
thin films [20,21].
Here, we report our results for heterojunction organic solar
cells based on a 1:1(w/w) blend of the regioregular polymer, rr-
P3HT, to the fullerene, PCBM, where the active layers are
deposited by spin-coating of solutions using chlorobenzene, with
different concentrations of 1,3,5-trichlorobenzene (TCB; 0–28 mg/
ml), as crystallizable aromatic solvents. We correlate these results
with atomic force microscopy (AFM) images of the morphologies
of the formed heterojunction materials. Fig. 1 schematically
shows the typical structure of a polymer photovoltaic
cell fabricated in this study, and the chemical structures of
the used materials. Details of the device fabrication process and
the characterization techniques are given in the experimental
part.
2. Experimental details
2.1. Materials
All reactions were carried out under an argon atmosphere.
Regioregular poly(3-hexylthiophene) was prepared by the
Grignard metathesis procedure according to McCullough [22],
which involves the polymerization of the Grignard reagent 2-
bromo-5-bromomanesio-3-hexylthiophene. The average molecu-
lar weight (Mw) of P3HT was determined by GPC analysis against
polystyrene standards and found to be 44,700 g/mol with a
polydispersity index (PDI) of 1.53. PCBM was synthesized from
the reaction of fullerene and methyl-4-benzoylbutyrate-p-tosyl-
hydrazone, in close analogy to the method already described in
the literature [23].
2.2. P3HT/PCBM ratio and concentration
The blend solution of bulk-heterojunction solar cells had a
P3HT/PCBM ratio of 1.0:1.0 (wt/wt%); with a concentration of
10 mg/ml P3HT plus 10 mg/ml PCBM and TCB (Aldrich) at 0, 6, 12,
20 and 28 mg/ml in chlorobenzene.
2.3. Calibration and measurement
The optical absorption spectrum was investigated by means of
UV–vis spectroscopy (Perkin Elmer, Lamda 650). The surface
morphological features of the films were examined using a Seiko
Instruments SPA-400 atomic force microscope (AFM) system
simultaneously. The current density–voltage (J–V) characteristics
of the bulk-heterojunction solar cells were measured under
illumination at 100 mW/cm2 using an AM 1.5 solar simulator
under ambient conditions. The solar cells were illuminated
through the side of the ITO-coated glass plate.
2.4. Device fabrication
Polymer solar cells were prepared according to the following
procedure: The ITO-coated glass substrate (with a sheet resistivity
of 15 O/sq, Semiconductor wafer, Inc) was first sequentially
cleaned with detergent, methanol, acetone and isopropyl alcohol
for 15 min, in an ultrasonic bath and subsequently dried with N2.
Conductive grade PEDOT:PSS (Aldrich; conductive grade) was
spun-cast (2000 rpm) from an aqueous solution (after passing
through a 0.45 mm filter). The substrate was dried for 60 min at
80 1C under reduced pressure and then spun-cast as the bulk-
heterojunction layer. All P3HT and PCBM blend solutions were
stirred for 24 h before spin-coating to ensure that the PCBM has
completely dissolved in the P3HT. The chlorobenzene and TCB
solution, used as a crystallizable solvent, was composed of 1% (w/
w) P3HT and 1% (w/w) PCBM and was then spin-cast at 1500 rpm
on top of the PEDOT:PSS layer. The active layer was annealed at
63, 110, 150 and 180 1C (TCB melting point=63 1C) for 30 min
under a nitrogen atmosphere. Subsequently, TCB was removed by
evaporation under reduced pressure. Finally, the samples were
transferred into the vacuum chamber to deposit Al ( 200 nm
thick) on top of the spin-coated polymer film. The deposited Al
electrode area defined the active area of the devices as 0.18 cm2.
3. Results and discussion
The bulk-heterojunction approach (formed by blending donor
type conjugated polymers with the acceptors like fullerenes) is
attractive and offers significant progress in improving the PCE of
these devices. One of the possible improvements in this type of
solar cell is the implementation of a material that can absorb the
red and near infrared part of the solar spectrum, where the
maximal photon flux of the sun is located. Consequentially, this
has been one of the fundamental strategies and main focus in
improving the performance of organic solar cells. One of the
advantages of polymer photovoltaic devices is the solution
process ability of the active materials. However, the solvents
used for the preparation of the active layer have a strong impact
on its morphology, which in turn influences the performance of
the solar cells [24]. The atomic force microscopy (AFM) topo-
graphy images indicate the smoothened film surface of the
P3HT:PCBM polymer/fullerene as the TCB concentration in the
blend is increased, as shown in Fig. 2 for data obtained with an
annealing temperature of 150 1C. The grain sizes are continuously
reduced as the TCB concentration is increased up to 12 mg/ml,
and thereafter the roughness increases as the TCB concentration is
increased further. Therefore, only the roughness development can
be observed as the TCB concentration is varied. This tendency can
also be observed with all the other tested annealing temperature
regimes, as summarized in Table 1.
From the data summarized in Table 1, the rms roughness is
abruptly reduced as the TCB is added, particularly at the 63 1C (TCB
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A. Keawprajak et al. / Solar Energy Materials & Solar Cells 94 (2010) 531–536 533

Fig. 2. Representative AFM topography images of the 1:1 (w/w) P3HT:PCBM active laver after annealing at 150 1C for 30 min with TCB concentrations of 0, 12, 20 and
28 mg/ml for panels a, b, c and d respectively. Note that the study area is 25 mm2.

Table 1
Summary of the root-mean-square (rms) roughness for different annealing temperatures and various TCB concentrations. Note that the bold type represents the optimized
amount of TCB for roughness minimization.

Concentration of TCB (mg/ml) Root-mean-square (rms) roughness for annealing temperature (nm)

63 1C 110 1C 150 1C 180 1C

0 6.45 8.70 1.43 1.45

6 6.12 7.92 1.46 1.40
12 2.31 1.47 1.28 1.10
20 3.80 4.75 3.91 4.10
28 6.35 5.94 8.04 3.33

melting point) and 110 1C regimes, whilst the same TCB crystalline
solvent gradually smoothens the roughness at the high tempera-
ture range. However, the rebuilt roughness increases dramatically
as the TCB concentration in the blend is increased above 12 mg/ml,
and some of the measured roughness is even greater than that of
the non-TCB association sample at a TCB concentration of 28 mg/
ml. This may indicate the enhanced polymer nucleation in the film.
The UV–vis spectroscopy of P3HT:PCBM samples spun-cast with
various TCB concentrations on quartz substrates are shown in
Fig. 3, and reveal a considerable change in the absorption spectra
with different TCB concentrations (0–28 mg/ml) and annealing
temperatures (63–80 1C). The films were annealed in a Glass oven
(Büchi) under argon at atmospheric pressure.
The reduction in the roughness of the polymer/fullerene thin
film that was achieved by adding TCB to the blend solution can be
ascribed to its role as two folds: firstly, it behaves like a normal
solvent since annealing at above its melting point (Tm) is carried
out. Secondly, it becomes the nucleating and orienting substrate
for polymer as the temperature falls to lower than its Tm [25].
Therefore, the morphology between P3HT and PCBM is an orderly
intermixing with nucleating on the TCB during the annealing
process, and also an enhancement of the P3HT self-organization.
However, this experiment did not use a temperature gradient, as
reported elsewhere [25], so the authors believe instead that the
TCB improves the polymer/fullerene dissolving, mixing and
nucleating before and during the annealing. The film roughness
increases again as the TCB concentration in the blend is increased
over 12 mg/ml, under these conditions, due to the accelerated
solidification rate during the spin-coating process, which results
in a higher level of polymer self-organization [26]. Since the
thickness of all investigated samples remained within the
approximate range of 60–70 nm, as determined by the AFM
profile analysis, increasing the TCB concentration had no
significant effect on the thickness of the active layer. The film
obtained from addition of the TCB solvent association had a
higher annealing sensitivity than the film spun from a normal
solvent. Indeed, this process could lead to better spin-cast film
reproducibility, since the normal solvent process suffers from
poor mixing and ends up with the fullerene surrounding the
polymer causing a low efficiency due to the high recombination
rate [17]. In Fig. 3a, the absorption spectra of the 1:1 (w/w)
P3HT:PCBM polymer/fullerene blend with increasing concentra-
tions of TCB shows a red shift of up to 8 nm from the original
spectra as the concentration of TCB is increased.
The clear peaks at 558 and 606 nm appear with the highest tested
TCB concentration (28 mg/ml). The red shift monotonically moves
towards the longer wavelength with increasing concentrations of TCB,
and the absorption edge also indicates a small movement to long
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534 A. Keawprajak et al. / Solar Energy Materials & Solar Cells 94 (2010) 531–536

HOMO–LUMO transition [10]. The increasing absorption peak at

606 nm observed with the inclusion of TCB implies an improved
molecular order of the polymer in these films since the long
wavelength absorption depends on the intermolecular order of
microcrystalline domains. Furthermore, the highest absorption,
occurring in the 28 mg/ml TCB associated film (Fig. 3), is carried
out by internal reflection due to the height roughness [10] as seen
in Fig. 2d. Additionally, the decrease in the PCBM absorption peak
upon annealing can be explained by the clustering of PCBM, as
suggested by Bertho et al. [15]. For the devices investigated, the
performance was evaluated as the J–V characteristic (Fig. 4),
where the inclusion of TCB at 12 mg/ml, only, can optimize the
device short circuit current (Jsc), whilst the open circuit voltage
(Voc) is less than that obtained at other TCB concentrations. The
highest Jsc was observed by annealing at 150 1C with 12 mg/ml of
TCB, whilst the Voc is given at higher than other temperature
regimes (Fig. 4b).
The characteristics of the investigated devices are summarized
in Fig. 5, and indicate that the inclusion of TCB in the polymer/
fullerene blend can optimize the performance of the resultant
device when the TCB was included at 12 mg/ml and annealed at a
temperature of more than 63 1C. A short circuit current of up to
7.53 mA/cm2, after annealing at 150 1C, was observed, which

Fig. 3. Representative UV–vis spectra of (a) the 1:1 (w/w) P3HT:PCBM blend with
the indicated TCB concentrations (mg/ml) and annealed at 63 1C for 30 min and (b)
the spectra of 12 mg/ml TCB in a 1:1 (w/w) P3HT:PCBM blend annealed at the
indicated temperatures.

wavelengths, which indicates an energy gap lowering in the polymer.

However, a slight absorption drop occurs at around the 500 nm
region in samples with TCB at 20 and 28 mg/ml compared with the
other samples suggesting that the correct amount of TCB can
effectively improve the solar spectrum matching of active layer. The
absorption is also enhanced as the annealing temperature is
increased, as shown in Fig. 3b. However, the distinctive development
can be found in the samples annealed at up to 180 1C, whilst small
improvements in absorbance within the range of 450–580 nm were
found in the samples that were annealed at a lower temperature.
Additionally, the PCBM absorption peak at around 335 nm is also
reduced as the annealing temperature is increased, which would
indicate that the polymer structure dominates over the fullerene as
the temperature increases, which is likely to be due to thermal
diffusion and aggregation into smaller clusters of PCBM molecules, as
already described elsewhere [12,14,26].
The absorption shift towards longer wavelengths as the TCB
concentration is increased is attributed to increasing the inter-
chain interactions amongst the P3HT chains due to a stronger self-
organization [27,28]. Since interchain interactions are enhanced, Fig. 4. J–V characteristics of a 1:1 (w/w) P3HT:PCBM bulk-heterojunction solar
cells annealed (a) at 110 1C with various TCB concentrations (mg/ml) and (b) with
the delocalized p electrons are increased in the entire polymer TCB at 12 mg/ml and annealed at various temperatures. The J–V characteristics of
lowering the band gap between p and pn (the HOMO of the all devices are investigated under AM 1.5 illumination with a calibrated solar
acceptor and the LUMO of the donor) and increasing the optical simulator with an intensity of 100 mW/cm2.
 ARTICLE IN PRESS
A. Keawprajak et al. / Solar Energy Materials & Solar Cells 94 (2010) 531–536 535

0.55

Voc [V]
0.50
0.45
7

Jsc [mA/cm2]
6
5
4
3
0.5
0.4
0.3
FF

0.2
0.1
2
PCE [%]

0
0 5 10 15 20 25 30
TCB concentration [mg/ml]

Fig. 5. Affects of TCB concentration (mg/ml) on the open circuit voltage (Voc), short circuit current (Jsc), field factor (FF) and power conversion efficiency (PCE) at various
annealing temperatures: ’ 63 1C, K 110 1C, m150 1C and . 180 1C.

likely reflects that a smoother surfaced film morphology was
obtained leading to a better contact with the metal electrode [14].
The open circuit voltage of these devices varied around 0.45–
0.55 V, depending on the TCB content and the annealing
temperature used. The lowest Voc was found at 0.43 V in a
device that had 12 mg/ml TCB incorporation and was annealed at
180 1C, an observation which emphasizes the LUMO–HOMO gap
reduction in the polymer by TCB incorporation, since the Voc is
mainly governed by the polymer energy gap [29].
Additionally, this also agrees with the observed high absorp-
tion (Fig. 3b). The device field factor (FF) shows obvious
separation between devices annealed at 63 1C and with more
than 12 mg/ml TCB in the blend, where the highest FF is obtained
in the devices annealed at 110 and 180 1C. However, the PCE plot,
which expresses the total effect from these three parameters,
indicates the highest efficiency of up to 1.67% in the device
derived from the incorporation of 12 mg/ml TCB and annealed at
150 1C. This annealing temperature is the only regime that gives
the highest Jsc and, therefore, any method that can increase Jsc is
likely to be a critical factor for efficiency enhancement, as has
been suggested elsewhere [30].
To enhance Jsc, apart from improvement of the organic/metal
contact as discussed previously, the active layer spectral response
must be matched to the solar spectrum as far as possible [31],
which is also consistent with the observed red shift shown in
Fig. 3. By comparing the rms roughness results with the device
performances, the rough surface may effectively reduce the
charge-transport barrier and increase the Jsc, whilst a nano-scaled
texture further enhances the internal light scattering and then
improves light absorption of the active layer [10].
4. Conclusions
We investigated the influence of a crystallizable solvent on the
morphology and performance of bulk-heterojunction solar cells
based on a 1:1 (w/w) P3HT:PCBM regioregular polymer/fullerene
blend, using chlorobenzene with different concentrations of TCB
(0–28 mg/ml) as crystallizable aromatic solvents. The best
performance, with a short-circuit current density Jsc = 7.53 mA/
cm2, a fill factor FF= 0.42, an open-circuit voltage Voc = 0.53 V and a
resulting power conversion efficiency PCE of 1.67%, could be
reached for a cell annealed at 150 1C with a TCB concentration of
12 mg/ml. This yielded a 20% improvement over devices obtained
under the same conditions but without the inclusion of TCB. The
decelerated release of the residual solvent during the solidifica-
tion of the blend film improves the self-organization, and the
surface of film becomes smoother with the addition of TCB at
12 mg/ml, which in turn improves the organic/cathode contact.
The polymer blend film formed with a TCB crystallizable solvent
exhibited a better crystallinity, optical absorption and polymer
morphology than the polymer blend film formed without the TCB
crystallizable solvent. The power conversion efficiency of such
fabricated solar cells was higher than that of cells formed without
TCB solvent.
Acknowledgements
This work was supported by the National Science and
Technology Development Agency in Thailand. The authors would
like to thank Dr. Robert Butcher for fruitful discussions.
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