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Journal of
Nanoelectronics and Optoelectronics
Vol. 6, 288292, 2011

Optical and Transport Properties of

Poly(3-Hexylthiophene)-Single-WalledCarbon-Nanotube Composites
Hee Jin Kim1 , Mohammad Rezaul Karim2 , and Chul Jae Lee3

RESEARCH ARTICLE

Department of Chemical Engineering, Pohang University of Science and Technology (POSTECH) San 31,
Hyoja-Dong, Nam Gu, Pohang, Gyungbuk 790-784, Republic of Korea
2
Center of Excellence for Research in Engineering Materials, College of Engineering,
King Saud University, Riyadh 11421, Saudi Arabia
3
School of Chemical Industry, Yeungnam College of Science and Technology,
170 Hyeonchung-ro, Nam-gu, Daegu 705-703, Republic of Korea

Conducting polymers are attractive materials for solar-cell applications as they can be easily processed from a solution via spin-coating even over a large area and on exible substrates, for
lightweight devices. Their extremely high surface area, low percolation threshold, composite reinforcement, and thermal management make single-walled carbon nanotubes (SWNTs) much more
attractive in relation to polymeric photovoltaic development. In this paper, soluble and undoped
poly(3-hexylthiophene) (P3HT) and P3HT-SWNT composites were synthesized via in-situ polymerization with FeCl3 . Ultraviolet-visible
and photoluminescence
measurements were made to underDelivered
by Ingenta to:
stand their electronic properties in the ground
and
excited
states. The work function and IV
chul-jae lee
measurements indicate the important and useful transport property of P3HT-SWNT composites for
IP : 58.237.121.62
solar-cell applications.

Thu, 15 Sep 2011 13:08:29

Keywords: Carbon Nanotubes, Nanocomposites, Conjugated Polymers, Conducting Polymers.

1. INTRODUCTION
Since the discovery of highly efcient photo-induced electron transfer in an interpenetrating network of two different organic semiconducting materials over a decade
ago,1
2 organic photovoltaic (OPV) devices based on a
bulk heterojunction (BHJ) architecture have been extensively investigated.3 To date, the best performance has
been achieved using a blend of an electron-donating
conjugated polymer and an electron-accepting fullerene,
although the focus has been placed of late on the optimization of the optical and electronic properties of both
components.46 Several unique properties of single-walled
carbon nanotubes (SWNTs) have motivated their investigation as potential replacements for fullerene derivatives as
the acceptor phase.7 The excellent charge transport properties arising from the high aspect ratios and the extremely
high conductivity at the level of both the single tubes8
and networks9 suggest that SWNTs should yield a more
efcient percolation network and potentially higher mobility than fullerenes.

Author to whom correspondence should be addressed.

288

J. Nanoelectron. Optoelectron. 2011, Vol. 6, No. 3

Conducting polymers are attractive materials for solarcell applications as they can be easily processed from
a solution via spin-coating even over a large area and
on exible substrates, for lightweight devices.10
11 In this
direction, poly(3-hexylthiophene) (P3HT) is considered
the best candidate as it possesses all the necessary requisites. The donoracceptor blend made from the polymer and carbon nanotubes (CNTs) provides a wide contact
area and is considered an appropriate material structure
for organic solar cells.12 Quite often, however, the inhomogeneities in the blend prepared via simple sonication,
and the incompatibility of the donoracceptor interface,
remain challenging problems. Perhaps the in-situ polymerization of the donoracceptor molecules could be a solution. In this direction, a paper on the in-situ synthesis of
the multiwalled carbon nanotube (MWNT)/P3HT composite is reported.13 Its extremely high surface area, low percolation threshold, composite reinforcement, and thermal
management make SWNT much more attractive in relation
to polymeric photovoltaic development.14
Therefore, the principle aim of the current work is to
exhibit the preparation of P3HT-SWNT composites. The
1555-130X/2011/6/288/005

doi:10.1166/jno.2011.1170

Kim et al.

Optical and Transport Properties of Poly(3-Hexylthiophene)-Single-Walled-Carbon-Nanotube Composites

morphology of the resulting composites was characterized,

and the physical properties were discussed in detail.

2. EXPERIMENTAL DETAILS

The SWNTs (AP grade; diameter: 11.2 nm; length:

220 m) that were used in this work were purchased
from Iljin Nanotech Co., Ltd. in South Korea and were
used as procured. The 3-hexylthiophene (3HT) monomer
(97%), chloroform, iron (III) chloride anhydrous (oxidant), and other organic solvents were purchased from
Aldrich in the reagent grade and were used without further
purication.
A gel permeation chromatograph from Waters, Alliance
GPCV 2000 with a Waters 2414 refractive-index detector, and a column of Ultrastyragel linear P/N 10681 from
Waters were used to measure the molecular-weight distribution relative to the polystyrene standards. The calibration curve was determined based on the 10 MW standards
from MW 2000 to 106 . The carrier solvent that was used
was tetrahydrofuran at a ow rate of 1 ml/min.
The Raman spectra of the solid samples were taken
at the excitation wavelength of 780 nm using a Thermo
Almega XR model. The Fourier transform infrared (FTIR)
spectra of the samples were performed from a KBr pellet of the nanocomposites in a Thermo 5700 model
Delivered
instrument. The ultraviolet-visible (UV-Vis) spectra
of the by
chul-jae lee
P3HT and SWNT-P3HT composites were recorded using
: 58.237.121.62
a UV-Vis spectrophotometer (Shimatzu Model IP
UV-160)
3. 13:08:29
RESULTS AND DISCUSSION
15 Sep 2011
in a 1,2,4-trichlorobenzene solvent, at roomThu,
temperature,
from 200 to 800 nm. The polymer and nanocomposite
The molecular weights determined through GPC were
solution photoluminescence experiments were performed
39717 (Mw ) and 12778 (Mn ) for the polymer with 3.11
using a Hitachi instrument (FL-4500 uorescence specas a measure of polydispersity. The molecular weight of
trometer). The photoexcitation was made at 450 nm excitathe polymer was noted to be a medium that will be usetion wavelengths. For the eld emission scanning electron
ful for photovoltaic applications, with easy processibility.
microscopy (FESEM) study, a dried lm of the polymer
It is reported that there is some slight variation in molecand composites was platinum-coated and was observed
ular weight with the extent of CNT loading in the case of
through a eld emission scanning electron microscope
the composites.13 This is understandable as the polymer(FESEM, Hitachi S-4200) at 20 kV. The DC conductivization process is to be of the heterogeneous nucleation
ity of the P3HT and P3HT-SWNT nanocomposite pellets
type, involving the surfaces of the nanotubes.15

(a)
Fig. 1.

(b)

(a) FESEM image of P3HT and (b) TEM image of the 20-wt.% P3HT/SWNT composite.

J. Nanoelectron. Optoelectron. 6, 288292, 2011

289

RESEARCH ARTICLE

were measured at room temperature using a Keithley/Luft

semiconductor device analysis system, via IV measurement. The work function of the P3HT and P3HT-SWNT
nanocomposite pellets were measured using photoelectron
spectrometer AC-2, a device used in a low-energy electron
countermethod.
A typical in-situ chemical oxidative polymerization for
3HT and SWNT-3HT was carried out. A 250-ml doubleneck, round-bottomed ask carrying a magnetic Teoncoated stirrer was charged with a 100 ml CHCl3 solution
containing a SWNT (in varying amounts, to obtain 1, 5,
10, and 20 wt.% with respect to the monomer weight).
The mixture was sonicated for 1 h at room temperature to
disperse the SWNT. 2 g FeCl3 in a 100 ml CHCl3 solution
was added to the above solution, after which the solution was further sonicated for 30 min. 3-hexylthiophene
monomer (0.5 ml) in a 25 ml CHCl3 solution was placed
in a condenser and was added dropwise to the SWNT and
FeCl3 solution, with constant stirring. The reaction mixture
was stirred for an additional 24 h under the same conditions. The resultant SWNT-P3HT composite was precipitated in methanol, was ltered using a Buchner funnel, and
was then carefully washed several times with methanol,
0.1 M HCl, distilled water, and acetone. The obtained
brownish-black powder was dried under a vacuum dryer at
room temperature for 24 h. The polymer was synthesized
Ingenta
followingto:
the same procedure.

RESEARCH ARTICLE

Optical and Transport Properties of Poly(3-Hexylthiophene)-Single-Walled-Carbon-Nanotube Composites

Fig. 2.

Raman spectra of the P3HT and P3HT/SWNT composites.

Kim et al.

Fig. 4. UV-Vis absorption spectra of the P3HT and P3HT/SWNT

composites.

A typical FESEM image of P3HT and a TEM image

Table I. Bandgap results from the UV-Vis and PL max .
of the 20-wt.% P3HT/SWNT composite are presented in
max
max
Bandgap, eV
Figures 1(a and b). The nodular structure of the polymer
System
(UV-Vis), nm
(PL), nm
(UV-Vis)
and the polymer coverage on the SWNT to the thickness
of 5.6 nm are evident in the TEM image.
P3HT
4328
5696
237
P3HT-SWNT (1%)
4392
5683
235
The Raman spectra of the pure P3HT and SWNT and
P3HT-SWNT
(5%)
4347
5704
236
P3HT-SWNT composites are presented in Figure 2. In
P3HT-SWNT (10%)
4344
5674
236
the signals of SWNT, the important peaks at 1300 and
P3HT-SWNT (20%)
4375
5692
235
1590 cm1 represent the sp3 mode (D band) and the tanDelivered16 by Ingenta to:
gential mode (G band) of the nanotubes, respectively.
chul-jaeCNT
lee composites, the tangential-mode G band frequency
This spectrum of P3HT is as per the previous results
: 58.237.121.62
for rrP3HT, with all the vibrational frequencies IP
expected
appeared around the 1592 1 cm1 value, conrming the
Thu,
15 Sep 2011
13:08:29
19
for the conjugate polymer.17
18 Wise et al.
predicted,
presence
of SWNT in the polymer matrix.
from the upshifting of the G band and a downshift in the
In the FTIR spectra of the SWNT, P3HT, and P3HTRaman D band, a possible electron-donoracceptor-type
SWNT composites, the peak that appeared at 1621 cm1
interaction between the polymer and CNT. The intensity
for the as-procured SWNT sample can be assigned the
ratio of the D to G bands has also been used as a meaC=C stretch.21
22 The important frequencies correspondsure of the above parameter. In the present study with a
ing to different groups/moieties of the polymer are pre1-wt.% composite, the frequency position of the thiophene
sented in Figure 3. The CH2 stretch vibration and CH3
ring mode, which appeared at 1450 cm1 , was noted to
asymmetric-stretch frequencies were centered around 2917
be present at 1447 cm1 .20 With a higher proportion of
and 2849 cm1 for the composites, indicating no change.

Fig. 3.

290

FTIR spectra of the P3HT and P3HT/SWNT composites.

Fig. 5. PL of the P3HT and P3HT/SWNT composites.

J. Nanoelectron. Optoelectron. 6, 288292, 2011

Kim et al.

Optical and Transport Properties of Poly(3-Hexylthiophene)-Single-Walled-Carbon-Nanotube Composites

Table II. DC electrical-conductivity results at room temperature.

Samples

P3HT

Conductivity (S/cm)

574 10

1% SWNT
9

367 10

5% SWNT
73 10

10% SWNT
66 10

20% SWNT
106 102

Fig. 6.

IV conductivity measurement.

J. Nanoelectron. Optoelectron. 6, 288292, 2011

Fig. 7. Plot of the logs versus log(p-pc )t of the P3HT/SWNT composites at room temperature.

291

RESEARCH ARTICLE

The C=C symmetric-stretch frequency was positioned at

in the polymer, proving the effectiveness of the polymer/nanotube interface.28
29
around 14511453 cm1 , and the in-plane and out-of-plane
The DC electrical-conductivity results of the polymer
rocking vibrations of CH2 appeared at 719 and 1148
and its composites are presented in Table II.
1 cm1 for the composites, conrming that the polymer
The conductivities were measured using approximately
was physically wrapped over the CNTs.
0.04 g of the samples, pressed into pellet form 1.2 cm in
The UV-Vis absorption spectra of the P3HT and P3HTdiameter and 0.556 mm thick using 600 kgf/cm2 pressures
SWNT composites in 1,2,4-trichlorobenzene are presented
by a manual hydraulic press for 15 min. The electrical
in Figure 4. The spectral contribution of SWNT is known
conductivity of the conducting polymers is governed by
to be insignicant.23 In conjugated polymers, the extent
the conjugation and the dopants present in them.30 In the
of conjugation affects the absorbed energy of the 
case of composites made of CNTs, it is decided by the
transition, which is reected in the maximum absorption
purity, alignment, and the amount of nanotubes present
with these materials. Thus, the values of max will give
in them.31 Chen and Ni have reported conductivity valan insight into the extent of conjugation of the polymer
ues between 109 and 108 S/cm for pure P3HT neutral
when it is free and in the bound state onto the walls of the
polymers. The conductivity of P3HT at room temperature
nanotube. The value of max of P3HT (432.8 nm) is as per
24
was found to be 574 109 S/cm. The conductivity of the
the value reported for the sample prepared with FeCl3 .
polymer increases with the increased addition of SWNT, as
In the case of the composites, the values were found to
is normally expected, as the nanotubes serve as a pathway
be 435 3 nm, indicating no signicant shift. This could
for the electrons. The ohmic contact between the polymer
indicate the absence of any signicant ground state interand the nanotube is evident when the IV curve exhibits
action between the polymer and the SWNT. Such obserno hysteresis
Delivered by Ingenta
to: on a cycle (Fig. 6).
vations have been reported in the case of P3OT/SWNT
25
The
model
conductivity was found to follow the form
lee
The
blend composites and also in the work of Ref. [26].chul-jae
0
t
27

=

(p-p
)
IP : 58.237.121.62 c for p > pc (Fig. 7). As shown in Figure 7,
bandgap values measured from the UV-Vis absorbance
the 13:08:29
linearity of 20 wt.% deviated from the normal value.
Thu, are
15 Sep
results for the polymer and for the composites
pre- 2011
This
is the cause of the interaction between P3HT and
sented in Table I.
SWNT.
The PL spectra of P3HT and its composites in 1,2,4The work function values measured for SWNT, the
trichlorobenzene (C6 H3 Cl3 ) for an excitation wavelength
polymer,
and the 20 wt.% composite using photoelectron
of 450 nm are presented in Figure 5.
emission
methods were 4.92, 4.79, and 4.77 eV, respecThe polymer and the composites showed emissions
tively.
As
there was no variation in the values for the
within the 564569 nm range, again suggesting the
polymer
and
the composite, the absence of any signicant
absence of any covalent complexation between the polyground
state
interaction
between them can be understood.
mer and the nanotubes. The photoluminescence quenching of the composites suggest, however, that the SWNT
acts as the pathway for the singlet excitons generated

Optical and Transport Properties of Poly(3-Hexylthiophene)-Single-Walled-Carbon-Nanotube Composites

Kim et al.

RESEARCH ARTICLE

4. CONCLUSION

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Mater. 21, 3210 (2009).
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In this paper, homogenous poly(3-hexylthiophene)
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ites prepared via in-situ polymerization are exhibited. The
13, 85 (2003).
characteristics of the P3HT/SWNT composites were iden12. S. S. Sun and N. S. Saricftci, Organic Photovoltaics, CRC Press,
tied via Fourier transform infrared spectroscopy, Raman
Boca Raton (2005).
13. B. K. Kuila, S. Malik, S. K. Batabyal, and A. K. Nandi, Macrospectroscopy, and X-ray diffraction. There are indications
molecules 40, 278 (2007).
that physical interaction occurred between P3HT and
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SWNT, and the physical wrapping of the polymer onto
(1995).
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15. Y. L. Liu and W. H. Chen, Macromolecules 40, 8881 (2007).
the ultraviolet-visible and photoluminescence studies with
16. R. Osterbacka, C. P. An, X. M. Jiang, and Z. V. Vardeny, Synth. Met.
116, 317 (2001).
the nearly unchanged max also indicate the absence of
17. A. W. Musumeci, G. S. Glaura, J. W. Liu, W. N. Martens, and E. R.
any ground state electron transfer between the moieties.
Waclawik, Polymer 48, 1667 (2007).
Finally, the impressive conductivity values for the com18. F. Du, J. E. Fischer, and K. I. Winey, Phys Rev B: Cond. Matter.
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Mater. Phys. 72, 121404 (2005).
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J02401.
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Received: 20 April 2011. Accepted: 8 June 2011.

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J. Nanoelectron. Optoelectron. 6, 288292, 2011