APPLIED PHYSICS LETTERS VOLUME 80, NUMBER 1 7 JANUARY 2002

Single-wall carbon nanotubeÕconjugated polymer photovoltaic devices

E. Kymakisa) and G. A. J. Amaratunga
Engineering Department, Cambridge University, Cambridge CB2 1PZ, United Kingdom
共Received 4 June 2001; accepted for publication 2 October 2001兲
We report the optoelectronic properties occurring in single-walled carbon nanotubes 共SWNTs兲—
conjugated polymer, poly共3-octylthiophene兲 composites. Composite films were drop or spin cast
from a solution on indium–tin oxide 共ITO兲 and quartz substrates and studied using absorption
spectroscopy and electrical characterization methods. Diodes 共Al/polymer-nanotube composite/
ITO兲 with a low nanotube concentration (⬍1%) show photovoltaic behavior, with an open circuit
voltage of 0.7–0.9 V. The short circuit current is increased by two orders of magnitude compared
with the pristine polymer diodes and the fill factor also increases from 0.3 to 0.4 for the nanotube/
polymer cells. It is proposed that the main reason for this increase is the photoinduced electron
transfer at the polymer/nanotube interface. The results show that the conjugated polymer-SWNTs
composite represents an alternative class of organic semiconducting material that is promising for
organic photovoltaic cells with improved performance. © 2002 American Institute of Physics.
关DOI: 10.1063/1.1428416兴

Over the last decade, organic thin-film photovoltaic de- tallic or semiconducting depending on their diameters and
vices based on soluble conducting polymers have attracted a chirality. Carbon nanotube polymer composites have also
great deal of attention.1,2 Organic materials can be regarded been investigated for improved electrical conductivity and
as promising candidates for low cost solar cells and large- high strength composites.8,9
area photodetectors due to their low energy payback time. A schematic of the photovoltaic SWNTs/P3OT blend
The photovoltaic effect involves the generation of elec- photovoltaic cell is shown in Fig. 1. SWNTs 共Carbolex, Inc兲
tron and hole pairs and their subsequent collection at the synthesized by the arc discharge method were used in this
opposite electrodes. In inorganic materials, the photon ab- study. The SWNTs powder contains SWNTs self-organized
sorption produces free charge directly, while in organic ma- into bundle-like crystallites 共diameter 1.4 nm兲 and carbon-
terials, the photon absorption causes a delocalization of the encased metal nanoparticles. The powder purity was esti-
excited states, which leads to a generation of bound mated to be about 60% from transmission electron micro-
electron–hole pairs, excitons.3 These excitons have to disso- scopy. As-prepared SWNTs were purified using the hydro-
ciate into free charges in order to be transported to the elec- thermal method.10 The P3OTs used were from Sigma–
trodes. Exciton dissociation is known to occur in strong elec- Aldrich. The powder of the SWNTs was added to a chloro-
tric fields normally found at polymer–metal interfaces and at form solution and a high power ultrasonic probe was used to
dissociation centers, such as oxygen impurities acting as disperse the nanotubes. Then, the dispersed nanotubes were
electron traps.4,5 This feature has led several researchers to blended with a P3OT solution and sonicated for 1 h.
the idea of blending polymers with 共electron兲 acceptor mol- Diodes were fabricated in the sandwich configuration
ecules, having a larger electron affinity than the polymer. shown in Fig. 1. Organic films were deposited by drop and
Under these conditions, internal junctions between the poly- spin coating from a 10 mg/ml chloroform solution onto a
mer 共electron donating and hole accepting兲 and the electron
acceptor molecule 共hole donating兲 are created. This allows
the preferential transfer of the electrons into the electron ac-
ceptor molecule while leaving the holes to be preferentially
transported through the polymer, a process known as photo-
induced charge transfer.
Since the discovery of photoinduced charge transfer be-
tween conjugated polymers 共as donor兲 and buckminster-
fullerene C 60 and its derivatives 共as acceptor兲, several effi-
cient photovoltaic systems using a combination of polymer
and fullerene have been fabricated.6,7 In our work, poly共3-
octylthiophene兲 共P3OT兲, acting as the photoexcited electron
donors, is blended with single walled carbon nanotubes,
which act as the electron acceptors. The single wall nano-
tubes 共SWNTs兲 also allow the transferred electrons to be
transported by providing percolation paths. They can be me-
FIG. 1. Chemical structures of P3OT, SWNTs and device architecture of the
a兲
Electronic mail: ek224@eng.cam.ac.uk photovoltaic cells.

0003-6951/2002/80(1)/112/3/$19.00 112 © 2002 American Institute of Physics

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Appl. Phys. Lett., Vol. 80, No. 1, 7 January 2002 E. Kymakis and G. A. Amartunga 113

FIG. 2. Absorption spectra of a 60 nm thick layer of P3OT and of a P3OT-

SWNTs composite 共1 wt % Nts兲 on a quartz substrate. The optical band gap
of the composite is at 2.4 eV.

glass substrate coated with indium-tin oxide 共ITO兲. Alumi- FIG. 3. 共a兲 I–V characteristics of an ITO/P3OT/Al device in dark 共filled
num electrodes were thermally evaporated under a vacuum. circles兲 and under illumination 共open circles兲. 共b兲 The same data for an
The devices were kept in a nitrogen-filled glove box before ITO/P3OT-SWNTs/Al device.
characterization. The devices were tested under dark and il-
luminated 共AM 1.5兲 conditions through the glass/ITO side. and V oc⫽0.35 V. The I–V characteristics for the ITO/
An HP 4140B voltage source was used to drive the device, composite/Al device 共Fig. 4兲 show an anomalous behavior in
and an HP 3458A multimeter monitored the current through the range ⫺2.5 to 0 V, indicating a negative resistance. The
the device. All samples used in optical experiments were origin of this kind of behavior can not be explained at
very thin films, spin cast from solutions onto quartz sub- present.
strates, in order to keep the optical transparency. Absorption In the metal–insulator–metal 共MIM兲 diode model, the
was determined using a combination of UV-visible transmis- workfunction difference of the two electrodes defines the up-
sion and reflection spectra measured with a UniCam UV2 per limit of the V oc , which, for the pristine device, yields a
UV/VIS spectrophotometer. maximum V oc of 0.4 V 共Al 4.3 eV and ITO 4.7 eV兲. Thus,
Figure 2 shows the unnormalized absorption spectra of the V oc 共0.35 V兲 of the pristine diode does follow the differ-
P3OT and P3OT/SWNTs composite films at room tempera- ence in electrodes work function. However, in some cases,
ture. Both films were 60 nm thick. The absorption spectra of the V oc of polymer, and in particular polythiophene12 MIM
the P3OT show no significant change upon adding 1% of diodes, has been found larger than the workfunction differ-
nanotubes by weight. This implies that in the blend, no sig- ence of the two electrodes. This may be due to different ITO
nificant ground state interaction is taking place between the substrates used in each case. The ITO workfunction is as-
two materials, and hence, no charge transfer occurs in the sumed to be 4.7 eV, but its workfunction depends on the
ground state. In the photoexcited state, however charge trans- manufacturing conditions and the handling environment.
fer from the photoexcited P3OT to the nanotubes is expected Several studies discussing the factors that effect the ITO
to occur.11 From the absorption spectra of the P3OT, an op-
tical band gap of 2.4 eV can be derived. The spectrum indi-
cates that more than 60% of the incident light is absorbed
between 2.2 and 2.8 eV.
The current–voltage 共I–V兲 characteristics of the ITO/
P3OT/Al and ITO/P3OT/P3OT-SWNTs/Al devices in dark
and under white light illumination 共AM 1.5, 100 mW/cm2兲
from the ITO side, are depicted in Figs. 3共a兲 and 3共b兲, re-
spectively. Forward bias is defined as positive voltage ap-
plied to the ITO electrode. The dark current is considerably
higher in forward bias than in reverse bias, indicating a dis-
tinct diode behavior. The rectification ratio at 2 V in the dark
is higher than 104 . Under illumination, the blend device
shows short-circuit photocurrent density (I sc) of
0.12 mA/cm2 and an open-circuit voltage (V oc) of 0.75 V FIG. 4. I–V characteristics of an ITO/P3OT-SWNTs/Al device measured in
共Fig. 4兲, while the pristine device shows I sc⫽0.7 ␮ A/cm2 the dark 共filled circles兲 and under illumination 共open circles兲 as a linear plot.
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114 Appl. Phys. Lett., Vol. 80, No. 1, 7 January 2002
workfunction in terms of preparation methods and surface
treatments,13 support this argument. The published values of
the ITO workfunction range from 4.1 to 5.5 eV.14
Hence, one would expect the V oc of an ITO/
composite/Al device to be no larger than 0.4 V. However, the
V oc of the blend device 共0.75 V兲 is significantly higher. An
explanation for this higher V oc is that the photovoltaic char-
acteristics being measured are mainly those of an ITO/
polymer/nanotube MIM diode, with Al forming ohmic con-
tacts to the nanotube percolation paths. The existence of an
ohmic contact between the ITO electrode and the nanotubes,
was prevented by the placing of an ultrathin P3OT transition
layer between the ITO and the composite. Following the
MIM model, the V oc of the cell would then be determined by
the ITO-SWNT workfunction difference rather than that be-
tween ITO and Al. This would imply that the SWNTs used
had a workfunction of 3.95 eV, at maximum. This is in keep-
ing with reports in the literature on field emission from car-
bon nanotubes where the low threshold fields measured can
only be explained on the basis of them having a much
smaller workfunction than that of graphite 共5 eV兲.15 The
workfunction of SWNTs ranges from 3.4 to 4 eV, while for
the MWNTs the range is from 4.6 to 5.1 eV.16 The workfunc-
tion extracted from the measurements assuming such a
model is therefore within the expected range. The diode for-
ward turn-on voltage would be different from V oc and domi-
nated by the largest barrier. For an approximate 3.95 eV
workfunction of a SWNT, this would be between the SWNT
and polymer, and be equal to 1.1 eV. 共P3OT electron
affinity⫽2.85 eV兲17 The measured forward voltage of the Al/
SWNT/P3OT/ITO structure is ⬃1 V. This would be there-
fore consistent with the existence of an SWNT/polymer
junction.
One of the characteristics which indicates the power de-
livery capability of a photovoltaic cell is the fill factor. The
fill factor, 共FF兲, is calculated by FF⫽(V m I m )/(I sc V oc),
where V m and I m are defined as the intersection of the I–V
curve with the maximum power rectangle. Typical FF values
of these devices with pure P3OT and P3OT-SWNTs is about
0.3 and 0.4, respectively. The power conversion efficiency n
was calculated according to
FF⫻I sc共 A/cm2 兲 ⫻V oc共 V 兲
n⫽ , 共1兲
Pin 共 W/cm2 兲
where V oc , I sc , FF, and Pin are the open circuit voltage, the
short-circuit current, the FF, and the incident light power,
respectively. The power efficiency of the blend device is dra-
matically increased from 2.5⫻10⫺5 to 0.04% with respect to
the pristine one. The important comparison here is the rela-
tive performance. The active cell efficiency values may be
higher if the input power coupled into the cell is lower than
the incident optical power Pin in Eq. 共1兲. For both the P3OT
and P3OT/SWNT blend films of equal thickness tested, the
optical power coupled is expected to be very similar based
on the absorption spectrum shown in Fig. 2.
Thus, a considerable improvement of photovoltaic effect
is observed with the P3OT/SWNTs blend structure. The I sc
in the blend device is larger than that in the pristine device
by about two orders of magnitude. Moreover, the V oc and the
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E. Kymakis and G. A. Amartunga
FF in the blend device are also significantly larger than those
in the pristine diode. It is proposed that the enhancement in
the photovoltaic properties of the blend device is due to the
introduction of internal polymer/nanotube junctions within
the polymer matrix. These junctions act as dissociation cen-
ters, which are able to split up the excitons and also create a
continuous pathway for the electrons to be efficiently trans-
ported to the negative electrode. This results in an increase in
the electron mobility, and hence, balances the charge carrier
transport to the electrodes. In addition, the conductivity of
the composite is increased by a factor of 10, indicating per-
colation paths within the material.
In summary, we have demonstrated a photovoltaic de-
vice based on SWNTs and a conjugated polymer, P3OT. The
operating principle of this device is that the interaction of the
carbon nanotubes with the polymer, allows charge separation
of the photogenerated excitons in the polymer and efficient
electron transport to the electrode through the nanotubes.
SWNTs doping was found to dramatically improve the pho-
tovoltaic performance of P3OT devices revealing a photocur-
rent larger than two orders of magnitude compared to that of
the pristine diodes, and a doubling of the open-circuit volt-
age. The results show that the conjugated polymer-SWNTs
composite represents an alternative class of organic semicon-
ducting material that can be used to manufacture organic
photovoltaic cells with improved performance. Further im-
provements in device performance are expected with more
controlled film preparation and polymer doping.
This work was supported by the Engineering and Physi-
cal Sciences Research Council 共EPSRC兲.
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