Cutting carbon nanotubes for solar cell

application
Cite as: Appl. Phys. Lett. 92, 123508 (2008); https://doi.org/10.1063/1.2903493
Submitted: 12 February 2008 . Accepted: 07 March 2008 . Published Online: 26 March 2008

Golap Kalita, Sudip Adhikari, Hare Ram Aryal, Masayoshi Umeno, Rakesh Afre, Tetsuo Soga, and
Maheshwar Sharon

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Appl. Phys. Lett. 92, 123508 (2008); https://doi.org/10.1063/1.2903493 92, 123508

© 2008 American Institute of Physics.

 APPLIED PHYSICS LETTERS 92, 123508 共2008兲

Cutting carbon nanotubes for solar cell application

Golap Kalita,1,a兲 Sudip Adhikari,1 Hare Ram Aryal,1 Masayoshi Umeno,1 Rakesh Afre,2
Tetsuo Soga,2 and Maheshwar Sharon3
1
Department of Electrical and Electronics Engineering, Chubu University, 1200 Matsumoto-cho 487-8501,
Japan
2
Department of Environmental Technology and Urban Planning, Nagoya Institute of Technology,
Nagoya 4668555, Japan
3
Nanotechnology Research Center, Birla College, Kalyan-421304, India
共Received 12 February 2008; accepted 7 March 2008; published online 26 March 2008兲
This paper presents the application of cutting multiwalled carbon nanotubes 共cut-MWNTs兲 in solar
cell. Cutting of MWNTs is performed by plasma fluorination and followed by defluorination.
Cut-MWNTs with lengths of 50– 200 nm are incorporated in a poly共3-octylthiophene兲 / n-Si
heterojunction solar cell. We found that a device fabricated with cut-MWNTs shows much better
performance than that of a device with pristine MWNTs. The device with cut-MWNTs shows short
circuit current density, open circuit voltage, fill factor, and power conversion efficiency as
7.65 mA/ cm2, 0.23 V, 31%, and 0.54%, respectively. Here, we proposed that cut-MWNTs provide
efficient hole transportation having a few nanometer transportation path, hence suppressing
recombination. Cut-MWNTs can be the solution to the shorting and shunting effects generally
observed in the MWNT solar cell. © 2008 American Institute of Physics.
关DOI: 10.1063/1.2903493兴

Application of carbon nanotubes 共CNTs兲 in organic pho- incorporation of cut-MWNTs in a heterojunction photovol-
tovoltaic device is of great interest.1,2 It has been demon- taic device. Pristine MWNTs and cut-MWNTs were incorpo-
strated that CNTs along with conjugated polymers favor rated in poly共3-octylthiophene兲 共P3OT兲 and n-Si heterojunc-
charge transportation and exciton dissociation.3,4 CNTs can tion photovoltaic device. It was observed that with cut-
improve exciton dissociation by providing field at the poly- MWNTs, much better device performance can be obtained
mer nanotube interface. A blend of CNTs with conducting than that of pristine MWNTs. We expect that cut-MWNTs
polymer allows formation of devices with high interfacial provide efficient hole transportation having a few nanometer
area, which can lead to a large pair dissociation region.5–8 transportation path hence suppressing recombination. Cut-
These properties of CNTs with conjugated polymer have MWNTs can be the solution to the shorting and shunting
generated a great interest in developing photovoltaic devices. effects generally observed in the MWNT solar cell.
Pradhan et al. have demonstrated incorporation of function- MWNTs were synthesized as previously described17 by
alized multiwalled carbon nanotubes 共MWNTs兲 in a donor- using precursor turpentine oil by spray pyrolysis at 800 ° C.
acceptor type of photovoltaic device.9 We have demonstrated Purified MWNTs were placed in a surface wave microwave
the application of oxygen plasma treated MWNTs combined plasma chamber for fluorination. CF4 gas was introduced in
with fullerene for photovoltaic application.10 Although the chamber along with argon with flow rates of 20 and
charge transportation and exciton dissociation are desirable 15 SCCM 共SCCM denotes cubic centimeter per minute at
properties of CNTs, in the case of a CNT-polymer composite STP兲, respectively. Fluorine plasma was generated via a sur-
film for photovoltaic devices, the CNT length may need to be face guide supplied by a 2.45 GHz microwave generator at
controlled. For example, thickness of the composite active
film is of a few nanometers 共⬍1 ␮m兲, but the average length
of purified CNTs is in micrometers 共⬃100 ␮m兲. As a result,
the actual length of the fabricated device is of the order of
micrometers as that of CNT length.11 In the fabricated device
with CNT-polymer composite, there can be shunting and
shorting effects through the micrometer long CNTs.12–14
Therefore, controlled cutting of CNTs is necessary for blend-
ing with the conducing polymer. Cut-CNTs can reduce the
shunting effect in these devices while maintaining the high
electrical conductivity necessary to extract charges out of the
polymer layer.
Controlled cutting of CNTs in the range of a few nanom-
eters can be obtained through fluorination.15,16 Gu et al. have
demonstrated cutting of single walled CNTs in the range of
50 nm through fluorination and followed by annealing.15
Here, we report cutting of MWNTs in nanometer range and
FIG. 1. 共Color online兲 XPS C 1s spectra of 共a兲 cut-CNTs 共defluorinated
a兲
Electronic mail: golapkalita@yahoo.co.in. CNTs兲, 共b兲 fluorinated CNTs, and 共c兲 as synthesized CNTs.

0003-6951/2008/92共12兲/123508/3/$23.00 92, 123508-1 © 2008 American Institute of Physics

123508-2 Kalita et al.
gas composition pressure of 40 Pa. Fluorination of the
MWNTs was performed at 450 ° C for 1 h. Defluorination of
fluorinated MWNTs was performed in argon atmosphere at
700 ° C for 45 min. Pristine MWNTs and cut-MWNTs were
dispersed in a chloroform solvent with 0.2 mg/ ml concentra-
tion respectively. Pristine MWNTs and cut-MWNTs were
mixed with a P3OT solution 共6 mg/ ml兲 with the concentra-
tion ratio 1:1, respectively. Prepared solutions were spin
coated at 600 rpm over n-Si substrates. Fabricated films were
annealed at 120 ° C for 15 min. Finally, semitransparent top
gold electrodes 共10– 15 nm兲 were deposited by sputtering.
X-ray photoelectron spectroscopy 共XPS兲 measurements
of MWNTs were carried out on a SSX-100 photoelectron
spectrometer. Transmission electron microscopy 共TEM兲
measurements were carried out by using a field emission
TEM, JEOL-2100F. Gold electrodes were deposited by sput-
tering of gold target in E-1030 ion sputter. Current-voltage
共I-V兲 characteristics were measured by using JASCO SS-200
W solar simulator in the dark and under AM 1.5 simulated
solar radiation.
Figure 1 shows XPS C 1s spectra of as synthesized,
fluorinated and defluorinated MWNTs. The spectrum of pris-
tine MWNTs shows photoelectron emission from the C 1s
core level peak centered at 284.5 eV corresponding to sp2
carbon. After fluorination, the intensity of the sp2 peak sig-
nificantly reduced and showed a broad intense peak at
293.5 eV. The broad C 1s peak observed at 293.5 eV was
ascribed to sp3 hybridized carbon with covalent C–F bonds,
which are similar to graphite fluorides, 共CF兲n and 共C2F兲n.18
Quantitative analysis shows the presence of 57% fluorine
atoms along with carbon and a small amount of oxygen at-
oms. With annealing of fluorinated MWNTs, fluorine atoms
were released from the MWNT surface. The XPS study of
defluorinated MWNTs shows photoelectron emission from C
1s core level peak centered at 284.5 eV re-establishing sp2
carbon by releasing the C–F bond. Quantitative analysis of
defluorinated MWNTs shows reduction of fluorine concen-
Appl. Phys. Lett. 92, 123508 共2008兲
FIG. 2. 共Color online兲 TEM study
of 共a兲 as synthesized MWNTs and
共b兲 cutting MWNTs 共cut-MWNTs兲
through fluorination.
tration of up to 1.25% and an increase in oxygen content of
up to 5.2%. It was observed that with low fluorine incorpo-
ration in MWNTs, cutting of all MWNTs was not achieved.
With fluorination of MWNTs, fluorine atoms form band-
like fluorinated areas along the nanotube sidewall. In the
case of partially fluorinated MWNTs, the transition between
the fluorinated and nonfluorinated bands typically remains
quite abrupt and orthogonal to the MWNT axis.19 Since the
fluorine atoms are localized in certain regions along the
MWNTs and leave certain lengths of the MWNTs intact,
hence defluorination would only affect the fluorinated part
of the MWNTs and leave behind the intact parts of the
MWNTs, resulting to cut-MWNTs.15
From the TEM study, it was observed that as synthesized
MWNTs were of micrometer long having diameter distribu-
tion of 10– 30 nm. Figure 2共a兲 presents the TEM image of
pristine MWNTs having a length in the micrometer range.
Figure 2共b兲 presents the TEM image of the cut-MWNTs
clearly showing an open end of the cutting nanotubes. It was
observed that cut-MWNTs were having length in the range
of 50– 200 nm. It shows through fluorination, cutting of
MWNTs was achieved in nanometer range.
Figures 3共a兲 and 3共b兲 presents I-V characteristics under
dark and white light illumination of the device fabricated
with pristine MWNTs and cut-MWNTs. Composite films of
pristine MWNTs and cut-MWNTs with P3OT were having
thickness around 400 nm. The fabricated device with pristine
MWNTs shows short circuit current density 共Jsc兲, open cir-
cuit voltage 共Voc兲, fill factor FF, and conversion efficiency as
0.51 mA/ cm2, 0.18 V, 25%, and 0.023%, respectively. Simi-
larly, device fabricated incorporating cut-MWNTs shows Jsc,
Voc, FF, and conversion efficiency as 7.65 mA/ cm2, 0.23 V,
31%, and 0.54%, respectively. It was observed that with in-
corporation of cut-MWNTs, there were much better device
performance than that of device with pristine MWNTs. En-
hancement of device performance is due to a large improve-
ment in the Jsc 共from 0.51 to 7.65 mA/ cm2兲. This may be
FIG. 3. 共Color online兲 I-V characteris-
tics of the device fabricated with 共a兲
pristine MWNTs and 共b兲 cut-MWNTs
with the structure n-Si/ cut-MWNTs
+ P3OT/ Au under dark and illumina-
tion 共AM 1.5 100 mW/ cm2兲.
123508-3 Kalita et al.
FIG. 4. 共Color online兲 Energy band diagram of the fabricated device show-
ing band alignment for pristine MWNTs and cut-MWNTs.
due to the fact that cut-MWNTs provide efficient hole trans-
portation having a few nanometer transportation path hence
suppressing recombination. Whereas with micrometer long
pristine MWNTs, the charge transportation path is in order of
micrometer in the device. This may favor the recombination
process as the hole was transported through the nanotube
length and then tunneled to the next nanotubes. Work func-
tion of MWNTs is in the range of 4.5– 5.1 eV, which is close
to the valence band of P3OT; it signifies possible hole trans-
portation through MWNTs.20 It is expected that with surface
chemical groups attached to MWNTs during fluorination
and defluorination processes disrupt the ␲ conjugation and
introduce surface dipole moments, leading to higher work
functions.21 With an increased work function of cut-MWNTs,
it will be much closer to the valence band of P3OT and
would provide efficient hole transportation. At present, we
are unaware of the exact work function of cut-MWNTs. En-
ergetically favorable charge transportation and band align-
ment for pristine MWNTs and cut-MWNTs are shown in Fig.
4. On the other hand, with the micrometer long MWNTs,
there can be a shunting effect in the fabricated device
through the highly conductive path provided by pristine
MWNTs. It may cause significant reduction of Jsc in the
fabricated device with pristine MWNTs. Cut-MWNTs re-
main well embedded within the photoactive polymer layer,
which can significantly reduce the shunting effect in the de-
vice and thereby improve device performance.
Incorporation of a high percentage of pristine MWNTs
into the polymer matrix causes short circuits since the
lengths of CNTs are comparable to the total thickness of
photovoltaic films. It can be overcome with the incorporation
of cut-CNTs, which is well embedded within the polymer.
Again, the presence of charge recombination pathways
through the pristine MWNTs, which is randomly dispersed
within the polymer, affects the device performance. Cut-
MWNTs appear to be readily dispersed in chloroform solu-
tion due to the presence of surface functional groups. Here,
we expect that cut-MWNTs form homogeneous dispersion
Appl. Phys. Lett. 92, 123508 共2008兲
within the polymer, suppress the recombination path, and
thereby enhance device performance.
We have demonstrated the application of cutting
MWNTs 共cut-MWNTs兲 in photovoltaic devices. Cut-
MWNTs were obtained by plasma fluorination and followed
by defluorination. The TEM study shows cutting of MWNTs
having length in the range of 50– 200 nm. The fabricated
device incorporating cut-MWNTs shows much better perfor-
mance than that of the device with pristine MWNTs. Device
with cut-MWNTs shows Jsc, Voc, FF, and conversion effi-
ciency as 7.65 mA/ cm2, 0.23 V, 31%, and 0.54%, respec-
tively. Here, we proposed that cut-MWNTs can be the solu-
tion of the shorting and shunting effects generally observed
in MWNT solar cell. Cut-MWNTs can be well embedded
within the polymer film, proving efficient hole transporta-
tion.
The author is grateful to the Ministry of Education, Cul-
ture, Sports, Science and Technology, Japan for providing
fellowship.
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