Influence of single-walled carbon nanotubes

induced exciton dissociation improvement

on hybrid organic photovoltaic devices
Cite as: J. Appl. Phys. 126, 113101 (2019); https://doi.org/10.1063/1.5105388
Submitted: 27 April 2019 . Accepted: 23 August 2019 . Published Online: 16 September 2019

B. Aïssa , A. Ali , A. Bentouaf, W. Khan, Y. Zakaria, K. A. Mahmoud , K. Ali, N. Malik Muhammad, and
S. A. Mansour

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 Journal of ARTICLE scitation.org/journal/jap
Applied Physics

Influence of single-walled carbon nanotubes

induced exciton dissociation improvement on
hybrid organic photovoltaic devices
Cite as: J. Appl. Phys. 126, 113101 (2019); doi: 10.1063/1.5105388
Submitted: 27 April 2019 · Accepted: 23 August 2019 · View Online Export Citation CrossMark
Published Online: 16 September 2019

B. Aïssa,1,2,a) A. Ali,2 A. Bentouaf,3 W. Khan,4 Y. Zakaria,2 K. A. Mahmoud,2 K. Ali,2 N. Malik Muhammad,5

and S. A. Mansour2

AFFILIATIONS
1
MPB Communications Inc., Space & Photonics Division, 151 Hymus Boulv., Pointe Claire, Quebec H9R 1E9, Canada
2
Qatar Environment and Energy Research Institute, Hamad Bin Khalifa University, Qatar Foundation, P.O. Box 34110, Doha, Qatar
3
Laboratory of Physico-Chemistry of Advanced Materials, University of Djillali Liabès, Sidi Bel Abbès 22000, Algeria
4
NanoLund and Solid State Physics, Lund University, Box 118, 22100 Lund, Sweden
5
Faculty of Integrated Technologies, Universiti Brunei Darussalam, 1680 Jalan Tungku Link, Bandar Seri Begawan BE 1410,
Brunei Darussalam

a)
Author to whom correspondence should be addressed: brahim.aissa@mpbc.ca

ABSTRACT
Torch-plasma-grown single-walled carbon nanotubes (SWCNTs) are integrated with regioregular poly(3-hexylthiophene) (P3HT) and a
fullerene derivative 1-(3-methoxycarbonyl) propyl-1-phenyl[6,6]C61 (PCBM) as a hybrid photoactive layer for bulk heterojunction solar
cell devices. We demonstrate that molecular information could be accurately obtained by time-of-flight secondary ion mass spectrometry
throughout the hybrid organic photoactive solar cell layers when sputtering is performed using a Cs+ 2000 eV ion source. Furthermore,
the photovoltaic (PV) performance of the fabricated devices show an increase in the short-circuit current density (Jsc) and the fill factor
(FF) as compared to the pristine devices fabricated without SWCNTs. The best results are obtained with 0.5 wt. % SWCNT loads, where
an open-circuit voltage (VOC) of 660 mV is achieved, with a Jsc of 9.95 mA cm−2 and a FF of 54%, leading to a power conversion
efficiency of 3.54% (measured at standard test conditions, AM1.5 g). At this optimum SWCNT concentration of 0.5 wt. %, and to further
understand the charge-transfer mechanisms taking place at the interfaces of P3HT:PCBM:SWCNT, Jsc is measured with respect to the
light intensity and shows a linear dependency (in the double logarithmic scale), which implies that losses in the charge carrier are rather
governed by monomolecular recombination. Finally, our results show that our hybrid devices benefit from the fullerene electron accept-
ing nature and from the SWCNT fast electron transportation feature that improve substantially the exciton dissociation efficiency. The
influence of the SWCNTs on the Fermi level and the work function of the photoactive composite and its impact on the PV performance
is also investigated.

Published under license by AIP Publishing. https://doi.org/10.1063/1.5105388

I. INTRODUCTION interplayed phenomena and optimizing the basic organic PV

Organic materials have demonstrated a true capacity for
incorporation into photovoltaic (PV) devices for cost effectiveness
and large area green fabrication processing on light and flexible
substrates. Although power conversion efficiencies at the module
level are still too low to be considered for utility scale energy con-
version, compared to those of their inorganic counterpart, there
is still tremendous activity in further understanding the physical
(OPV) device structure.1–3 Presently, the highest performance
OPV cells incorporate bulk heterojunctions (BHJs) using fuller-
enes as the acceptor material, where the photophysical processes
consist of (i) optical photon absorption, (ii) singlet exciton crea-
tion and diffusion, (iii) exciton dissociation, and finally (iv) carrier
collection.4–7 The organic solar cells concept has been extensively
investigated during the last two decades, and power conversion

J. Appl. Phys. 126, 113101 (2019); doi: 10.1063/1.5105388 126, 113101-1

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efficiencies surpassing 13% have already been obtained and
recorded.8,9
In this avenue, the identification of high-performance
photoactive materials and the optimum design of device structure
are critical for achieving high-efficiency organic PV systems.
The introduction of carbon nanotubes (CNTs) in OPV devices has
been proposed as one of several strategies, which include (i) the
direct incorporation of carbon nanotubes within a BHJ photosensi-
tive film, (ii) composites synthesis, i.e., CNT-polymers, (iii) use the
CNT thin films for hole transportation, and (iv) the hole collecting
flexible transparent electrodes fabrication.10–14 However, due to the
hopping mechanism for transportation and fullerenes clustering,
charge mobility was rather low and hence device efficiency was
limited.15 The main motivation for the addition of CNTs in the
BHJ architecture is to replace the low-electrically conductive and
limited air-stable fullerenes and to conglomerate the physico-
chemical features of the organic conjugated polymers with the
high-speed transportation characteristics of CNTs, i.e., adding
CNTs charge transportation to hopping transportation mechanism.
This promises the possibility to obtain an effectual knitted network
with highly effective exciton dissociation in polymeric BHJs, where
the electron donor is the conjugated polymer and CNTs act as elec-
tron acceptors.15
In OPV systems, single-walled carbon nanotubes (SWCNTs)
were first employed as an acceptor material by Kymakis and
Amaratunga who intermingled poly(3-oxylthiophene-2.5-diyl)
(P3OT) with 1 wt. % CNTs.3 Solar cell performance increased
remarkably as evidenced by the open-circuit voltage (VOC) and the
short-circuit current (Jsc). The addition of SWCNTs simultaneously
introduces internal polymer–nanotube junctions that enhance the
exciton dissociation interfaces (i.e., between charge donor and
charge acceptor regions) and supplies continuous paths (via an
electrically percolating network) for electron transport to the
cathode.16,17 It has also been established that SWCNTs can carry
holes.18,19 In recent times, boron and nitrogen are also used as
dopants in CNTs for showing improvement in charge transporta-
tion when CNTs were incorporated into P3HT:PCBM based BHJ
solar cells.20 It was noticed that with boron doped CNTs, mobility
was balanced and it resulted in an increase in VOC and Jsc thereby
increasing the cell efficiency from 3% to 4.1%. Conversely, dispers-
ing high loads of carbon nanotubes into the polymer matrix is not
straightforward and remains a very challenging task, especially
when the length of the carbon nanotube is in the range of the
thickness of the photopolymer, consequently resulting in the gener-
ation of short-circuit effects. Accordingly, when the nanotubes are
integrated at low concentrations into the matrix of a polymer and
fullerene, it could improve the efficiency of excitons dissociation at
the polymer–fullerene and polymer–nanotube interfaces. Moreover,
it can enhance the capacity of electron transportation through the
carbon nanotubes. In this regard, many research groups across the
world have materialized this idea and have successfully introduced
carbon nanotubes in standard donor–acceptor photovoltaic solar
cells devices.10–17
Here, we investigate the impact of the incorporation of
functionalized single-walled carbon nanotubes (f-SWCNTs) with
regioregular poly(3-hexylthiophene) (P3HT) and a fullerene deriva-
tive 1-(3-methoxycarbonyl) propyl-1-phenyl[6,6]C61 (PCBM) as a
J. Appl. Phys. 126, 113101 (2019); doi: 10.1063/1.5105388
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ARTICLE scitation.org/journal/jap
photoactive layer for bulk heterojunction photovoltaic (PV) devices.
Our hybrid OPV devices show a clear improvement in the important
PV characteristics including the short-circuit current and the fill
factor (FF). Superior results are achieved with 0.5 wt. % single-walled
carbon nanotubes, leading to an improvement up to 3.54% in the
power conversion efficiency (PCE).
II. EXPERIMENTAL DETAILS
P3HT (regioregular) and PCBM were purchased from Sigma
Aldrich™. The plasma torch synthesis process was utilized to grow
single-walled carbon nanotubes (SWCNTs).21 In the plasma torch
synthesis, precursors of carbon and metal catalysts were decom-
posed by an inductively coupled plasma (ICP) torch and then
cooled in the gas phase state. This cooling process led to the nucle-
ation and eventually the growth of single-walled CNTs. The yield
of this growth process is >85 wt. %. To minimize the effect of resid-
ual metallic contents (<15 wt. %), the as synthesized material was
treated with nitric acid by refluxing in a 3M-HNO3 solution (Sigma
Aldrich™); the SWCNTs were dispersed into a 1:3 proportion of
3M-HNO3 and sonicated for 5 h at 60 °C to remove metal impuri-
ties and to generate shortened SWCNTs with terminal —COOH
groups.22–24 PCBM and regioregular P3HT in a 1:1 proportion
were first dissolved in 1,2-dichlorobenzene (DCB) solvent and
stirred for 2 h at 55 °C. The obtained solution was further diluted
with the addition of water, and large aggregates were separated by
centrifugation at 7200 rpm for 3 h.
A polytetrafluoroethylene filter with 200 nm-pore size
(Sigma Aldrich™) was used to filter the supernatant. The
remaining was intensively rinsed with de-ionized water by
decantation in order to remove any surplus acid. After this opera-
tion, a drying process in an electrical oven at 110 °C was carried
out. The functionalized SWCNT sample thus obtained was redis-
solved again in chlorobenzene solvent under ultrasonication at
60 °C for 2 h. Finally, its composites of different volumes were
synthesized by adding it to a P3HT:PCBM solution while sonicat-
ing for 2 h.
Sn doped In2O3 [indium–tin oxide (ITO)] coated borosilicate
glass substrates with a sheet resistance of 8–12 Ω/sq and dimensions
25 × 25 mm2 were used for photovoltaic fabrication. The ITO sub-
strate was first rinsed with acetone, isopropanol, and de-ionized
water and rinsed under ultrasonication for 20 min, and then dried by
nitrogen. ITO substrate surface energy was increased through a reac-
tive ion etching process into an ICP chamber to make it more hydro-
philic. A 40 nm buffer layer of poly(3,4-ethylenedioxythiophene)
poly(styrenesulfonate) (PEDOT:PSS, Sigma Aldrich™) was spun
coated at 2500 rpm onto the ITO substrate and then annealed at
110 °C for 30 min (surface resistance < 40 Ω/sq). It was then heat
treated at 100 °C inside a nitrogen-filled glovebox for 4 h. On the top
of it, the P3HT:PCBM:SWCNT photosensitive composite was spun
coated at 1200 rpm for 55 s from a mixture of P3HT:PCBM:
SWCNTs already dissolved in chlorobenzene. An ∼42 nm thick film
of a photoactive layer was hence obtained. The films were desiccated
for 1.5 h at room temperature, and then heat treated for another
35 min at 85 °C inside the glovebox filled with nitrogen. Metal elec-
trodes of aluminum were deposited by thermal evaporation through
a shadow mask. After evaporation of Al electrodes, postannealing
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treatment was carried out at a temperature of 110 °C for 15 min
under a nitrogen environment.
Bright field transmission electron microscopy (TEM) was per-
formed using a Jeol JEM-2100 F FEG-TEM (200 kV) microscope.
Atomic force microscopy (AFM) (NanoScope III, Digital
Instrument, operated at room temperature in ambient air) and
scanning electron microscopy equipped with EDS (Jeol-JSM-6300F
at 15 kV accelerating voltage) were used without any additional
coating. Micro Raman spectroscopy was performed with the
514.5 nm (2.41 eV) green laser radiation of an Ar+ ion focused
onto the sample with a very low intensity (5 mW/μm2) to prevent
the samples from any photodegradation (microRaman spectro-
scopy, Renishaw Imaging Microscope Wire™). X-ray photoelectron
spectroscopy (XPS, Escalab 220i-XL system, VG instruments) was
performed using monochromatic Al Ka radiation as the excitation
source (1486.6 eV, full width at half-maximum of the Ag 3d5/2
line = 1 eV at 20 eV pass energy). Depth profiling was carried out
on the deposited film using the IONTOF TOF-SIMS5 model.
Primary analysis was performed by a positive Bi+ ion beam at
30 keV and ∼1.29 pA current over a 100 × 100 μm2 analyzed area
using the sawtooth rastering mode. The depth profile has been con-
ducted in negative polarity, which targets the negative ions with
secondary sputtering source performed by the Cs+ ions beam at
2000 eV energy and ∼31 nA current over a 300 × 300 μm2 sputtered
area. Flood gun was used for charge neutralization at the sample
surface during profiling. At negative polarity, the sensitivity for
negative ions is much higher than positive ones. Hall measure-
ments were performed with a HMS-5000 system using the van der
Pauw method. Photon absorption by the active thin film material
was observed via a UV-Vis spectrophotometer (Specord® 210 plus,
Germany), and electrical properties were measured at room tempera-
ture in dark and under white light in air with a semiconductor
parameter analyzer (HP4155C, Agilent Technologies) and a solar
simulator (TELTEC) with an AM1.5 filter through the glass/ITO
side under an irradiation intensity of 100 mW/cm2 [i.e., at Standard
Test Conditions (STC), 1 sun]. Photoluminescence (PL) spectra were
achieved in air under room temperature conditions and implement-
ing a λ = 488 nm laser excitation wavelength. The collection of
emitted PL signal was performed through an optical fiber coupled to
an integrated optical spectrometer (HR 4000, Ocean Optics). All the
measurements were performed in air environment shortly after fabri-
cation of devices. The following equation has been used for the
power conversion efficiency (PCE or η) calculation:
η ¼ (VOC xJsc xFF)=Pin , (1)
where VOC, Jsc, FF, and Pin are the open-circuit voltage, the short-
circuit current density, the fill factor, and the incident light power,
respectively.
III. RESULTS AND DISCUSSION
Representative high resolution TEM image of Fig. 1(a) shows
the acid treated torch-plasma-grown SWCNT soot material, where
nanotubes are organized in ropes as well as single entities. These
SWCNTs feature high structural quality. In Fig. 1(a), SWCNTs
with an average diameter of ∼1.2 nm are the most observed.
J. Appl. Phys. 126, 113101 (2019); doi: 10.1063/1.5105388
Published under license by AIP Publishing.
ARTICLE scitation.org/journal/jap
Furthermore, Raman spectroscopy was used for structural informa-
tion on the diameter of nanotubes. Figure 1(b) shows the spectrum
of the purified (or functionalized) SWCNTs, where the radial
breathing mode (RBM) is clearly activated in the low frequency
region (which is the typical signature of the single-walled structure
of the nanotubes).The frequency positions of the RBM vibrational
mode can be used to determine the nanotubes’ diameters by means
of the relationship reported by Bandow et al.,25
dt (nm) ¼ 223:75=w(cm1 ), (2)
where dt and w are the diameter of nanotubes and the frequency of
the RBM vibrational mode, respectively. Our SWCNTs are found
to have a narrow diameter distribution centered around 1.20 nm
(which corresponds approximately to a bandgap around 0.7 eV),26
in total accordance with the real space observations by TEM [inset
in Fig. 1(a)]. The RBM band consists rather of four main compo-
nents [by the RBM peak deconvolution, displayed in the inset in
Fig. 1(b)] at 177, 186, 197, and 208 cm−1 (the 186 cm−1 peak being
the most prominent one and represents almost 65% of the peak
area). These peaks can be assigned to nanotube diameters of 1.26,
1.20, 1.13, and 1.07 nm, respectively.26–28 On the other hand,
according to the well known diameter-chirality dependence
formula26–28 and by considering all the possible (n m) chiralities
[namely, (5 13), (13 5), (4 13), (13 4), (4 12), (12 4), (14 1), (1 14),
(3 12), and (12 3)] for the four nanotube diameters identified
above, we find that more than 80% of these nanotubes are expected
to be semiconducting. Now, this percentage of s-CNTs might even
be higher and goes beyond 90% if the occurrence of the nanotubes
is weighted, for example, by the percentage of their associated RBM
peak area. It is worth noting here that even if the quantification of
the electronic population of the nanotubes is habitually achieved by
the optical absorbance process, resonance Raman scattering analysis
could also permit to have an accurate idea about the nanotube’s
species (for more details, see Ref. 28). In the present case, systematic
Raman scattering mapping was conducted on ten different batches
of SWCNT materials. The obtained percentage is found to be much
higher than the statistically expected 66%/33% of s-CNT/m-CNT
(which is obtained when all nanotubes diameters and associated
chiralities are produced by the same growth process). In fact, the
ratio of s-CNTs to m-CNTs has been shown to be growth process
dependent. For examples, Jorio and co-workers29 reported a
semiconducting-to metallic ratio of 11:1 (i.e., ∼92% of s-CNT),
while Li et al.30 showed that ∼90% of their nanotubes are semi-
conducting. However, it is worth mentioning here that even if all
diameters determined by Raman scattering do agree perfectly
with those observed by TEM, these results have to be taken with
due care, since ideally the whole Raman wavelengths should be
involved (from a theoretical viewpoint, the entire UV-IR light
spectrum) to point-out all the existing diameters and all their cor-
responding chiralities.
Surface topography of the P3HT:PCBM:SWCNT thin films is
determined by atomic force microscopy (AFM) in the tapping
mode and indicating a 4.37 nm surface roughness (RMS), while the
mean roughness (Ra) was found about 4.12 nm and the maximum
height (Rmax) is 35.8 nm. AFM analyses show as well that the film
has nanometer bumps that can be attributed to P3HT chains
126, 113101-3
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overlapping and entanglements during film preparation. It is well
established that the functionalization of carbon nanotubes is inherent
to the generation of structural defects. This includes sp3-hybridized
carbon, dislocations, and the appearance of pentagon and heptagon
defects in the lattice structure of the sidewall and/or the caps of the
nanotubes. Among this set, pentagonal defects are those that induce
the most charge localization. It is known that in the thiophene
segments on the polymer chain, sulfurs are electron rich owing to
the electron pair on the S atom (i.e., showing a 3s2 3p4 electron
configuration). Consequently, a strong interaction takes place
between the carbon nanotube and the P3HT polymer via the
interplay of the thiophene rings on the P3HT chains and the pen-
tagonal defects on the carbon nanotubes. A related binding was
already noticed and reported between an alkoxy phenylene section
on poly(m-phenylenevinylene-co-2,5-dioctoxy-p-phenylenevinylene)
(PmPV) chain and a pentagon defect on carbon nanotubes.31 As a
matter of fact, once P3HT molecules line up like a rope along the
tiny filament of a carbon nanotube (having individual diameters of
about 1.2 nm or tens of nanometers in the case of a bundlelike struc-
ture), the SWCNT bundle becomes hardly detected and barely
observed unless we solubilize the P3HT polymer. This additionally
supports the interfacial interactions between SWCNTs and P3HT
microcrystals and as a supplementary establishes the strong electron
J. Appl. Phys. 126, 113101 (2019); doi: 10.1063/1.5105388
Published under license by AIP Publishing.
ARTICLE scitation.org/journal/jap
FIG. 1. (a) TEM micrograph of single-
walled carbon nanotube ropes, the
inset is a close up view showing
bundle containing single-walled CNTs
of 1.2 nm-diameter. (b) The associated
Micro Raman spectrum. The inset
shows a magnification of the deconvo-
luted RBM peak. (c) 2D and 3D
Topography of P3HT:PCBM:SWCNT
thin film surface.
transfer from the conjugated polymer chain to the carbon nanotubes
through the interaction sites that are densely distributed along the
sidewall of SWCNTs.
On the other hand, the interfacial interactions between
SWCNTs and the conjugated polymers are also supported by XPS
analysis. Figure 2 displays the photoelectron spectra of C 1s of
as-grown and purified SWCNTs that show that the C 1s core level
peak consists of three clear components, while that of as-grown
SWCNTs samples exhibit a relatively narrow C=C peak. For the
purified nanotubes, in addition to the main component centered
around 284.5 eV, which is due to the sp2 C=C bonding forming the
bulk structure of SWCNTs, the two shoulders appearing at 286 eV
and 288 eV are attributed to C—O and/or C—NHx bonds and to
COO group of carboxylic acid groups.32,33 The XPS results confirm
that the purification process has led to carboxylic groups grafting
onto the SWCNTs surfaces (i.e., covalent functionalization), which
could offer additional interaction possibility with the conjugated
polymer, potentially leading to an enhanced charge transfer
between the polymer and the nanotubes.
Figures 3(a) and 3(b) show the surface morphology and cross-
sectional FE-SEM views of the Glass/ITO/PEDOT:PSS/P3HT:
PCBM:SWCNT layers before the electrode deposition. No evident
defects or pinholes (i.e., pinhole-free) could be observed on the top
126, 113101-4
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FIG. 2. Photoelectron spectra of C 1s of as-grown and purified SWCNTs.
FIG. 3. (a) Top view FE-SEM of P3HT:PCBM:SWCNT thin film deposited on
buffer layer PEDOT:PSS on ITO/Glass substrate and (b) its cross-sectional view
showing a very good layering of the different films.
J. Appl. Phys. 126, 113101 (2019); doi: 10.1063/1.5105388
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ARTICLE scitation.org/journal/jap
of the films that look rather very smooth and continuous, corrobo-
rating the very low RMS value estimated by AFM analysis. The
cross-sectional micrograph of Fig. 3(b) indicates very distinguished
layers and clear interfaces between them.
Furthermore, time-of-flight secondary ion mass spectrometry
(TOF-SIMS) was employed to analyze deposited thin films and
interfaces and detect associated molecular species.
Indeed, TOF-SIMS is a genuine robust capability for analyzing
the peripheral layers of organic and biological materials. The ion
fluence in static SIMS is commonly maintained low enough to
avoid decomposition of the organic/molecular varieties and hence
TOF-SIMS is capable to identify and even image high mass molec-
ular species, including polymer additives. Conversely, depth
profiling SIMS employs high ion fluence to sputter off materials for
the analysis cycle. However, the high ion fluence not only leads to
erosion but also to the decomposition of the organic species.
Nowadays, high mass cluster ion sources have been developed and
become applicable for depth profiling through organic layers.
Figure 4 shows the depth distribution of the elemental species.
O− and H− reveal a uniform intensity through the sampled depth,
which is to be expected as these are small fragments of the studied
molecules. The intensity of the C‒ fragment, attributed to PCBM,
is shown to decrease progressively upon erosion. This decrease is
associated with the decomposition of the molecular integrity, result-
ing in the loss of information upon erosion (material removal).
Hence, the depth profile trace of C− therefore does not represent the
change in molecular composition of the layer but rather decomposi-
tion of the molecular species into lower mass fragments. The C_4S−
are fragments associated with the P3HT molecule, and InO−, SnO−,
and InSnO− are associated with the ITO coating the glass substrate.
In sum, TOF-SIMS analyses reveal (i) a clear increasing trend
for ITO related SIMS species, (ii) a clear decreasing trend for
FIG. 4. Negative ion depth profile traces collected using IONTOF TOF-SIMS5
instrument [30 keV Bi3+ ion source for analysis and a low energy (2000 eV) Cs+
ion source for depth profiling].
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Applied Physics

organics related parts, and (iii) clear and chemically distinguished

interfaces as supported and corroborated by the SEM cross-
sectional view.
However, it is worth noting at this level that due to the lack of
specific certified standard samples, TOF-SIMS profiles were not cal-
ibrated to provide concentration instead of intensities. These inten-
sities have to be taken with high care and cannot be interpreted as
a concentration because of the different sputtering yield for each
element. This sputtering yield can indeed vary when the matrix
changes as well.
Hybrid organic solar cell performance was studied with
respect to SWCNT concentrations in the photoactive layer. A sche-
matic of the fabricated device is shown in Fig. 5(a). Both the solu-
bility and miscibility of the solvent with SWCNTs are very
important factors for developing successfully an active layer com-
posite. Chlorobenzene is a popular solvent for the P3HT:PCBM
composite, but pristine SWCNTs do not disperse readily in this
solvent. Dispersion can be improved by adding a functional group
to the SWCNTs as performed by acid treatment for instance (i.e.,
covalent functionalization). On the other hand, solubility in chloro-
benzene is improved by the formation of a coating of SWCNTs
with the linker (amination) that permits the ensuing attachment of
C60 molecules (i.e., noncovalent functionalization). In thin film
device structures, the length of CNTs is a crucial factor because it
is related to the photoactive layer thickness. Indeed, to produce a
film with less than 100 nm thickness containing SWCNTs, which
are more than 1 μm long, is very unlikely without protruding
through either side. A higher concentration of low aspect ratio
CNTs may have a positive effect. Results indicated that the success-
ful hybrid composite consisted of CNTs functionalized with linked
C60 molecules, because of improved entanglement, film uniformity,
and charge assembling at the electrodes. Shortened SWCNTs lose
special properties such as swift conductivity and high-speed trans-
portation compared with long CNTs. However, this effect is largely
compensated by the fact that smaller CNTs bring two changes in
their properties: firstly, there is less “chance” of metallic SWCNTs
to short-circuit the devices; secondly, C—C bond lengths change
result in shortened and functionalized SWCNT-C60 having different
electronic transport properties. However, these discussed effects are
rather more related to high concentrations CNT. Now, in the
present scenario, first, the CNT loads are very low (≤1 wt. %);
second, not only the SWCNTs were functionalized by acid treat-
ment as discussed above, which improves their attachment to the FIG. 5. (a) Schematic of the hybrid OPV heterojunction device structure and (b)
conjugated polymer and promote thereby their dispersion, but the the corresponding energy levels diagram. (c) HOMO and LUMO energy levels
mixed solutions were also spun coated onto the substrate, which for the photoinduced charges transfer within BHJ Solar cell.
favored mainly a lateral dispersion rather than vertical ones (the
lateral dimensions of the samples are 25 × 25 mm2, which are much
larger than the CNTs’ lateral dimensions). Indeed, the surface (although rarely), and not all the tested samples were functional.
topography of the photoactive films showed a very low surface As a matter of fact, ∼8% of them did not show any PV effect and
roughness (<5 nm), witnessing rather smooth and homogenous were simply shorted. This is believed to be due to the presence of
film quality. Moreover, from a transportation point of view, the metallic-CNTs but also to other amorphous carbon nanostructures
f-SWCNTs are found to be mainly semiconducting (by more than or simply caused by fabrication imperfections.
80%) and the chances that a metallic and percolated network of In Figs. 5(b)–5(c), a schematic of the possible energy level
m-SWCNT is formed and short-circuit the entire sample are very diagram is given, which is related to the charge transportation
low—but not excluded however—otherwise, m-CNT will just act as process. The electrochemical method is used for determining the
a metal interconnect between semiconducting CNT. Nonetheless, highest occupied molecular orbital (HOMO) and the lowest unoc-
this scenario (of short circuiting the devices) did happen in fact cupied molecular orbital (LUMO) of P3HT and PCBM. It is

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 Journal of
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observed to be approximately 5.25 and 2.85 eV for the P3HT below
the vacuum level and 6.1 and 3.75 eV for the PCBM, respectively.
Work function of SWCNT is determined by the thermionic
method, which is 4.7–4.9 eV.34,35 In this model, the generation of
excitons is made both in the polymer as well as in the fullerene,
and the excitons could be dissociated in three best possible ways
which are (i) the interfaces of the polymer/fullerene, (ii) the fuller-
ene/nanotube, and (iii) the polymer/nanotube. The energetically
favorable mechanism for electron transfer is the transportation of
electrons being captured by the polymer to the fullerenes and the
movement of electrons captured by the fullerenes to the SWCNTs.
Thus, it leads to the faster transportation of electrons compared to
hopping, which occurs only through fullerenes in pristine devices.
Now, as the SWCNTs were mixed with P3HT:PCBM, they could
possibly also be located between P3HT and PCBM materials (but
unlikely between P3HT and PDOT:PSS as the buffer layer was
deposited separately on ITO substrate). This configuration should
not constitute an issue since the very small concentrations of
SWCNT (less than 1 wt. %) could even promote faster transfer of
disassociated electron/holes, on either way of the abovementioned
interfacial possibilities, and minimize the recombination probabilities
to the lowest. As a matter of fact, Kymakis et al. demonstrated in
Ref. 36 that the incorporation of SWCNTs in the P3HT:PEDOT:SS
polymer matrix contributes to a reduction of the localized states in
the bandgap of the polymer, resulting in improved carrier conduc-
tion and mobility. Finally, the decrease in the hall mobility for
SWCNT concentrations >0.5% can be attributed to the formation of
shallow hole traps in the conjugated polymer bandgap. This is sup-
ported by the theoretical work of Xu et al.37 who reported that the
effective mobility of carriers in doped organic systems decreases at
high doping levels. The presence of metallic SWCNTs has an impact
mainly on the hole transportation, as m-SWCNT can act as recombi-
nation and trap centers in the gap, which could block hole transport
in the polymer matrix. However, this effect should be balanced with
the very small probability of the presence of a percolated m-SWCNT
in the photoactive composite as discussed in Sec. II.
The results of optical absorption spectra of pure poly
(3-hexiltiophene-2,5-diyl) and produced films with different
SWCNTs concentrations are displayed in Fig. 6. It is evident from
characterization that, with increasing SWCNTs concentration, the
absorption spectra peak moved to the right direction from 520 nm
to 533 nm (cyan shift, i.e., greenish blueshift). Another interesting
point is that, a new peak formed at 550 nm and two absorption
shoulders around 400 and 600 nm were observed. Based on this
result, the insertion of SWCNTs modified the absorption spectrum,
which means that carbon nanotubes modified effectively the polymer
conformation, structure, and ordering properties. SWCNTs increased
inter-chain interactions in the P3HT and modified the charge trans-
port by transforming the structure from 1D to 3D character. Indeed,
by increasing film thickness, the surface resistivity decreased and
absorption increased. Overall, thin films not only can be used as
transparent conductive layer in organic photovoltaics but also could
improve their performance due to the 3D connection with the pho-
toactive composite.
Photoluminescence (PL) spectroscopy is an adequate mecha-
nism to assess the donor/acceptor interface for charge transfer.38–40
Figure 7(a) displays the PL spectra recorded for the photoactive
J. Appl. Phys. 126, 113101 (2019); doi: 10.1063/1.5105388
Published under license by AIP Publishing.
ARTICLE scitation.org/journal/jap
FIG. 6. Normalized absorption spectra of P3HT:PCBM film and with different
wt. % of SWCNTs.
layer containing different SWCNT loadings, recorded for an excita-
tion wavelength of 488 nm. The integration of SWCNTs is seen
clearly to produce a quenching of the PL spectra, which not only
supports the strong interaction between P3HT:PCBM blend and
the SWCNT but also an electron transfer from the conjugated
polymer to the SWCNT. This increase in electron transfer at higher
SWCNT loading is due to the enhancement of the charge dissocia-
tion efficiency at the P3HT:PCBM/SWCNTs interface area, fol-
lowed by an increment in the number of available electron paths.
Su et al.41 established the rule that π-interactions between donor
and acceptor molecules and the carbonaceous basal plane are
responsible for a charge-transfer at their interfaces.
We then investigated the behavior of photovoltaic ITO/
PEDOT:PSS/P3HT:PCBM:SWCNTs/Al with SWCNT concentra-
tions ranging from 0 (reference cell) to 1 wt. %, under AM1.5 illu-
mination. The correlation between the main solar cell parameters,
namely, the short-circuit current density (Jsc), the open-circuit
voltage (VOC), FF, and the power conversion efficiency (η), together
with the measured Hall mobility as a function of the SWCNT loads
are given in Table I (results are averaged over 22 devices). It is
evident that all of the device parameters are directly influenced by
the nanotube doping. As a matter of fact, the Jsc of the pristine
polymer/fullerene cell is of 3.75 mA/cm2, and then improved by
more than 265% to reach its maximum of 9.95 mA/cm2 when
doped with SWCNTs (obtained at 0.5 wt. % loading), and then col-
lapses to 4.28 mA/cm2 at 1 wt. % CNT. The VOC is found to stay
somehow constant (at around 650 mV), while for concentrations
above 0.5 wt. % (i.e., 0.75–1 wt. %), it decays to 550 mV. In distinc-
tion, the FF is enhanced with respect to the SWCNT loads from
48% to 55%. Consequently, the highest PCE is attained for a
SWCNT of 0.5 wt. %. Previously, similar kind of tendency in the
dependency of photocurrent was noticed in polymer/nanotube
solar cells, in which the photocurrent and the carrier mobility
increase as a function of the SWCNT concentrations, with the
maximum value reached at 1 wt. %. The perceived improvement in
126, 113101-7
 Journal of ARTICLE scitation.org/journal/jap
Applied Physics

The integration of SWCNTs in the photoactive layer results in

the creation of extra electron paths through the dispersed carbon
nanotube percolation network, minimizing thereby the charge
recombination phenomenon and improving the transportation of
electrons. In the case of increased concentrations of SWCNTs, it is
believed that the generated photocurrent is restricted by the higher
recombination rate and reduced effective mobility because of
the probable presence of partially and/or totally percolated
m-SWCNTs network. Note that for the conversion of a whole
CNT-bundle to the state of quasimetallic, only one metallic nano-
tube is theoretically sufficient.
The quest for a high open-circuit voltage has always been of a
primary importance and has been of a central focus and discussion
since the beginning of hybrid organic photovoltaic devices system.
Definitely, the classical metal–insulator–metal model suggested by
Parker for the diode scheme39 is not able to interpret the occur-
rence of such a VOC in the present case as our experimental results
show a much higher open-circuit voltage than the calculated one,
i.e., VOC = 0.4 V from ΦITO = 4.7 eV and ΦAl = 4.3 eV.39 Indeed, this
model implies that the photoactive layer has negligible numbers of
intrinsic charge carriers and can be consequently viewed as a perfect
insulator. As a matter of fact, this scheme was already reported for
organic photovoltaic devices based on the pure P3OT polymer.3
Back to our scenario, the photoactive layer formed by the P3HT:
PCBM:SWCNT composite should not be regarded as an insulator at
all because of the electrical contribution of the metallic and semicon-
ducting carbon nanotubes in it. In addition, an Ohmiclike behavior
between SWCNTs and the negative electrode contact is an impera-
tive presumption to apply this mechanism. In this scenario, the
upper limit of VOC could be decided via the calculation of difference
of carbon nanotubes work function and the P3HT:PCBM composite
HOMO level.
Tailoring the carbon nanotube work function has been success-
fully achieved through the intercalation of alkali-metal, including
rubidium, potassium, and cesium,40 and was observed to decrease
FIG. 7. Effect of SWCNTs concentration on (a) photoluminescence spectra and considerably with respect of the amount of the integrated alkali-
the associated (b) J–V curves. metals. As an additional consequence, the Fermi level of the system
is accordingly modified and, hence, metallic and semiconducting
tube bundles become somewhat equivalent (i.e., indistinguishable).
the generated photocurrent is accredited to more effective transpor- The decrease of the work function can be interpreted by the
tation of electrons through the incorporated nanotube percolation charge transfer from the alkali-metal to the CNT, inducing a shift
networks. In the reference device, the dissociation of photogener- of the Fermi level from the conduction band to the vacuum
ated excitons occurs at the interfaces of P3HT:PCBM, and the elec- level.40,41 By adapting this concept to our P3HT:PCBM:SWCNT
trons are transferred to the Al electrodes only by hopping between system, the Fermi level of carbon nanotubes could be affected by
the fullerenes. the bonding of the polythiophene molecules to their sidewall,
further reducing the overall work function. The Fermi level moves
toward the vacuum level after SWCNTs are attached with P3HT:
TABLE I. Device performance with respect to the SWCNT loads.
PCBM. For the photovoltaic device system, reducing the work func-
Photovoltaic cell PEDOT:PSS/P3HT:PCBM:SWCNT/Al tion with the integration of SWCNTs will lead to higher VOC and
should be also driven by the change of the contact resistance at the
SWCNT Hall mobility carbon nanotubes and electrodes interface.
wt. % Jsc (mA/cm2) VOC (V) FF η (%) (cm2/V s) To further understand the charge-transfer mechanisms taking
0 3.75 0.65 0.48 1.17 4.85 × 10−5 place at the interfaces of P3HT:PCBM:SWCNT in devices (for
0.1 4.17 0.63 0.50 1.31 6.55 × 10−4 0.5 wt.% SWCNT), the short-circuit current density was measured
0.5 9.95 0.66 0.54 3.54 9.12 × 10−4 with respect to the light intensity in the 1–100 mW/cm2 range and
1 4.28 0.55 0.55 1.29 2.33 × 10−4 the results are plotted in double logarithmic scale and displayed in
Fig. 8. The attributes of a pristine polymer–fullerene (i.e., P3HT:

J. Appl. Phys. 126, 113101 (2019); doi: 10.1063/1.5105388 126, 113101-8

Published under license by AIP Publishing.
 Journal of
Applied Physics
FIG. 8. Short-current density dependency with the light intensity for configura-
tion with and without SWCNT doping.
PCBM) based device are also displayed for the sake of comparison.
The short-circuit photocurrent (Jsc) is found to follow a power law
dependence expressed by Jsc = Pα, with scaling exponent factors
α = 0.96 and 0.92 for the devices in cases with and without the
doping of carbon nanotubes, respectively. Note that even if this
difference seems small, it is rather about a power law dependency
where α is an exponent factor. Moreover, similar difference values
were already reported in the relevant literature.42,43
The linear dependency of the generated photocurrent suggests
that the losses of charge carrier in the photoactive layer are gov-
erned by monomolecular recombination. The raised value of the
exponent factor α after the tallying of the nanotubes suggests a
decrease in the recombination losses phenomenon due to the
quicker electron transportation via the formed percolated nano-
tubes network.42,43 For both devices, no bimolecular recombination
was observed (i.e., a photocurrent following a square-root depend-
ency with α = 0.5), even at the maximum illumination intensity.
This observation is in good fit with the scheme of the generation
and transport of photocharge carriers in a bulk heterojunction
picture. Indeed, an ultrafast electron–hole separation followed by
their respective transport within the spatially separated networks.
The electrons along the percolated fullerenes and nanotubes move
toward the region of Al electrode while the holes within the
polymer matrix move toward the PEDOT:PSS layer and conse-
quently to the region of ITO electrode.
The observed fall in the mobility for SWCNT concentrations
above 0.5 wt.% (Table I) is most probably due to the increase of
trapping sites, which in turn lead to a suppressed carrier collection
(i.e., the number of extracted carriers decreases) and, hence, the
generated photocurrent decreases. Compared with the pristine
layer, the rougher volume of the photoactive layer when integrating
SWCNTs could decrease the series resistance leading to an increase
in the FF. As a result, the contact area between the photoactive
J. Appl. Phys. 126, 113101 (2019); doi: 10.1063/1.5105388
Published under license by AIP Publishing.
ARTICLE scitation.org/journal/jap
layer and the Al interface increases and hence reduces the series
resistance. As a matter of fact, Abeygunasekara et al.44 reported an
improvement of the power conversion efficiency of PTB7/PC70BM
solar cells by the addition of small quantities of pristine SWCNTs
in the photoactive layer. SWCNTs and purified semiconducting
SWCNTs were added in very low quantities (0.02%–0.04%), which
are two orders of magnitude lower than previously reported value
and resulted in a reduction in the series resistance of the solar cell
with minor changes on the shunt resistance. At higher SWCNTs
concentrations (i.e., above 0.5 wt. %), VOC is observed to decrease.
At these concentrations, the development of electrical short-circuits
resulting from electrically percolated SWCNTs bundles that extend
across the photoactive is highly likely and could be the reason
behind these short-circuits. In sum, the integration of small con-
centrations of SWCNTs within the photoactive layer is seen to con-
siderably improve the device short-circuit current by more than
∼260% resulting in a frank improvement of the PCE by 300%.
Even though these reported PCEs are still relatively low and far
below those attained by the inorganic materials; however, the rela-
tive improvement of the PV performance due to the SWCNTs
incorporation is substantial.
IV. SUMMARY
We have successfully integrated different concentrations
of SWCNTs into P3HT:PCBM polymer/fullerene based hybrid
organic photovoltaic devices. The SWCNT tallying was shown to
enhance both the device short-circuit current and FF, resulting in
an intensification in the photoconversion efficiency by more than
300% compared to the pristine conjugated polymer alone. This
enhancement in the performance of PV is accredited to an
improvement in the excitons’ dissociation efficiency at the
SWCNT/polymer interface and to the faster electron transfer
through the incorporated nanotubes’ percolation paths.
ACKNOWLEDGMENTS
We acknowledge the support from the Natural Science
and Engineering Research Council (NSERC) of Canada for a
Collaborative Research and Development project (No. CRDPJ
461087-13) in partnership with the Raymor Industry Inc. and the
Quebec Prompt Financing ICT R&D Program. We also acknowl-
edge the support from the Qatar Environment and Energy
Research Institute, at Hamad Bin Khalifa University, member of
Qatar Foundation.
The authors declare that they have no conflict of interest.
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