Proceedings of the 15th
IEEE International Conference on Nanotechnology
July 27-30, 2015, Rome, Italy
Perovskite solar cells stabilized by carbon
nanostructure-P3HT blends
S. Casaluci, A. Di Carlo
CHOSE, Center for Hybrid and Organic Solar Energy,
Dept. of Electronic Engineering,
University of Rome “Tor Vergata”, Rome, Italy
e-mail: simone.casaluci@uniroma2.it
Abstract—We present the use of covalently functionalized
carbon nanostructures (CNSs) such as single-wall carbon
nanotubes (SWCNTs) and graphene nanoplatelets (GNPs), as
conductive nanofillers in a P3HT matrix. We propose a simple
approach for the preparation of the active blends used as hole
transport layer (HTL) in mesoporous perovskite solar cells
(PSCs). We demonstrate that for both SWCNT and GNP
nanofillers, power conversion efficiencies (~10%) and shelf life
stabilities (over 3240 hours) are improved with respect to PSCs
using bare P3HT as the HTL.
Keywords—Perovskite Solar Cell; Solar Cell; HTL; Stability;
Carbon nanotubes; Graphene
I. INTRODUCTION
In the last five years, perovskite materials were introduced
as light absorbers in solar cell devices with power conversion
efficiency (Ș) up to 20.1% (certified) [1]. This very high Ș is
correlated to the excellent (opto)electronic properties of this
material such as: direct band gap, broad absorption spectra, and
high mobility of charge carriers [2]. The typical perovskite
solar cells (PSCs) are fabricated using compact and
mesoporous TiO2 as electron transporting layer and 2,20,7,70-
tetrakis-(N,N-di-p-methoxyphenylamine)9,90-spirobifluorene
(Spiro-OMeTAD) as the hole transporting material (HTL) [3].
In order to reduce the costs of PSC technology, conjugated
polymers such as poly(3-hexylthiophene) (P3HT) have been
proposed as a cheaper alternative to Spiro-OMeTAD for both
small and large area devices [4]. Furthermore, Li salts and
pyridine molecules are necessary additives in HTL to achieve
the desired film morphology as well as to improve inter-chain
hopping, with the final aim to increase the PSCs Ș [5].
However, it is well-known that the aforementioned compounds
are corrosive for the perovskite active layer, being detrimental
for the stability and lifetime of PSCs themselves [6]. Thus, in
order to overcome such issues, new materials are currently
investigated both as possible HTL replacements and as
additives. Here, we demonstrate that carbon nanostructures
(CNSs), such as organic functionalized single-wall carbon
nanotubes (SWCNTs) and graphene-oxide derived
nanoplatelets (GNPs), can act as conductive nanofillers of a
P3HT layer used as HTL for hybrid PSCs based on
CH3NH3PbI3, thus providing better performances and
endurance to devices. The use of SWCNTs in HTLs for hybrid
perovskite solar cells has been already reported by the Snaith’s
group [7]. They exploited a P3HT/SWCNTs composite
978-1-4673-8156-7/15/$31.00 © 2015 IEEE
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F. Bonaccorso
Istituto Italiano di Tecnologia, Graphene Labs, Genova,
Italy
T. Gatti, E. Menna
University of Padova, Dept. of Chemical Sciences
Padova, Italy
embedded in a PMMA matrix, with the aim to increase the
devices thermal stability [7]. Snaith and co-workers used
composite material in which P3HT was physisorbed on the
surface of SWCNTs through ʌ-ʌ stacking interactions [7].
Here, we propose an alternative approach making use of
covalently functionalized CNSs as conductive nanofillers in a
P3HT matrix. Moreover, we propose a simpler approach, with
respect to the one reported by Snaith and co-workers [7], for
the preparation of the active blends, avoiding the formation of
clusters (GNPs) or bundles (SWCNTs). These might originate
shortcuts within the HTL, thus lowering the device
performance.
II. SYNTESIS AND MATERIALS
4-Methoxyphenyl substituents were selected to be
covalently bound to the surface of CNSs in order to allow their
efficient dispersion in the semiconducting polymer matrix. The
functionalization reaction was carried out by generating in situ
the diazonium salt of 4-methoxyaniline in the presence of
isopentylnitrite, using 1-cyclohexyl-2-pyrrolidone (CHP) as the
solvent, thus obtaining 4-methoxyphenyl functionalized
SWCNTs (SWCNT-PhOMe) and GNPs (GNP-PhOMe)
(Figure 1) [8].
Fig. 1. Functionalization of SWCNTs and GNPs via addition of the
diazonium salt of 4-methoxyaniline.
The effective incorporation of the functionalized CNSs into
the P3HT matrix has been achieved by means of a thorough
protocol of ultrasonication/centrifugation steps as depicted in
Figure 2 (see experimental section) [9]. Sedimentation-based
separation, as also shown in the past [10][11], permits to
eliminate the insoluble residues. Weight percentages of 4-
methoxyphenyl functionalized CNSs with respect to P3HT
41
were determined by weighting the solid residues after removal
of the supernatant. They were 3% for the SWCNT-
PhOMe/P3HT blend and 4% for the GNP-PhOMe/P3HT
blend. Each mother dispersion thus derived, was further diluted
with the original P3HT dispersion in chlorobenzene, in order to
end up with three different blends having a decreasing weight
percentage of CNSs in P3HT (1%, 2% and 3% for the
SWCNT-PhOMe/P3HT blend and 1%, 2% and 4% for the
GNP-PhOMe/P3HT blend, respectively).

Fig. 4. Optical bandgaps of undoped P3HT and P3HT-CNS Blends.

The optical bandgaps increase upon addition of CNSs to the

P3HT blend, although they remain close (within 0.06eV) to the
value found for P3HT. A similar result was also reported by
Saini [13]. Figure 5 reports the Ș (average on 4 devices) for the
endurance tests of PSCs fabricated with different amounts of
4-methoxyphenyl functionalized SWCNTs (Figure 5a) and
GNPs (Figure 5b) added to P3HT as HTL.
Fig. 2. Scheme of the process carried out to obtain the homogeneous 4-
methoxyphenyl functionalized CNSs/P3HT blends.

III. RESULT AND DISCUSSION

Figure 3 reports the UV-Vis-NIR absorption spectra of
spin-coated films of 3% SWCNT-PhOMe/P3HT blend (red
line), 4% GNP-PhOMe/P3HT blend (blue line) on glass slides.
The spectrum of P3HT (black line) is also reported for
comparison.

Fig. 3. UV-Vis-NIR absorption spectra of spin-coated P3HT, 3% SWCNT-

PhOMe/P3HT blend and 4% GNP-PhOMe/P3HT blend on glass slides.

The absorption spectra of the CNS-P3HT films do not show

significant variations with respect to the one of P3HT film.
This result suggests that the addition of CNSs, in the reported
amounts, does not influence the HTL absorption properties.
The only relevant feature is the slight increase of the absorption
in the NIR region for the 4% GNP-PhOMe/P3HT blend, likely
due to the higher GNP content with respect to SWCNTs in the
blend. Van Hove singularities for SWCNTs are not visible in
the spectrum both due to the low CNS/P3HT ratio and their
partial depression following functionalization [12]. Using
spectrophotometry, by measuring transmittance spectra and
calculating the absorption coefficient, we report in Figure 4 the
optical bandgap value of P3HT and P3HT-CNS blends
extrapolated from direct allowed transitions of the Tauc
formula [13].
Fig. 5. Endurance test for a) devices based on 1%, 2%, 3% SWCNT-
PhOMe/P3HT blends and b) 1%, 2%, 4% GNP-PhOMe/P3HT blends as HTL.
In both graphs the trend efficiency of the same device based on an undoped
P3HT HTL is reported. After 15h all devices were encapsulated.
The best PSCs based on 1% SWCNT-PhOMe/P3HT blends
as HTLs has shown, after 310 hours, higher Ș (Ș= 11.1%) with
respect to the best reference PSC P3HT-based (Ș= 5.2%). Fig.
5a also shows an increase in Ș for all the SWNT-based PSCs
after 310 hour of aging with respect to the as-prepared devices.
The higher Ș is associated with the increase of the photo-
generated current (JSC), being the other device figure of merit,
i.e., open circuit voltage (VOC ~864 mV) and fill factor (FF

42

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~52%), almost unchanged during the endurance test. The
devices we fabricated with the GNP-PhOMe/P3HT blends
have, instead, a different trend with respect to the one reported
for the SWCNTs-based PSCs. Although all the as-prepared
GNP-based PSCs have reported higher Ș (~8-9%) with respect
to the reference PSC (Ș ~6.5%), only the device with 4% GNP-
PhOMe/P3HT blend as HTL maintains constant its Ș during
the endurance test. In fact, the other PSCs reported a drastic
reduction, following the trend of the PSC based on bare P3HT,
in Ș just after encapsulation (15 h) and even higher after 75 h.
Notably, the endurance test (310 h) has demonstrated that the
4% GNP-PhOMe/P3HT and SWCNT-PhOMe/P3HT blend-
based devices have shown in average Ș, 8.8 % 10 %,
respectively, both higher with respect to the reference P3HT-
based PSC (Ș=4%). To further investigate the stability of CNS-
P3HT-based PSCs, we stressed more the endurance tests. In
Figure 6 we report a picture of the devices after 3240 hours
(the PSCs were kept in dark) of aging.
Fig. 6. Photos of PSCs after 3240 h of aging. Top: PSC fabricated with
P3HT. Middle (left to right): devices with 1%, 2% and 4% w/w GNP-
PhOMe/P3HT blend as HTL, respectively. Bottom (left to right): devices with
1%, 2% and 3% w/w SWCNT-PhOMe/P3HT blend as HTL, respectively.
From a simple visual inspection, we have noticed that the
PSC realized with P3HT (see section IV for details) has
undergone color changes from dark/brown to yellow, as show
in Figure 6. Contrary, we did not see such color variation in
CNSs-P3HT devices. Photoelectrochemical tests confirm the
preliminary visual inspection. In fact, as reported in Table 1,
only the CNSs-P3HT-based devices have all cells still active
after 3240 h of endurance tests.
TABLE I. PCE (%) AND NUMBER OF ACTIVE CELLS AFTER 3240 H
After 3240 hours
HTM Average Number of active
PCE (%) cells
P3HT Null Null
1% GNP-PhOMe/P3HT 4.7 2 MR23i Jouan ultracentrifuge equipped with a SWM 180.5
2% GNP-PhOMe/P3HT 3.9 4 swinging bucket rotor (Thermo electron corporation) at 3000
4% GNP-PhOMe/P3HT 3.4 3 rpm for 10 minutes. Absorption spectra of spin coated films
1% SWCNT-PhOMe/P3HT 5.7 4 were carried out with a Varian Cary 5000 spectrophotometer.
2% SWCNT-PhOMe/P3HT 8.7 4
3% SWCNT-PhOMe/P3HT 3.6 4 A. CNSs functionalization
To get insight the mechanism leading to the increase in Ș of
the PSCs based on 4-methoxyphenyl functionalized CNSs-
P3HT as HTL with respect to the bare P3HT counterpart, we
carried out further experiments. Space charge limit current,
SCLC, [14] experiments permitted us to determine the hole
mobility values, see Figure 7 and section IV.C for details.
From the obtained data we can exclude the increase in charge
transport properties as the main mechanism responsible for the
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Ș enhancement. In fact, PSCs based on P3HT-CNS have all
shown a lower hole mobility (e.g., ~2.4×10-4cm2V-1s-1 for 3%
SWCNT-PhOMe/P3HT) with respect to the one based on
P3HT (~3.4×10-4 cm2V-1s-1).
Fig. 7. Hole mobility of bare P3HT and P3HT- GNP-PhOMe and P3HT-
SWCNT-PhOMe extracted by SCLC method.
Possible alternative explanations might derive from
photoinduced electron transfer processes taking place within
the CNSs-P3HT blends themselves or at the
perovskite/polymer and/or polymer/top electrode interfaces. In
fact, these interfaces might be modified by the presence of the
functionalized CNSs. Interface engineering has a key role in
guiding photo-generated processes taking place between
different materials [15]. Charge transfer processes between the
different layers of the PSC can also have a role in determining
the final device performance. In this context, the presence of
CNSs at the aforementioned interfaces might improve local
electrical contacts, driving charge transfer across interfaces
themselves. Further insights into the basic working
mechanisms of these devices are clearly needed and we are
performing other experiments to fully corroborate the
experimental findings that could help to advance both the
performances and stabilities of PSCs over time.
IV. EXPERIMENTAL
All reagents and solvents were purchased from Sigma-
Aldrich and used as received. P3HT was purchased from
Merck (MW = 94.100 g mol-1). HiPco® SWCNTs were
purchased from UnidymTM (lot # P2150) and used as received.
GNPs were purchased from ACS Material, LLC and used as
received. CNSs were dispersed in P3HT by using the
ultrasonicator 3000 (Misonix) with the following pulse
parameters: time on = 3 sec, time off = 3 sec, power level = 2
(4-6 W) for 10 minutes. ultracentrifugation was performed on a
Sonicated dispersions of CNSs (20 mg) in CHP (15 ml)
were treated with 4-methoxyaniline (102 mg, 0.83 mmol) and
heated up to 80 °C while stirring under a nitrogen atmosphere.
Isopentylnitrite (0.11 ml, 0.83 mmol) was then added and the
reaction mixture was left at 80 °C for 4 h. Then, the mixture
was cooled down to room temperature and poured into
methanol (100 ml). The resulting dispersion was centrifuged,
the supernatant was collected and the black residue pelleted at
the bottom of the ultracentrifuge tube was washed with
methanol (5 x 10 ml). The residual carbon material was dried
under vacuum and used in solid form for the subsequent
blending with P3HT.
B. CNSs/P3HT blend formation
P3HT dispersions were prepared by dispersing the polymer
in chlorobenzene at the concentration of 15 mg/ml and by
leaving the resulting dispersion to stir overnight on a hot- plate
at a temperature of 70 °C. 4-methoxyphenyl functionalized
CNSs/P3HT blends were then prepared by mixing the
functionalized carbonaceous nanomaterials (15 mg) in 10 ml of
the P3HT dispersion, followed by ultrasonication,
centrifugation and collection of the supernatant. Weight
percentages of functionalized CNSs with respect to P3HT were
determined by weighting the solid residues left at the bottom of
the ultracentrifugation tube after drying it under vacuum.
C. Device fabrication and characterization
In order to achieve the desired electrode pattern, transparent
glass substrates pre-coated with fluorine-doped tin oxide (FTO)
(Pilkington, 8 Ohm/Square, 25 mm x 25 mm) were etched via
raster scanning laser (Nd:YVO4 pulsed at 30 kHz with average
output power of P =10 W). Patterned substrates were cleaned
by ultrasonic bath, using detergent, acetone and isopropanol. A
compact TiO2 film was deposited onto the FTO surface by
Spray Pyrolysis Deposition technique [16]. In air double
sequential step procedure was used to realize the perovskite
active layer [17]. The HTL was deposited by spin coating at
2000 rpm for 40 s in nitrogen ambient condition. Samples were
introduced into a high vacuum chamber (10-6 mbar) in order to
evaporate Au top electrode (thickness 100 nm) by thermal
evaporation through a shadow mask. Each PSC has an active
area of 0.1 cm2 the anode (2 mm) and the cathode (5 mm)
overlap. Four cells were fabricated on each substrate. After
fabrication, PSCs were kept in a glove box and after 15 hours
were encapsulated with methacrylate glue and glass, and then
left in air. Masked devices (3 x 6 mm aperture) were tested
under a Class A solar simulator (ABET Technologies,
Sun2000) at AM1.5 and 100 mW/cm2. Current-Voltage (IV)
characteristics of the devices were defined by intensity,
measured with a source-meter (Keithley 2420). The light
irradiation level is verified at the quote and position where the
solar cell is placed by means of a calibrated Pyranometer (Skye
SKS1110). To extrapolate the P3HT mobility value, a diode
structure (ITO/PEDOT/P3HT/Al) was fabricated. On a clean
glass/ITO substrate, with identical pattern of solar cell devices,
was spin coated a PEDOT:PSS (Clevios) dispersion. After
annealing at 150 °C for 10 minutes the P3HT was deposed by
spin coating to obtain a thickness of 150 nm. Then 100 nm of
aluminum metal top contact was evaporated. Dedicated shadow
mask was used to realize device with active area of 0.05 cm2.
An automatic custom-made measurement equipment was used
to evaluate IV dark curve from -5V to 5V.
ACKNOWLEDGMENT
We acknowledge PRIN project DSSCX (MIUR) and EU
Graphene Flagship under contract n. 604391
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