Synthetic Metals 269 (2020) 116552

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Synthetic Metals
journal homepage: www.elsevier.com/locate/synmet

Reduced graphene oxide and perylene derivative nanohybrid as

multifunctional interlayer for organic solar cells
Leticia Patricio Christopholi a, Mariana Richelle Pereira da Cunha b, Edna Regina Spada b,
Anderson E.X. Gavim c, Fabio Seiti Hadano c, Wilson José da Silva c, Paula Cristina Rodrigues d,
Andreia Gerniski Macedo a, e, *, Roberto Mendonça Faria b, Jeferson Ferreira de Deus a
a
Graduate Program in Physics and Astronomy, Federal University of Technology, Curitiba, PR, Brazil
b
Institute of Physics, University of São Paulo, São Carlos, SP, Brazil
c
CPGEI, Federal University of Technology, Curitiba, PR, Brazil
d
Graduate Program in Chemistry, Federal University of Technology, Curitiba, PR, Brazil
e
Phantom-g, CICECO – Aveiro Institute of Materials, Department of Physics, University of Aveiro, 3810-193, Aveiro, Portugal

A R T I C L E I N F O A B S T R A C T

Keywords: In this work, reduced graphene oxide:3,4,9,10-perylenetetracarboxylic dianhydride nanohybrid was prepared by
Interlayer a modified Hummers method which resulted in effective functionalization of graphene sheets. In this procedure,
Perylene the perylene molecules were included at the reaction medium of graphene oxide, where the acid promotes
Dipoles
hydrolysis of the anhydride, forming carboxylic acids; these groups react with hydroxyl groups of graphene
Graphene
oxide, generating ester bonds between graphene oxide and perylene, followed by a reduction through thermal
annealing in air. The resulting interfacial nanohybrid film combines optical and electrical features of both ma­
terials, being a promising functional interlayer in organic-inorganic based devices. Herein, the thin film was
tested in organic solar cells; the photovoltaic response pointed out that the dipole character of the nanohybrid
enhances the fill factor and open circuit voltage parameters, when compared with the solar cell without buffer
layer or having a polymeric hole transporting layer. After that, the optimized solar cells displayed open circuit
voltage of 0.76 V, short circuit current density of 11.61 mA/cm2, fill factor of 53 % and power conversion ef­
ficiency of 4.70 % under AM1.5 illumination, where the nanohybrid film may act as a complementary absorbing
layer and as hole injection layer, pointing out the potential use of this compound to improve the photovoltaic
response in solar cells.

1. Introduction as an electrode in OPV devices. However, ITO presents some disad­

Increasing demand for new sources for clean and renewable energy
has leading researchers to synthesize and study new materials and
composites to be applied in organic photovoltaic (OPV) devices [1,2].
Moreover, in order to increase the potential of energy generation and
harvesting, as well as the use in outdoor conditions, this field requires
the development of new electrodes [3,4], air-stable charge injection/­
blocking layers [5,6] and more efficient materials for absorbing light
from the solar spectrum. Besides the intrinsic processes related to the
active layer, mainly at the donor-acceptor interface, the effective charge
collecting at the electrodes is a key factor that also impact the overall
power conversion efficiency. Transparent conducting oxides processed
as thin films, for instance indium tin oxide (ITO), have been widely used
vantages such as hydrophilic character which results in low compati­
bility with organic materials used at the active layer [5], migration of
indium from electrode to active layer, which reduces the stability in
ambient conditions [7], and the work function which does not favor the
charge collection. Therefore, an additional buffer layer is required,
generally being composed of molecules with dipole character and/or
redox active organic materials [8]; this thin layer can tune the work
function due to the presence of dipoles, enhancing the electrode/active
layer interface and the charge injection/collecting processes [9].
In this sense, graphene derivatives thin films have been used as
transparent electrodes in OPV devices [3,10–12]. These films were
produced by chemical vapour deposition and applied as hole trans­
ponting layer (HTL) in solar cells having 2,6-bis(trimethyltin)-4,8-bis

* Corresponding author.
E-mail addresses: gerniski@hotmail.com, agmacedo@utfpr.edu.br (A.G. Macedo).

https://doi.org/10.1016/j.synthmet.2020.116552
Received 7 July 2020; Received in revised form 25 August 2020; Accepted 28 August 2020
Available online 15 September 2020
0379-6779/© 2020 Elsevier B.V. All rights reserved.
L.P. Christopholi et al.
(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b′ ]-dithiophene
(PBDTTT-CT) blended with [6,6]-phenyl-C71-butyric acid methyl ester
(PC71BM) as active layer [10]. The best HTL performance was observed
at the device having graphene derivative growth at 790 ◦ C, attributed to
a higher sp3 character, resulting in average short circuit current (Jsc) of
11.08 mA/cm2, fill factor (FF) of 48.67 %, open circuit voltage (Voc) of
0.63 V and power conversion efficiency (PCE) of 3.43 %.
Improved electronic properties of graphene oxide (GO) have been
achievied by several methods such as partial reduction, thermal treat­
ment, surface modification via non-covalent/covalent bonding [12–16].
The last method involves covalent bonds on the basal plane of the car­
bon lattice, resulting in changes of electronic properties, improved sol­
ubility and processability [12]. This approach was applied for covalent
functionalization of graphene with fluorine and chlorine atoms [13,14],
ammonia [15] and polyaniline [16] with promising results in photo­
voltaics. Air-stable graphene based solar cells have been reported and,
the use of chemicaly stable materials in atmospheric environment, such
as perylene and graphene derivatives, can contribute to increase the
operation lifetime of such devices in air. For instance, GO:MoO3 com­
posite was prepared by mixing these materials in suspension, processed
as thin film (10 nm) through spin coating and applied as HTL in organic
photovoltaics having poly [N-9′ -heptadecanyl-2,7-carbazolealt-5,5-(4′ ,
7′ -di-2-thienyl-2′ ,1′ ,3′ benzothiadiazole)](PCDTBT):PC71BM as active
layer. These devices achieved Jsc of 14.00 mA/cm2, FF of 43.40 %, Voc of
0.64 V and PCE of 4.00 % [17], where the use of oxide-based HTL is an
alternative to increased the stability in air [5,18]. The stability of
PEDOT:PSS and functionalised graphene based devices was studied by J.
N. Colazzo et al. [19], the results pointed out a reduction in the PCE of
ca. 30 % after 30 days in both devices.
In another approach, the well-known perylene derivative denoted as
34,910-perylenetetracarboxylic dianhydride (PTCDA) small molecule
has been chemically modified and used as electron acceptor or as
interlayer in OPVs resulting in solar cells with efficiency up to 18 %
[20]. The pristine PTCDA has a perylene core with two carboxylic acid
anhydride side groups [21,22], this compound and derivatives have
absorption at the visible range with an extinction coefficient of about
104 M− 1 cm-1 [23], high charge mobility at the range of 10-6-10-3
cm2V− 1s− 1 [24–27] and large exciton diffusion length at the order of
several micrometers [28]. However, this compound tends to form iso­
lated domains within the polymer donor, within these domains occurs
the formation of excimers in two nearby PTCDA molecules [29–34].
These excimer states have lower energy and act as a depopulation path
for excited states and thus, limiting the exciton delocalization [35,36].
The photophysics of perylene crystals encapsulated by single layer of
graphene was studied by W. Li et al. [37], the lack of changes in the
emission decay times was attributed to a critical distance for a dipole
interacting with a 2D energy acceptor lower than 20 nm, or equiva­
lently, only the excitons near the top surface of the perylene crystal can
transfer energy to graphene.
In order to reduce the perylene aggregation and to combine the
optical/electrical features of both materials, non-covalent or covalent
functionalisation of graphene with perylene derivatives have also been
explored in OPVs. For instance, F. Pan et al. [38] reported a (N,
N-dimethyl-ammonium N-oxide)propyl perylene diimide doped gra­
phene oxide (PDINO-GO) as cathode for OPVs, their results pointed out
π-π interaction between the ionic functional group with the graphene
layers, the resulting work function could be tuned by changing the ratio
PDINO:GO at the composite and the alkyl group act as spacer for GO
sheets. As cathode in OPVS, the PDINO-GO reduced the surface charge
recombination and the time for charge extraction, these features
impacted positively the Jsc and Voc parameters. Applying the PDINO-GO
in a non-fullerene based device produced with oly[(2,6-(4,8-bis
(5-(2-ethylhexyl-3-fluoro)thiophen-2-yl)-benzo[1,2-b:4,5-b’]dithiophe­
ne))-alt-(5,5-(1′ ,3′ -di-2-thienyl-5′ ,7′ -bis(2-ethylhexyl)benzo[1′ ,2′ -c:4′ ,
5′ -c’]dithiophene-4,8-dione)] (PM6) and the Y6 acceptor molecule
resulted in average Jsc of 24.34 mA/cm2, FF of 73.43 %, Voc of 0.84 V
2
Synthetic Metals 269 (2020) 116552
and PCE of 15.10 %. The pioneer work of S. Wang et al. [39] reported a
hydrothermal treatment of GO and PDI in dimethylformamide, where
the GO acts as a seed to growth PDI wires. This graphene-PDI hybrid was
used at the active layer of OPVs as heterostructure with effective charge
injection from the organic wire to the rGO sheets. These multifunctional
composites have also been used as electrode in sensors [40,41] and as
cathode in batteries [42,43].
In order to obtain non aggregated PTCDA molecules with dipole at
the interface with rGO, herein we report the rGO_PTCDA nanohybrid,
where PTCDA molecules are assembled between the rGO sheets through
a one-pot synthesis method. The potential use of this composite as a
complementary light absorbing interlayer in OPV devices was also
evaluated. PTCDA molecules were added at the synthesis of graphene
oxide, processed as thin films followed by a reduction step using thermal
annealing. This procedure presents advantages when compared with
gas-phase deposition in ultra-vacuum, where the PTCDA molecules are
deposited only at the surface of graphene [44], using mechanical
mixture of GO and PTCDA in solution, which requires a post-deposition
thermal annealing up to 400 ◦ C [43] or hydrothermal treatment [45].
The insertion of PTCDA molecules at the interlayer region of graphene
can improve the interaction between these two materials and principally
reduces the tendency of PTCDA to form isolated and micro-sized ag­
gregates in suspensions. As described previously, this tendency limits
the application of PTCDA in OPV devices.
2. Materials and Methods
2.1. Materials
Graphite powder (40 μm in size, spectral pure, Synth), 34,910-pery­
lenetetracarboxylic dianhydride (PTCDA, Aldrich®), potassium per­
manganate (KMnO4, Reatec), sodium nitrate (NaNO3, Dinâmica),
surfuric acid (H2SO4, 100 %, Reatec), hydrogen peroxide (H2O2,
Dinâmica), poly[[4,8-bis[5-(2-ethylhexyl)-2-thienyl]benzo[1,2-b:4,5-
b′ ]dithiophene-2,6-diyl][2-(2-ethyl-1-oxohexyl)thieno[3,4-b]thio­
phenediyl]] copolymer (PBDTTT-CT, Aldrich) and poly({4,8-bis[(2-
ethylhexyl)oxy]benzo[1,2-b:4,5-b′ ]dithiophene-2,6-diyl}{3-fluoro-2-
[(2-ethylhexyl)carbonyl]thieno[3,4-b]thiophenediyl}):phenyl-C71-
butyricacidmethylester (PC71BM,American Dye Source, Inc) were used
without further purification.
2.2. Synthesis of GO_PTCDA and rGO_PTCDA nanohybrid
GO_PTCDA nanohybrid composite was prepared by a modified
Hummers method from the route proposed by J. P. Roukeet al. [46]. This
synthesis was performed in the following steps:
a) intercalation step: a mixture of graphite (2 g) and PTCDA (2 g) was
washed and dried, then this graphite:PTCDA powder was added to a
beaker containing NaNO3 (3 g) dissolved in 100 mL of H2SO4.This
mixture was kept under magnetic stirring for 2 h;
b) oxidation step: KMnO4 (15 g)was slowly added into the suspension,
in order to control the temperature, the suspension remained under
magnetic stirring during 7 days.
c) exfoliation step: This procedure was performed by the addition of
100 mL of H2 SO4 / H2O2 solution (1:4 ratio), under magnetic stirring for
3 h; after each time 100 mL was added Therefore, the suspension was
filtered and the obtained material (sludge) was washed in 110 mL of
H2SO4/H2O2/H2O solution 1:5:5 ratios upon magnetic agitation for 2 h,
then filtered and washed with deionized water, kept under magnetic
stirring and filtered again. The resultant material (sludge) was sus­
pended in 1 L of water for storage. In order to convert the GO_PTCDA
nanohybrid to rGO_PTCDA nanohybrid, the sludge was filtered, dried at
room temperature and then thermally annealed at 300 ◦ C by 30 min in
air.
L.P. Christopholi et al.
2.3. Synthesis of GO_PTCDA and rGO_PTCDA blend
The GO compound was prepared following the procedure describe
above. However, in this case, 2 g of PTCDA was added to the as prepared
GO aqueous suspension, remaining upon ultrasonic stirring during 1 h
and magnetic stirring during 5 h. Then, the suspension was filtered and
washed with deionised water, kept under magnetic stirring and filtered
again. The resultant material (sludge) was suspended in 1 L of water for
storage. In order to convert the GO_PTCDA blend to rGO_PTCDA blend,
the sludge was filtered, dried at room temperature and then thermally
annealed at 300 ◦ C by 30 min in air.
2.4. Characterisation
Transmission electron micrographs (TEM) were obtained on a JEOL
JEM1200EX-II, operating at 120 kV, using Formvar/Carbon mesh 200
Cu grid substrates, in which drops of the nanohybrid suspension were
deposited and let to dry. Selected area electron diffraction (SAED) was
employed to crystal structure determination with the same apparatus
used for TEM. Atomic force microscopic (AFM) images were acquired
from films using a Nanoscope III scanning probe microscope (Digital
Instruments).
Ultraviolet-Visible (UV–vis) aborbance/transmittance spectra were
recorded using a FEMTO 800 XI and Shimadzu UV-3600 spectropho­
tometer. In order to acquire these spectra from rGO_PTCDA films, the
initial aqueous suspension was filtered using a 0.45 μm membrane and
then spin casted onto quartz or glass/ITO substrates at 2000 rpm. Sub­
sequently, to convert GO to rGO these films were thermally annealed at
300 ◦ C during 30 min in air. Raman scattering spectra were obtained
with a confocal Raman Alpha 300R microscope (WiTec), the laser
excitation at 532 nm was employed to acquirethe Raman scattering
response. Only freshly prepared nanohybrids were used. Fourier trans­
formed infrared spectroscopy (FTIR) spectra were recorded in the range
400–4000 cm− 1, using an attenuated total reflectance accessory in a
Varian 640-IR Spectrophotometer and KBr as the mulling agent. Crys­
talline structure was characterized by X-ray diffraction (XRD) carried
out from powders using a XRD-Shimadzu XRD-700 or an Empyrean X-
ray diffractometer with Cu Kα radiation, and X-ray photoelectron
spectroscopy (XPS) spectra were acquired in an Ultra High Vacuum
(UHV) system with a base pressure of 2 × 10–10 mbar located at TEMA,
University of Aveiro. The system is equipped with a hemispherical
electron energy analyzer (SPECS Phoibos 150), a delay-line detector and
a monochromatic AlKα (1486.74 eV) X-ray source. High resolution C 1s
spectra was recorded at normal emission take-off angle and with a pass-
energy of 20 eV, which provides an overall instrumental peak broad­
ening of 0.5 eV. UPS was performed in the same system but by using a He
I (21.2 eV) and He II (40.8 eV) UV lamp. Its resolution is slightly better
than 150 mV.
Emission and excitation spectra were recorded at 300 K on a Fluo­
rolog–3 JobinYvon–Spex (Model FL3− 2 T) with a modular double
grating excitation spectrometer (fitted with a 1200 grooves mm1 grating
blazed at 330 nm) and a TRIAX 320 single-emission monochromator
(fitted with a 1200 grooves/mm grating blazed at 500 nm, reciprocal
linear density of 2.6 nm mm-1), coupled to a R928 Hamamatsu photo­
multiplier, using the front face acquisition mode. The excitation source
was a 450 W Xe arc lamp, and the emission spectra were corrected for
detection and optical spectral response of the spectrofluorimeter, while
the excitation spectra were corrected for the spectral distribution of the
lamp intensity using a photodiode reference detector. Time resolved
fluorescence measurements were performed with a TRIAX 320 emission
monochromator (Fluorolog-3, Horiba Scientific) coupled to a TBX-04
photomultiplier tube module (950 V). For the excitation, pulsed diode
light sources (Nano-LED-390, peak at 388 nm) from Horiba Scientific
were used.
3
Synthetic Metals 269 (2020) 116552
2.5. Production of photovoltaic devices
In order to evaluate the performance of rGO_PTCDA film as an
intermediary layer in bulk heterojunction OPV devices, this material
was processed as a thin film onto cleaned and pre-patterned glass sub­
strate coated with a thin layer of ITO (8–12 Ω/sq, thickness 120 nm,
Delta Technologies). Prior the deposition of rGO_PTCDA, the glass/ITO
substrate was cleaned with sequential washing in ultrapure water,
Extran, acetone and isopropyl alcohol [47]. The GO and GO_PTCDA
aqueous suspension (4 mg/mL) were filtered using a 0.45 μm membrane
and then, spin casted onto glass/ITO substrate at 2000 rpm. Subse­
quently, in order to convert the GO to rGO and GO_PTCDA to
rGO_PTCDA, the films were thermally treated at 300 ◦ C for 30 min in air
[48–50]. In fact, this procedure results in partially reduced GO, since the
formation of carbonyl groups also occurs upon thermal annealing per­
formed in ambient atmosphere [51]. Further, the active layer composed
of PBDTTT-CT:PC71BM (1:1.5, 20 mg/mL in chlorobenzene, 3 % v/v 1,
8-diiodooctane) was deposited onto the substrate by spin coating at
1000 rpm during 60 s, at room temperature under inert atmosphere;
these PBDTTT-CT:PC71BM films exhibited thickness of about 110 nm.
Sequentially, the active layer was washed with 100 μL of anhydrous
methanol upon 4000 rpm during 40 s. Finally, Ca (15 nm) and Al (70
nm) films were thermally evaporated onto the active layer through a
shadow mask (active area of 4.5 mm2) Moreover, a reference device
(without buffer layer) was built for terms of efficiency comparison. The
photovoltaic parameters were evaluated upon white illumination (100
mW/cm2) from a Solar Simulator Oriel Class AAA (AM 1.5 G filter) and a
Keithley 2400 electrometer. Average PCE and the corresponding
standart deviation were obtained from 2 batches with 6 devices each.
3. Results and discussion
3.1. Morphology and structure of rGO_PTCDA
Fig. 1 shows SEM and TEM images acquired from PTCDA, which is
composed mainly by nanorods arising from the 1D stacking of perylene
molecules. Moreover, the rGO_PTCDA blend, produced by adding the
PTCDA at the suspension of GO followed by a reduction to convert GO to
rGO, presented morphology with heterogeneous distribution of PTCDA
onto the rGO stacked sheets, while the images acquired from
rGO_PTCDA nanohybrid also presented the typical morphology of gra­
phene sheets with size dimension ranging from 0.2 μm up to 20 μm with
no phase segregation of PTCDA molecules, indicating an effective
intercalation with rGO sheets. Moreover, the energy dispersive X-ray
(EDX) analyses pointed out the increase of the amount of oxygen at the
rGO_PTCDA nanohybrid, indicating that the PTCDA molecules are pre­
sent at the surface of rGO. TEM image also shows that the rGO sheets are
decorated with PTDCA molecules; this was evidenced at the SAED
pattern. Moreover, in accordance with the XRD results presented in
Fig. 2, a slight increase in the interplanar distance between the graphene
sheets (~ 0.1 Å) is an indication that the PDCTA molecules are
distributed along the surface of the rGO sheets. The absence of PDCTA
diffraction peaks suggests that the molecule is randomly dispersed in the
rGO matrix, similarly to the potassium-neutralized perylene tetra­
carboxylic derivative - rGO composite [52]. Moreover, the low intensity
peak around 2θ = 8− 11◦ (d~10 Å) is possible correlated with interca­
lated PTCDA molecules and rGO sheets [53,54].
FTIR spectra presented in Fig. 3 point out that in the rGO_PTCDA
nanohybrid the perylene can be covalently linked to rGO structure. By
adding perylene to the reaction medium, the acid would promote hy­
drolysis of the anhydride, forming carboxylic acid. Part of these groups
could react with − OH groups of rGO, generating an ester bond between
rGO and perylene. This assumption is based on the presence of peaks at
1730, 1175 and 1069 cm− 1 attributed to the stretching of the ester type
C=O and C− C− O bonds, respectively. A proposal for the structure of
rGO_PTCDA nanohybrid is presented in Fig. 4.
L.P. Christopholi et al. Synthetic Metals 269 (2020) 116552

Fig. 1. SEM, TEM images and SAED pattern acquired from PTCDA, rGO_PTCDA blend and rGO_PTCDA nanohybrid.

Fig. 3. FTIR spectra acquired from of rGO, PTCDA, rGO_PTCDA blend and
rGO_PTCDA nanohybrid.
Fig. 2. XRD patterns acquired from rGO_PTCDA, rGO and PTCDA powders.

4
L.P. Christopholi et al.
Fig. 4. Proposed chemical structure for rGO_PTCDA nanohybrid.
XPS and UPS measurements were used to evaluate possible chemical
interactions between the rGO sheets and PTCDA molecules. The C1s
spectrum of rGO_PTCDA (Figure S2) could be fitted by at least five
contributions arising from the presence of C− C/C=C (284.44 eV), C− N
(285.67 eV), C− O (286.55 eV), O− C− O (288.10 eV) and O− C=O (288.5
eV) bonds [50]. Comparatively with the XPS spectrum acquired from
rGO, the relative intensity of the O− C=O band (288.5 eV) increased at
the rGO_PTCDA composite due to increased amount of carboxyl groups,
probably due to the presence of the ester bond between perylene and
rGO, as suggested by the FTIR results. The He-I UPS valence band
spectra of rGO_PTCDA is presented in Fig. 5, and this curve shows a
broad band from 12.3 eV to 4 eV corresponding to the hybridization of
C2p and O2p in the neighboring molecules and graphene sheets along
with a shoulder at 5.4− 3.45 eV attributed to carbon-π [55]. Moreover,
the inset shows the high binding energy cut-off, this spectra region was
used to estimate the work function (φ) of the surface by the energy
difference between the Fermi level and the high binding energy cut-off
from the He I excitation energy (21.2 eV), resulting in a φ=4.32 eV
followed by a step at φ=4.42 eV, which can be possible assigned to the
rGO [56,57] and rGO_PTCDA nanohybrid, respectively. In this sense, P.
V. Kumar et al. [56] showed that the work function of rGO could be
increased by interaction with oxygen containing functional groups,
therefore this sight increase can be explained by the presence of the
carboxylic groups of PTCDA within the rGO sheets.
Furthermore, rGO_PTCDA nanohybrid film showed reduced sheet
resistance and higher conductivity when compared with rGO film, as
presented in Table 1. Lower electrical resistivity of rGO_PTCDA nano­
hybrid arises from both strong π–π conjugation architecture between the
high orderly arranged PTCDA molecules between the rGO sheets, which
enhances the charge carriers transfer perpendicularly to the rGO layer-
Fig. 5. UPS (He-I line) spectrum acquired from rGO_PTCDA nanohybrid. Inset:
a magnification of the high binding energy cut-off region.
5
Synthetic Metals 269 (2020) 116552
stacked perylene core planes, and the crystalline order of rGO, which
effectively avoids the carriers scattering from defects. Some values re­
ported at the literature from rGO and PEDOT:PSS based HTL [58–63] are
summarised at Table S1.
Results concerning the optical features (transmittance, UV–vis
absorbance and emission spectra) are presented in Figure S3 and Fig. 6.
The absorbance spectrum, Figure S3, acquired from rGO presents a band
with maxima at 264 nm and absence of absorption at the visible range, a
characteristic of graphene derivatives. Absorbance spectrum acquired
from PTCDA molecules presents sharp transitions assigned to the spin
allowed-singlet to singlet transitions at 428 nm, 455 nm, 483 nm and
520 nm and a low intensity shoulder at the region between 550 nm–650
nm assigned to aggregate state arising from the π-π orbital overlap of
closely stacked PTCDA molecules [64], which is similar to aggregate
states observed in organic crystals such as tetracene [65] and C60 [66].
Therefore, the combination of rGO and PTCDA materials is interesting
since they have complementary absorbance spectra, as indicated by the
resulting absorbance spectrum. Moreover, a rGO_PTCDA film with
thickness of 40 nm was prepared to allow ta comparison with the
absorbance spectrum of PBDTTT-CT donor copolymer used at the active
layer. Despites some overlapped regions, the results pointed out a
complementary absorbance contribution of rGO_PTCDA between
400− 550 nm. At the solar cells the thickness of rGO_PTCDA films were
~ 10 nm resulting in high transmittance at the visible range (80 ± 7 %)
and thus, they can be applied between the transparent electrode and the
active layer. The transmittance spectra acquired from substrate, rGO and
rGO_PTCDA are presented at Fig. 6a. Another feature observed at the
emission spectra refers to the aggregation of PTCDA molecules, Fig. 6b,
where the luminescence from PTCDA and rGO_PTCDA are compared.
The PTCDA solution presents a band centered at 672 nm attributed to
the excimer emission, while the nanohybrid display the characteristic
emission of the isolated perylene monomers (ca.534 nm, 575 nm and
622 nm) with a short decay time of 4.25 ns measured upon excitation at
390 nm while monitoring the emission at 532 nm (Figure S4). This result
also indicates that the PTCDA molecules are inserted between the rGO
lamellae instead form isolated aggregates.
3.2. Performance of rGO_PTCDA nanohybrid as interlayer in organic
photovoltaics
To evaluate the performance in OPV devices, rGO_PTCDA nano­
hybrid was processed as a thin film onto glass/ITO substrate by spin
coating method from aqueous suspension, resulting in a thickness of
approximately 5− 10 nm and root mean squared roughness (Rrms) of 3.5
nm. Moreover, as described at the experimental procedure, PBDTTT-CT
copolymer and PC71BM molecules were used at the active layer as donor
and acceptor materials, respectively. The chemical structures and
schematic representation of the resulting solar cell are presented at the
Fig. 7.
As indicated by the UPS results presented at Table 1, rGO_PTCDA
nanohybrid presents a work function at the range of 4.32− 4.42 eV. It is
well known that the charge transfer mediated by thermionic processes at
room temperature occurs until energy barrier values of about 0.5− 0.6
L.P. Christopholi et al.
Table 1
Values of work function, sheet resistance and conductivity measured from rGO, rGO_PTCDA nanohybrid films.
Compound Thickness Work function from UPS (eV)
rGO_PTCDA nanohybrid ~10 4.32− 4.42
rGO ~10 4.30
Fig. 6. a) Transmittance spectra acquired from glass/ITO substrate, glass/ITO/rgO and glass/ITO/rGO_PTCDA. The rGO and rGO_PTCDA films were both prepared
by spin coating 100 μL of aqueous suspension (4 mg/mL) at 2000 during 60 s in air, followed by a thermal annealing at 300 ◦ C in air and b) emission spectra acquired
from rGO_PTCDA and PTCDA.
eV [67] and thus, since the PTCDA molecules have absorbance at the
visible range, they can act as donor material for PC71BM molecules, due
to a low energy barrier of ca. 0.45 eV between the work function of
GO_PTCDA (nanohybrid) and the LUMO level of PC71BM. Moreover,
considering the presence of free PTCDA molecules with LUMO level
localized at the range of 4.6–4.8 eV [68], these free PTCDA molecules
can also act as hole injection material for PBDTTT-CT copolymer
because of the low energy barrier of ca. ~0.2− 0.4 eV between the LUMO
(free PTCDA) and the HOMO (PBDTTT-CT). Fig. 8a presents the relative
energy level position for all layers used at the solar cell device.
Solar cells without hole transporting/injection layer or with rGO film
were also prepared to allow a comparison with the device having the
rGO_PTCDA nanohybrid as an interlayer. J–V curves acquired at dark
from ITO/rGO_PTCDA/PBDTTT-CT:PC71BM/Ca/Al devices showed
diode characteristic behavior with rectification factor of about ~103, in
the -2 to 2 V range, while the corresponding device without HIL/HTL
exhibits a rectification factor of ~102 at the same voltage range (see
Fig. 9a). Table 2 shows the classical parameters of the built solar cells
(Jsc, Voc, FF, and η) as well as their series (Rs) and shunt (Rsh) resistances.
Both increased rectification and photovoltaic response in the solar cell
having rGO_PTCDA nanohybrid as interlayer, shown in Fig. 9, can be
attributed to enhanced built-in potential across the device due to the
presence of dipoles along the rGO and PTCDA bonds, which leads to
higher work function at the substrate and a better ohmic contact be­
tween the electrode and the active layer, increasing the photo generated
charge-carrier collection.
As indicated in Fig. 4, the covalent bond between PTCDA and rGO
surface induces the formation of dipoles. In accordance with U. Würfel
et al. [69], the presence of the negative end of the dipole facing the pho­
toactive layer would attract positive charge carriers and thus, leading
holes to accumulate next to the electrode, resulting in efficient separation
of photogenerated charge carriers. These authors showed that the oppo­
site configuration, with positive side of the dipole facing the photoactive
layer, resulted in a reduced work function, improving the electron
extraction and increasing FF and Voc parameters in this inverted solar
6
Synthetic Metals 269 (2020) 116552
Sheet resistance (kΩ/◻) Conductivity (S/m)
3.00 384
32.00 140
cells. Despite the large HOMO–LUMO gap from molecules such as histi­
dine, sarcosine and phenylalanine, the dipole layers contributed effec­
tively to the charge extraction by the modified electrode.In this sense,
PTCDA molecule does not exhibit a permanent dipole; however, the co­
valent bond at the rGO surface leads to the formation of several dipoles
along the PTCDA and rGO link. Due to the slightly increased work function
of ITO electrode modified with rGO_PTCDA, when compared with rGO,
the negative side of the overall resulting dipoles are facing the active layer
and thus, favoring the hole collecting and tunneling processes, as shown at
Fig. 8b, resulting in increased Voc parameter. The influence of the buffer
layer on the Voc values has been reported [6,69,70], being mainly influ­
enced for intensity of illumination, thickness of the active layer as well as
the concentration of holes. Moreover, as presented at Table 2, solar cells
produced with rGO_PTCDA presented superior photovoltaic response
even when compared with the standard devices produced without inter­
layer, which resulted in PCE of 2.84 %, with rGO or PEDOT:PSS as hole
transporting layer, which resulted in PCE values of 2.00 % and 3.70 %,
respectively. The rGO_PTCDA thin films were processed by spin-coating
from suspension, same method used to process the PEDOT:PSS films.
However, concerning the application of rGO_PTCDA in solar cells, the
filtering procedure prior the deposition allowed the removal of higher
sheets and production of uniform rGO_PTCDA films, scanning electronic
microscopy images are presented at Figure S5. Devices were produced
with filtered and non-filtered suspensions; the best results were achieved
with the films produced from filtered suspension. The low response ach­
ieved from device having the rGO film is related with the resulting
morphology of rGO film processed by spin coating, more inhomogeneous
when compared with the rGO_PTCDA film deposited using similar pa­
rameters (concentration, solvent and rotation during the deposition). The
rGO film presented black spots along the surface indicating non uniform
coating, even using a filtered suspension. However, comparing the PCE
achieved at the device having the rGO_PTCDA nanohybrid as interlayer
(PCE = 4.7 %) with a device reported using uniform graphene oxide de­
rivative film produced by CVD method at reference [11] with the same
active layer (PCE = 3.43 %), the rGO_PTCDA showed higher PCE
L.P. Christopholi et al. Synthetic Metals 269 (2020) 116552

Fig. 7. Chemical structure of a) PBDTTT-CT (donor), b) PC71BM (acceptor) and c) schematic representation of the glass/ITO/rGO_PTCDA/ PBDTTT-CT :PC71BM/Ca/
Al solar cell device used to test the rGO_PTCDA nanohybrid as interlayer for OPV devices.

Fig. 8. a) Energy level diagram for glass/ITO/rGO_PTCDA/

PBDTTT-CT:PC71BM/Ca/Al solar cell device (photogenerated
electron-hole pairs are depicted in red, while the hole injection
process is depicted in green, green dashed bar corresponds to
the LUMO level region of free PTCDA molecules) and b)
scheme presenting the dipole orientation at the ITO surface
and the positive charge collecting from the active layer (For
interpretation of the references to colour in this figure legend,
the reader is referred to the web version of this article).

indicating that, in fact, the synergy between the rGO and PTCDA mole­
cules is beneficial for the photovoltaic response.
At the literature, there are reports about optimized ITO/PEDOT:PSS/
PBDTTT-CT:PC71BM/Ca/Al devices with efficiencies over 6.00 % [71]
however, in this work to allow a comparison, the PEDOT:PSS based
device was fabricated with the same parameters used to produce the
control device (without interlayer) and having rGO as an interlayer.
Therefore, comparatively, the results point out that the rGO_PTCDA
nanohybrid is a promising material for interlayer in organic photovol­
taics; arising improved resulting Voc, reduced series resistance and

7
L.P. Christopholi et al. Synthetic Metals 269 (2020) 116552

Fig. 9. J-V curves acquired at the a) dark and b) upon illumination from glass/ITO/X/PBDTTT-CT:PC71BM/Ca/Al where X= without HTL, rGO, PEDOT:PSS
or rGO_PTCDA.

Table 2
Photovoltaic parameters.
interlayer Jsc (mA/cm2) Voc (V) FF (%) Rs (Ωcm2) Rsh (Ωcm2) PCEaverage (%) PCEmax (%)

– 10.23 0.64 44 21 203 2.60 ± 0.20 2.84

rGO 9.42 0.65 33 30 73 1.90 ± 0.10 2.00
PEDOT:PSS 11.43 0.73 44 24 237 3.31 ± 0.30 3.70
rGO_PTCDA nanohybrid 11.61 0.76 53 11 241 4.13 ± 0.40 4.70

improved charge extraction due to the presence of dipoles along with the
rGO_PTCDA bonds.
4. Conclusions
Covalent linked rGO_PTCDA nanohybrid was prepared through a
modified Hummers method; where the PTCDA molecules are included at
the reactional medium of GO. Using this procedure, the acid promotes
hydrolysis of the anhydride, forming carboxylic acids which react with
− OH groups of GO, generating an ester bond between GO and perylene.
As a result, there are dipoles along the GO (or rGO) and PTCDA bond,
improved electrical features such as low resistivity and increased work
function when compared with rGO. Applying this compound as an
interlayer in organic solar cells, it was verified superior photovoltaic
response, arising from the dipole contribution to the photovoltaic pa­
rameters and charge collecting at the modified electrode.
CRediT authorship contribution statement
Leticia Patricio Christopholi: Conceptualization, Investigation,
Data curation, Writing - original draft. Mariana Richelle Pereira da
Cunha: Investigation, Data curation, Writing - original draft. Edna
Regina Spada: Investigation, Data curation, Writing - original draft.
Anderson E.X. Gavim: Investigation, Data curation. Fabio Seiti
Hadano: Investigation, Data curation. Wilson José da Silva: Investi­
gation, Data curation, Resources. Paula Cristina Rodrigues: Concep­
tualization, Investigation, Data curation, Writing - original draft,
Resources. Andreia Gerniski Macedo: Investigation, Data curation,
Writing - original draft, Resources, Supervision, Project administration,
Funding acquisition. Roberto Mendonça Faria: Investigation, Funding
acquisition. Jeferson Ferreira de Deus: Investigation, Data curation,
Writing - original draft, Resources, Supervision, Project administration,
Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was financially supported by Fundação Araucária
(grants327/2014), Fundação Parque Tecnológico Itaipu (FPTI-BR, call
FA 21/2018), Conselho Nacional de Desenvolvimento Científico e Tec­
nológico (CNPq, grants PQ2 308129/2018-0, Equinor 440078/2019-9),
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES,
PVEX 88881.171856/2018-01 and Finance Code 001) and Serrapilheira
Institute (Grant number Serra-1709-17054). The authors also acknowl­
edge the INEO (Instituto Nacional de Eletrônica Orgânica), LAMAQ-
UTFPR by spectroscopy facilities, CME-UFPR and CMME-UTFPR by
AFM and SEM/TEM facilities, respectively. This work was also devel­
oped within the scope of the project CICECO-Aveiro Institute of Mate­
rials (UIDB/50011/2020 & UIDP/50011/2020) financed by national
funds through the Fundação para a Cieˆncia e a Tecnologia/Ministério da
Educação e Cieˆncia (FCT/MEC) and co-financed by FEDER under the
PT2020 Partnership Agreement.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.synthmet.2020.11
6552.
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