Review Article: A Review On The Efficiency of Graphene-Based BHJ Organic Solar Cells

Hindawi Publishing Corporation
Journal of Nanomaterials
Volume 2015, Article ID 406597, 15 pages
http://dx.doi.org/10.1155/2015/406597
Review Article
A Review on the Efficiency of Graphene-Based
BHJ Organic Solar Cells
Alejandro Manzano-Ramírez,1 Edgar J. López-Naranjo,2

Wole Soboyejo,3 Yunny Meas-Vong,4 and Bertrand Vilquin5
1
CINVESTAV-IPN Unidad Querétaro, 76230 Santiago de Querétaro, QRO, Mexico
2
Universidad Autónoma de Nayarit, Ciudad de la Cultura Amado Nervo s/n, 63190 Tepic, NAY, Mexico
3
Princeton Institute of Science and Technology of Materials (PRISM), Bowen Hall, 70 Prospect Street, Princeton, NJ 08544, USA
4
CIDETEQ, Parque Tecnológico Querétaro Sanfandila, 76703 Pedro Escobedo, QRO, Mexico
5
Univertisté de Lyon, École Centrale de Lyon, Institut des Nanotechnologies de Lyon, 36 Avenue Guy de Collongue,
69134 Ecully Cedex, France
Correspondence should be addressed to Alejandro Manzano-Ramı́rez; [email protected]
Received 19 May 2015; Revised 30 August 2015; Accepted 31 August 2015
Academic Editor: Michal Otyepka
Copyright © 2015 Alejandro Manzano-Ramı́rez et al. This is an open access article distributed under the Creative Commons
Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is
properly cited.
Graphene, a material composed of one-atom-thick planar sheets of sp2 -bonded carbon atoms with a two-dimensional honeycomb
structure, has been proposed for many applications due to its remarkable electronic, optical, thermal, and mechanical properties.
Its high transparency, conductivity, flexibility, and abundance make it an excellent material to be applied in the field of
organic photovoltaic cells, especially as a replacement for transparent conducting oxide electrodes. However, graphene has been
demonstrated to be useful not only as substitute for indium tin oxide electrodes, but also as cathode, electron acceptor, hole
transport, and electron extraction material. Thus, in this work, we summarize and discuss the efficiency of bulk heterojunction
devices using graphene as a main constituent.
1. Introduction develop viable devices: the donor-acceptor bilayer and the so-
called bulk heterojunction (BHJ), which is represented in the
Organic solar cells (OSCs) belong to the class of photovoltaic ideal case as a bicontinuous composite of donor and acceptor
devices known as excitonic solar cells, which are char- phases, thereby not only maximizing the donor/acceptor
acterized by strongly bound electron-hole pairs (excitons) interface for efficient exciton dissociation, but also forming
that are formed after excitation with light. Strongly bound a nanoscale interpenetrating network for charge transport to
excitons exist in these materials as a consequence of the the electrodes [1, 2] (Figure 1). Organic solar cell research and
low dielectric constants in the organic components, which device development still have a long way to go to compete
are insufficient to affect direct electron-hole dissociation, as with inorganic solar cells. The efficiency of inorganic devices
it is found in their high dielectric inorganic counterparts. can top 20% and the development of inorganic thin-layer and
In excitonic solar cells, exciton dissociation occurs almost multijunction instruments will likely lead to even better per-
exclusively at the interface between two materials of different formance. In contrast, the best OSCs, based on the BHJ con-
electron affinities (and/or ionization potentials): the electron cept, operate at a maximum of ∼8.0% efficiency. However, due
donor and the electron acceptor. To generate an effective to its low cost, lightweight, high availability of materials, and
photocurrent in these organic solar cells, an appropriate easy manufacturing, the OSCs technology turns very appeal-
donor-acceptor pair and device architecture must be selected. ing as it could theoretically produce highly efficient devices
Two main approaches have been explored in the effort to [3–5].
2 Journal of Nanomaterials
Solar light
Cathode
Anode
h+ e− h+ e− h+ e− h+ e−
(a) (b) (c) (d)
Figure 1: BHJ cell operation mechanism. (a) Exciton generation, (b) exciton dissociation, (c) charge formation, and (d) charge transport and
collection.
Based on the simple consideration that low band gap

materials have the possibility to improve the efficiency of
photovoltaic devices due to a better overlap with the solar
spectrum, it is expected that, for a maximum photon harvest-
ing in the OSCs, low band gap materials will be employed.
The use of this type of materials results in higher currents that
can lead to higher power conversion efficiency (PCE). Poly-
3-hexylthiophene (P3HT), one of the most used materials as
donor in a BHJ device, exhibits a band gap of 650 nm (1.9 eV)
and thus only has the possibility to harvest up to 22.4% of
the available photons giving a maximum theoretical current
density of 14.3 mAcm−2 . If P3HT is applied in a BHJ device,
coupled with the most commonly used acceptor (i.e., phenyl-
C61 -butyric acid methyl ester, PCBM), the band gap extends
to 1000 nm allowing for absorption of 53% of the available
photons giving a maximum current density of 33.9 mAcm−2 .
However, in practical terms these values cannot be achieved
and the real performance of a P3HT : PCBM system is around
its optimal of about 5% which is lower than a quarter of a
silicon solar cell’s optimal [6, 7].
Graphene, a zero-band-gap semiconductor is a rising star
in materials science (Figure 2). It shows a two-dimensional Figure 2: Representation of graphene structure.
(2D) structure consisting of sp2 -hybridized carbon and it
is also the thinnest known material in the universe and
the strongest ever measured [8–11]. It exhibits remarkable (silicon dioxide) layer on top. The third route involves
electronic and mechanical properties and a considerable the epitaxial growth of graphene on electrically insulating
number of new optical effects that have not been observed in substrates like silicon carbide [23]. However, the second and
other materials [12, 13]. Its remarkably high carrier mobility, third methods are unsuitable for large-scale preparation of
wide absorption spectral range, and high optical transparency graphene for the fabrication of polymer nanocomposites [19].
indicate graphene as a cost-effective and abundant material Thus, it appears that the only routes to prepare bulk quantities
that qualifies for application in optoelectronic devices such of graphene and chemically modified graphene (CMG) are
as displays, light-emitting diodes, and solar cells [14–17]. from graphene oxide (GO) and graphite intercalation com-
Different routes are available for the preparation of pounds (GICs). The presence of hydroxyl and epoxide groups
graphene [12, 18, 19]. The first involves chemical vapor depo- on the graphitic basal planes and carboxyl and carbonyl
sition (CVD) of monolayer of graphite on transition metal groups on the edges of layers makes GO water dispersible
surfaces [20, 21]. The second route is the micromechanical [24]. Thus, on sonication in aqueous media, GO exfoliates
exfoliation of graphite and involves peeling of the graphene readily into colloidal suspensions of single graphene oxide
from graphite using “Scotch” tape [22]. The “Scotch” tape layers. Chemical reduction of GO present in the colloidal
is then dipped in acetone to release the graphene, which suspension with reducing agents is necessary to convert the
is subsequently captured on a silicon wafer with a SiO2 electrically insulating GO layers back to conducting graphene
Journal of Nanomaterials 3
suitable for composite applications. The final route by which Acceptor material
bulk quantities of graphene can be prepared is by thermally
reducing GO. This technique involves rapidly heating GO in
inert (argon or nitrogen) environment to produce thermally Cathode
reduced expanded graphene oxide (TRGO) [25, 26]. Due Electron extraction layer
to its wrinkled nature, TRGO do not collapse back to GO Active layer
but remain highly agglomerated. However, McAllister et al. Hole transport layer
[27] observed that, after TRGO was dispersed by ultrasoni- Anode
cation in appropriate solvents, 80% of the flakes were single Substrate Donor material
graphene sheets.
Derivatives of graphene, such as GO and reduced Figure 3: Configuration of a typical BHJ solar cell.
graphene oxide (rGO), are also being widely investigated
from the point of view of primary and practical applications
[16]. rGO can be easily prepared by wet processes such as surface [13, 22, 35]. The high transparency, conductivity,
spin-, dip-, and spray-coating to give large-area GO films flexibility, and elemental abundance of graphene indicate that
and by hydrazine vapor treatment to reduce the GO films. it is an excellent replacement for transparent conducting
Secondary treatments, such as thermal annealing, have been oxide electrodes [38–40]. Graphene transparent electrodes
indicated to increase the photocurrent and device efficiency can be expected to be applied not only for the substitution
by removing defects and optimizing the morphology of of ITO that is usually used as anode but also for cathode for
graphene-based cell constituents [2, 16]. which low work function metals are used [41, 42].
Regarding the PCE in BHJ devices, the highest value was However, for chemically processed graphene, mainly the
observed to be ∼7.4% for the device with ITO/PEDOT : PSS/ contact resistance of the small graphene flakes and the
PBTTT-3 : PC70 BM/Ca/Al (indium tin oxide/poly(3,4-ethyl- insulating property of the graphene chemically reduced from
enedioxythiophene) : poly(styrenesulfonate)/poly(2,5-bis(3 : graphene oxide limit the device performance. The structural
tetradecylthiophen-2-yl)thieno(3,2-b)thiophene)/3 : phenyl- defects and lateral disorder of such chemically exfoliated
C70 -butyric acid methyl ester/calcium/aluminum) structure graphite affect the carrier mobility of the film negatively
[16]. Photovoltaic devices based on graphene are still not [43]. Therefore, although graphene could provide a low-
as efficient as, for example, devices with ITO electrodes cost alternative for ITO, there is still tremendous room
or organic acceptors mainly because the conductivities of for improvement in terms of enlarging the lateral scale of
graphene are relatively low [9, 28]. Theoretical PCEs as high graphene in these devices [44].
as 12% have been calculated for graphene-based organic
devices [29], and it has also been proposed that graphene
may favor charge carrier multiplication [30]. Graphene has 2.1. Anode. Xu et al. [45] reported on polymer organic photo-
proved to be useful not only as substitute for ITO electrodes, voltaic cells using pure graphene films as the transparent
but also as cathode, electron acceptor, hole transport, and anode directly fabricated from graphene solutions by spin-
electroextraction material (Figure 3) [15, 31, 32]. Therefore, coating, with P3HT as the electron donor and PCBM as
this review is intended to examine the efficiency of different the acceptor. The graphene films reduced with hydrazine
graphene-based devices and the newest trends in order to and annealed at temperatures of 300, 500, and 700∘ C had
maximize their efficiencies. transmittance of 75%, 73%, and 69% at a wavelength of
550 nm, respectively. Under these experimental conditions,
the reduced graphene films could have a sheet resistance
2. Electrode Material of 17.9 kΩ/sq and a conductivity of 22.3 S/cm which is
comparable with that obtained using more complicated
In BHJ devices, the conventional transparent conductive graphene composites. The current density-voltage (𝐽-𝑉)
electrode used to couple photons into the active layer is exten- characteristic of the device (hydrazine + 700∘ C) under
sively the ITO-based electrode that shows a sheet resistance illumination of simulated solar light shows a short-circuit
of less than 100 Ω/sq and an optical transparency of ∼90% photocurrent density (𝐽sc ) of 1.18 mA/cm2 with an open
[2, 33]. ITO electrodes consume as much as 30% of the fabri- circuit voltage (𝑉oc ) of 0.46 V, a calculated filling factor (FF)
cation cost in solar cells and their use seems to be increasingly of 24.58%, and an overall PCE of 0.13%. The ITO device
problematic due to the limited indium source, susceptibility used as a reference was fabricated under the same conditions
to ion diffusion into polymer layers, instability in acid or base, and had a PCE of 3.59%. The low PCE of the graphene-
and the brittle nature of metal oxide [34–36]. Additionally, based device is likely due to the hydrophobic graphene
Krebs et al. reported that the energy involved in processing film surface which makes it rather hard to get a uniform
the ITO electrode accounts for 87% in roll-to-roll based poly(3,4-ethylenedioxythiophene) : poly(styrenesulfonate)
OSCs fabrication [37]. Thus, a substitute for ITO with similar (PEDOT : PSS) layer. So, it is highly possible that, with
performance but lower cost is clearly needed. In this regard, optimized graphene-electrode conductivity and graphene
graphene has risen as a promising electrode material due to film surface wetting property, the performance of these
its high theoretical surface area of 2630 m2 /g and ability to graphene-electrodes cells could be improved significantly
facilitate electron or hole transfer along its two-dimensional [45]. Although this approach provides a cost-effective, simple
solution-based process, the overall PCE of the graphene- degrading the conductivity, the graphene film was noncova-
based device is lower than that reported for the best OSCs lent modified with pyrene buanoic acid succidymidyl ester
based on the BHJ concept (∼8.0%). (PBASE) as a result; the PCE was of 1.71%. This performance
Yin et al. [34] indicated that the performance of the corresponds to ∼55.2% of the PCE of a control device based
organic devices mainly depends on the charge transport on an ITO anode. The electronic energy levels of graphene
efficiency through rGO electrodes when the optical transmit- before and after modification with PBASE were investigated;
tance of rGO is above 65%. However, if the transmittance the results indicated that graphene maintained a nearly zero-
of rGO is less than 65%, the performance of the device is gap condition after the treatment. Thus, since the main draw-
dominated by the light transmission efficiency, that is, the back of graphene film is its poor hydrophilicity, which led to
transparency of rGO films. In this work, highly conductive a negative effect on the construction of solution-processed
rGO film was transferred onto a polyethylene terephthalate devices, PBASE treatment resulted to be an effective method
(PET) substrate, which was used as the transparent electrode. to overcome this issue successfully [44].
The authors reported that lowering the rGO sheet resistance Gómez De Arco et al. [47] reported on the implementa-
via increasing the rGO thickness notably enhanced the tion of continuous, highly flexible, and transparent graphene
current density of devices and thus the overall PCE. In order films obtained by CVD and used as transparent conductive
to study the effect of rGO thickness on the performance of electrodes. The thickness of CVD graphene was on the
the devices, rGO films with different thickness were prepared order of 1–3 nm. According to the authors, the use of CVD
(4 nm, 10 nm, 16 nm, and 21 nm). The highest optical trans- graphene is more attractive than the other graphene films,
mittance, 88%, was obtained in the 4 nm thick rGO films, but for example, those that are formed by stacked micrometer
the sheet resistance dramatically increased to 16.0 kΩ/sq. The sized flakes that suffer from flake to flake contact resistance
highest PCE obtained in the flexible rGO/PET devices was and high roughness. In the case of CVD graphene, the
0.78% and corresponded to the 16 nm thick rGO cells, which grain boundaries have the advantage of being formed in
showed the highest 𝐽sc and 𝑉oc . These devices showed an situ during synthesis; such process is expected to minimize
excellent stability after applying the bending-induced tension contact resistance between neighboring graphene domains
stress, and their performance was well maintained even after and may result in smoother films with better conducting
bending a thousand times [34]. properties. Solar cells made with CVD graphene exhibited
Wang et al. [46] described the fabrication and characteri- performance that compares to ITO device and surpasses that
zation of transparent graphene-constructed films (TGFs) to of ITO devices under bending conditions, exhibiting PCE of
be used as hole collecting electrodes in organic solar cells. 1.18%, which is nearly 93% of that shown by the ITO device.
The transparency of TGFs on quartz was tuned by controlling Contrary to the conventional materials used in BHJ OSCs, in
the film thickness by varying the solution concentration. this case, the multilayered configuration employed a copper
Different thicknesses (30, 22, 12, and 4 nm) had transmittance phthalocyanine (CuPc), fullerene (C60 ), and bathocuproine
of 55, 66, 80, and 90, respectively, at a wavelength of 500 nm. (BCP) mixture as active layer [47].
The electrical characteristics of the as-prepared 30 nm thick Jung et al. [48] reported the characteristics of two dif-
TGFs were evaluated by a four-point probe measurement, ferent types of OSCs fabricated on HNO3 - (nitric acid-)
which showed resistance of 1.6 kΩ/sq and a conductivity treated and untreated multilayer graphene (MLG) transpar-
of 206 Scm−1 . To demonstrate how the TGFs performed as ent electrodes prepared using chemical vapor deposition
anodes, organic solar cells were fabricated using a blend and a multitransfer process. MLG films were formed by
of P3HT and PCBM. The photoactive composite layer was stacking graphene films three times on the same substrate
sandwiched between TGFs/quartz and Ag electrode. The and were used as the device anodes. OSCs fabricated on
TGFs on quartz had a sheet resistance of 18 kΩ/sq and a untreated transparent electrodes had a 𝑉oc of 0.575 V, a 𝐽sc of
transmittance of 85% at 500 nm. The devices were illuminated 8.08 mA/CM2 , FF of 43.5%, and a PCE of 2.02%. In contrast,
with monochromatic light and the highest external quantum application of HNO3 -treated films as transparent electrodes
efficiency (EQE) of around 43% was achieved at a wavelength led to an improved performance with a 𝑉oc of 0.602 V, a
of 520 nm. This efficiency is comparable to the highest 𝐽sc of 8.26 mA/cm2 , FF of 5.75%, and a PCE of 2.68%. The
EQE value of 47% for a reference device fabricated under results suggested that HNO3 treatment is a promising method
similar conditions but with ITO/glass as the anode. The improving the performance of large-area OSCs [48].
current-voltage (𝐼-𝑉) characteristics of the device showed a Choe et al. [49] presented the results of applying mul-
distinct diode behavior under monochromatic light with a tilayer graphene (MLG) films as transparent conductive
wavelength of 510 nm. In this case, PCE was of 1.53%, and electrodes. The MLG films were synthesized into a CVD
under simulated solar light PCE was 0.29% [46]. chamber under a flow of H2 in Ar gas mixture at different
Wang et al. [44] produced large area, continuous, trans- growth temperatures. MLG films prepared at 800, 900, and
parent, and highly conducting few-layered graphene films 1000∘ C showed the sheet resistances of 1730 ± 600, 990 ± 400,
(FLGFs) by chemical vapor deposition method to be used as and 610 ± 140 Ω/sq and the mobility of 660 ± 270, 1030 ± 440,
anode for application in photovoltaic devices. In the solution- and 1180 ± 260 cm2 /V s, respectively. The performance of the
processed organic solar cells, the anode layer should possess devices with 1000∘ C grown MLG films was found to be the
good hydrophilicity to allow the spreading of the hole trans- best with a PCE of ∼1.3%. The PCE was further enhanced
port layer. In order to tune the surface wettability without when a hole-blocking titanium suboxide (TiO𝑥 ) layer was
Table 1: PCE of BHJ OSCs using graphene as anode.
Material Device conformation Highest PCE Reference

TGFs Quartz/TGFs/P3HT : PCBM/Ag 1.53% [46]
FLGFs FLGFs/PEDOT : PSS/P3HT : PCBM/LiF/Al 1.71% [44]
Graphene Quartz/graphene/PEDOT : PSS/P3HT : PCBM/LiF/Al 0.13% [45]
rGO PET : rGO : PEDOT : PSS/P3HT : PCBM/TiO2 /Al 0.78% [34]
Graphene PET : CVD graphene/PEDOT : PSS/CuPc/C60 /BCP/Al 1.18% [47]
MLG Glass/MLG/PEDOT : PSS/P3HT : PCBM/TiO𝑥 /Al 2.6% [49]
CCG CCG/PEDOT : PSS/P3HT : PCBM/Al 1.01% [51]
MLG MLG/MoO3 + PEDOT : PSS/P3HT : PCBM/LiF/Al 2.5% [36]
MLG MLG/PEDOT : PSS/P3HT : PCBM/Ca/Al 2.68% [48]
MLG Glass/MLG/PEDOT : PSS/P3HT : PCBM/Ca/Al 1.17% [50]
inserted in the device structure, resulting in a PCE of ∼2.6% reduction of exfoliated GO in the absence of dispersant to be
which is a significantly higher efficiency compared to the used as transparent electrodes in BHJ devices. After vacuum
other graphene-based photovoltaic cells [49]. filtration of the reduction-controlled CCG suspension and
Choi et al. [50] fabricated OSCs based on MLG electrodes, subsequent thermal annealing (optimal conditions were
which were prepared using the CVD method and a mul- 15 min at 800∘ C) of the CCG films, high conductive films
titransfer process on a glass substrate. The MLG electrode with a low sheet resistance on the order of 103 Ω/sq and high
transferred onto a glass substrate showed a sheet resistance transparency (80% at 550 nm) were obtained. Thermally
of 374 ± 3 Ω/sq and an optical transparency of 84.2%. The annealed CCG film showed a sheet resistance that was lower
sheet resistance of the MLG (4 layers) film was higher than than that of the thermally annealed GO films, apparently due
those reported elsewhere because in this case no chemical to the greater extent restoration of the sp2 carbon networks
treatment was performed on the film. The transparency of the during the two-step reduction of the CCG films. Devices
MLG film was fairly constant regardless of wavelength, unlike prepared with the CCG films as transparent electrodes
the conventional ITO film showing transparency modulation exhibited PCE of 1.01 ± 0.05%, which correspond to half
in the blue wavelength region. To prepare the MLG electrode the efficiency of solar cell devices in which the electrode was
on glass, a thin layer of graphene was grown on Cu foils made using ITO [51].
using CVD; the transfer process was repeated four times Table 1 summarizes the best PCE achieved by the different
on the transparent glass substrate until the MLG film was research groups presented in the previous section as well as
obtained. The PCE of the BHJ device was 1.17%, indicating the device conformation that rendered such PCE.
that MLG films are a promising indium-free transparent Although the overall PCE obtained by devices using
electrode substitute for the conventional ITO electrode for graphene-based materials as anode has not surpassed that of
use in cost-efficient OSCs [50]. cells using traditional materials, research groups around the
Wang et al. [36] developed a direct layer-by-layer (LBL) world have already identified the main aspects to improve
transfer method of graphene sheets to fabricate MLG films. graphene-based materials performance. It has been pointed
Stacking multilayers together and doping them rendered out that lowering graphene sheet resistance will increase the
higher extrinsic conductivity. HCl was used to dope the overall PCE of the BHJ devices. In order to lower the sheet
individual layers during the transfer process, followed by resistance, different strategies can be followed, for example,
HNO3 doping at the surface. Different types of devices were increasing the thickness of the graphene film. This goal can
fabricated to evaluate the effect of the various treatments be achieved following a simple procedure that consists in the
proposed in this work. To improve the hydrophilicity of modification of the solution concentration from which the
graphene, a thin layer of (∼20 Å) molybdenum oxide (MoO3 ) film is obtained. This route constitutes a very good option due
was evaporated on the graphene. The as-grown graphene- to its simplicity and to the fact that no additional chemicals
based devices showed a poor performance, yielding a low are needed, contrary to other techniques that require highly
PCE of 0.35%. After modifying the graphene with MoO3 + dangerous chemical agents to dope graphene. Thickness
PEDOT : PSS double interfacial layer, the PCE was dra- control also has an impact on the transparency of the film.
matically increased and 1.23% was achieved. Finally, the A higher transparency will originate a better light trans-
4-layer acid-doped graphene solar cell exhibited the best mission and a higher PCE. Thus, a proper balance between
performance in this work with PCE of 2.5%, which is about transparency and sheet resistance needs to be achieved to
83.3% that of the control device fabricated on ITO. The LBL, improve the performance of the device. Scientists have also
acid-doped, four-layer graphene film has a sheet resistance of identified that the optimization of the graphene conductivity
∼80 Ω/sq and a transmittance of ∼90% at 550 nm [36]. and graphene films surface wetting has a positive effect on the
Geng et al. [51] reported a simple method for preparing performance of graphene-based electrodes. Thermal treat-
transparent conductive films using a chemically converted ments (i.e., annealing) also play an important role regarding
graphene (CCG) suspension via controlled chemical final efficiency; by this simple procedure, notable increments
Table 2: PCE of BHJ OSCs using graphene as cathode.

MLG MLG/WPF-6-oxy-F/P3HT : PCBM/PEDOT : PSS/Al 1.23% [14]
MLG Glass/ITO/ZnO/P3HT : PCBM/MLG 2.50% [52]
SLG ITO/PEDOT/CuPC : C60 : TPBi/SLG 0.22% [53]
rGO PET : alkali + rGO-SWCNT/P3HT : PCBM/V2 O5 /Al 1.27% [55]
SLG Glass/ITO/ZnO/P3HT : PCBM/PEDOT : PSS/Au + SLG 2.7% [54]
have been achieved. In the specific case of anode-materials, was found as the best material because it reduces the effective
graphene constitutes a viable option to substitute traditional work function of MLG to a value that is close to the LUMO
materials, first due to its higher abundance compared to of the acceptor material. Therefore, the best PCE (1.23%)
indium and second to the considerable PCE reached so far. was obtained with WPF-6-oxy-F as the interfacial layer. The
performance of the OSCs with MLG electrodes is expected
2.2. Cathode. Although several studies have reported on to depend strongly on the quality and properties of the
the graphene-based electrode for replacing the ITO bottom MLG film. The CVD-synthesized MLG films exhibited high
electrode in organic photovoltaic devices, the use of the sheet resistance in the range of 850 to 520 Ω/sq, while the
graphene top electrode is still very limited [52]. The following transmittance changed from 90% to 85% at a wavelength of
section presents the research works related to this topic found 450 nm [14].
in the scientific literature. Table 2 summarizes the best PCE Cox et al. [53] demonstrated that a laminated single-
achieved by devices using graphene as cathode. layer graphene (SLG) grown through chemical vapor depo-
Lee et al. [52] reported a simple lamination process for sition can be used as a cathode for organic photovoltaic
depositing a graphene electrode on top of a polymer pho- devices. The PCE of graphene devices was limited by their
tovoltaic device replacing the conventional metal electrode, series resistance, indicating that the preparation of graphene
resulting in a semitransparent inverted polymer solar cell samples with lower sheet resistance could improve device
with a PCE of over 75% of that of the standard opaque performance. In this work, aluminum control devices were
device using an Ag metal electrode, which was fabricated used to evaluate the performance of the graphene OSCs. The
for comparison. For the preparation of the graphene top graphene devices exhibited a PCE of 0.02% and the aluminum
electrode, a graphene film was grown on copper foil using controls showed a PCE of 0.41%. The 𝑉oc for both types of
CVD processes. Since a single layer of graphene does not instruments was approximately 0.45 V. This large efficiency
have sufficiently high sheet conductivity, multilayer stacking disparity in conjunction with similar 𝑉oc ’s indicated that
of the graphene film was required to obtain higher sheet parasitic series resistance dominated the characteristics of
conductance. The Ag-based device yielded a PCE of 3.30% the graphene devices. To minimize the influence of the par-
and in the best case (10-layers device) the semitransparent asitic series resistance, the devices were studied under low-
device achieved a PCE of 2.50% when illuminated (AM1.5, intensity monochromatic illumination. At incident power of
100 mW/cm2 ) from the ITO side. By contrast, while illumi- 4.6 mW/cm2 , the graphene device exhibits a PCE of 0.22%
nated from the graphene side, the semitransparent device [53].
consisting of 8 layers of graphene exhibited an optimal PCE Liu et al. [54] reported the fabrication of a semitrans-
of 2.04% [52]. parent device with a SLG synthesized on copper foils with
Jo et al. [14] fabricated inverted-structure OSCs with CVD method used as top electrode. The device was opti-
graphene cathodes. The graphene film used in this work was mized by tuning the active layer thickness and changing the
work function-engineered with an interfacial dipole layer to conductance and the work function of single-layer graphene
reduce the work function of graphene, which resulted in by doping Au nanoparticles and PEDOT : PSS. For each syn-
an increase in the built-in potential and enhancement of thesis condition, three identical cells were fabricated and the
the charge extraction, thereby enhancing the overall device average PCE was calculated. The devices were illuminated on
performance. MLG film was grown through CVD on nickel each side under an AM1.5 solar simulator with the intensity
films as reported elsewhere. The work function of the of 100 mW/cm2 . The maximum PCE of the semitransparent
untreated MLG film was 4.58 ± 0.08 eV, which is close to the cell was 2.7% for an active area of 20 mm2 when illuminated
work function of highly ordered pyrolytic graphite (4.5 eV). from the graphene side, which is much higher than the value
The work function of the MLG film was reduced by the from the ITO side (2.2%). It was also found that the PCE of
use of different interfacial layers made of poly-ethylene the device decreased from 3% to 2.3% with the increase of
oxide (PEO), poly[9,9-bis((6’(N,N,N-trimethylammonium) the size from 6 to 50 mm2 , which was attributed to both the
hexyl)-2,7-fluorene)-alt-(9,9-bis(2-(2-(2-methoxyethoxy) increased series resistance and the decreased edge effect of the
ethoxy)ethyl)-9-fluorene)] dibromide (denoted by WPF- device [54].
6-oxy-F), and Cs2 CO3 . These interfacial layers formed Huang et al. [55] found that the work functions (𝜙𝑤 ) of
interfacial dipoles that pointed away from the MLG surface, solution-processable, functional graphene/carbon nanotube-
thereby decreasing the MLG work function. WPF-6-oxy-F based transparent conductors were readily manipulated,
Table 3: PCE of BHJ OSCs using graphene as acceptor material.

SPFGraphene ITO/PEDOT : PSS/P3OT : SPFGraphene/LiF/Al 1.40% [56]
SPFGraphene Glass/ITO/PEDOT : PSS/P3HT : SPFGraphene/LiF/Al 0.69% [58]
SPFGraphene ITO/PEDOT : PSS/P3HT : SPFGraphene/LIF/Al 1.10% [64]
Graphene Glass/ITO/PEDOT : PSS/P3HT : PDI-G hybrid/LiF/Al 1.04% [63]
SPFGraphene ITO/PEDOT : PSS/P3HT : PCBM : SPFGraphene/Al 1.40% [67]
Graphene Glass/ITO/PEDOT : PSS/C60 -G : P3HT/Al 1.22% [62]
BCFG-F Glass/ITO/PEDOT : PSS/P3HT : BCFG-F/LiF/Al 1.10% [60]
SPFGraphene Glass/ITO/PEDOT : PSS/P3HT : MDMO-PPV : SPFGraphene/LiF/Al 1.506% [65]
Graphene Glass/ITO/PEDOT : PSS/P3HT : PCBM : graphene/LiF/Al 0.70% [59]
varying between 5.1 and 3.4 eV, depending on the nature of 3. Active Layer Material
the doping alkali carbonate salt used. Highly conductive and
transparent graphene-based electrodes with tunable work The active layer of an ideal BHJ solar cell is defined as a
functions were prepared by combining single walled carbon bicontinuous interpenetrating network of donor and accep-
nanotubes (SWCNTs) with chemically reduced graphene tor at the nanometer scale with maximum interfacial area.
(rGO). Composite films were doped with alkali carbonates, In this case, excitons can always reach the D/A interface
which were decomposed into alkali oxides by means of within their limited diffusion length and charge separation
thermal annealing that covered the carbon-based materi- can occur efficiently. So far, the most successful active layer
als. Graphene-based electrodes possessing lower values of with BHJ architecture is based on either soluble P3HT or
𝜙𝑤 were used as cathodes in inverted-architecture poly- poly-3-octylthiophene (P3OT) as the donor and PCBM or
mer photovoltaic devices to effectively collect electrons. As PC70 BM (6,6-phenyl-C70 -butyric acid methyl ester) as the
expected, increasing the number of spin-layers from one acceptor. Solar cells based on P3HT have exhibited PCE
to five provided thicker carbon composite films, thereby values approaching 5%, depending on the architecture of the
decreasing the optical transmittance at 550 nm from 88.8 (1 device. On the other hand, it is known that PCBM is not
layer) to 58.7% (5 layers). Therefore, an optimal rGO-SWCNT the optimum acceptor material and limits the efficiency of
thickness exists for optimal PV performance. The best the organic devices. Thus, new materials for both donor and
PCE of the P3HT : PCBM photovoltaic device was achieved acceptor with better HOMO/LUMO matching, stronger light
when incorporating the four-layer rGO-SWCNT (1.27%) absorption, and higher charge mobility with good stability
[55]. are much needed [6, 56, 57]. In this section, the use of
According to the results presented in the previous section, graphene as acceptor material is described, and the PCE
the control of the work function of graphene layers consti- and the conformation of BHJ devices using graphene are
tutes the main strategy to improve the conductivity and the summarized in Table 3.
overall power conversion efficiency of BHJ solar cells using Liu et al. [58] used graphene as the acceptor material in
graphene as cathode material. This goal may be achieved BHJ organic photovoltaic cells. To achieve good dispersion
following different procedures, for example, using interfacial of graphene, a solution-processable functionalized graphene
layers or doping graphene films with different kind of agents. (SPFGraphene) was prepared by a two-step method con-
Other strategies to enhance the PCE include the tuning of sisting of an oxidation step followed by an organic func-
the active layer thickness to maximize light absorption and tionalization step. The oxidation treatment using a modified
charge transport. Regarding the preparation of the graphene Hummers’ method of the flake gave out graphene oxide
electrode, CVD is the most used route, while lamination is sheets having a thickness of ∼0.7 nm and a dimension of
the most commonly method used to deposit the electrode. several hundreds of nanometers. Then, a phenyl isocyanate
However, the high processing temperature required for CVD treatment gave out SPFGraphene that could be dissolved in
limits the growth of graphene to a restricted number of organic solvent. The active layer was prepared by spin-coating
substrates, which could have a negative impact on the using a P3HT/SPFGraphene solution in 1,2-dichlorobenzene
performance of the BHJ device. Thus, it is clear that further (SPFGraphene content: 0%, 2.5%, 5%, 10%, and 15%). The
enhancement in the conductivity of the graphene electrode is current-voltage (𝐽-𝑉) curves of the photovoltaic devices were
needed and constitutes the next step in order to increase the determined using an AM1.5G standard operating with an
overall performance of the cathode-graphene-based devices. illumination intensity of 100 mW/cm2 . Under illumination,
In the same way, the development of alternative methods for the device based on pristine P3HT gave PCE of 0.005%, while
preparing large-area graphene films is required, since massive the P3HT/10%-SPFGraphene based device gave a maximum
preparation of graphene films would be needed to satisfy PCE value of 0.15%, which is much higher than that of
global demand. the control device based on pristine P3HT. The authors
also reported that after annealing at 160∘ C for 10 min a top circuit voltage of 0.77 V, and a short-circuit current density
PCE of 0.69% for the P3HT/5%-SPFGraphene was registered of 3.72 mA/cm2 . SPFGraphene content was the main factor
[58]. improving PCE. For smaller concentrations, such as 1 wt%
Yu and Kuppa [59] investigated BHJ devices employing and 2.5 wt%, the SPFGraphene film was too small to form a
graphene nanosheets in the active layer. Solar cells based on continuous donor/acceptor interface and the transport path-
P3HT : PCBM : graphene showed device physics significantly way for the active layer P3HT matrix. Therefore, the electron
different from traditional BHJs and displayed a monotonic cannot effectively meet the donor/acceptor interface and
increase in performance with graphene concentration. The transport smoothly through the active layer. However, if SPF-
PCE of a device based on a P3HT : PCBM blend at a 20 : 2 Graphene is further increased to a concentration of 10 wt%,
concentration ratio was about 0.2%, while the addition of only the SPFGraphene film can form a continuous donor/acceptor
small amounts of graphene (concentration ratio 20 : 2 : 0.01 interface and produce a better way to be transported
for P3HT : PCBM : graphene) led to a better performance of smoothly through P3HT matrix, improving the electronic
about 0.7%. Hence, although the introduction of graphene transport. However, if there is a further increase in the
sheets may have had a slightly negative effect on the 𝑉oc concentration of SPFGraphene, such as 12.5 wt% and 15 wt%,
and FF, the subsequent improvement in charge mobility and then the aggregation of SPFGraphene occurred, reducing
increase in 𝐽sc compensated more for these drawbacks and led hole mobility and decreasing the number of extracted carriers
to an increase in efficiency [59]. [61].
Ye et al. [60] grafted a benzoic acid group onto pristine Yu et al. [62] developed a lithiation reaction to covalently
graphene (BCFG, graphene functionalized with benzoic attach monosubstituted fullerene (C60 ) onto graphene (G)
acid) to improve its solubility and open a band gap of the nanosheets to be used as electron acceptors in P3HT-based
resultant graphene. BCFG was esterified with 1H,1H,2H,2H- BHJ solar cells. Graphene nanosheets were produced through
perfluoro-1-octanol to obtain BCFG-F, which was blended reduction of GO in pure hydrazine and purified with toluene
with P3HT to be used as the active layer in BHJ devices. and methanol. Using C60 -G : P3HT (1 : 1 wt/wt), C60 : P3HT
Solar cells of P3HT/BCFG-F with functionalized graphene (1 : 1 wt/wt), and C60 /G mixture (i.e., 12 wt% graphene,
content of 5 wt%, 7.5 wt%, 10 wt%, and 12.5 wt% (ratio to physical blend without chemical functionalization) : P3HT
P3HT) were fabricated. PCEs of 0.24, 0.46, 1.1, and 0.48 were (1 : 1 wt/wt) as a control, the device performance of a series of
obtained for these devices, respectively. In order to realize the BHJ solar cells using such materials as active layer was tested
dependence of the photovoltaic performance on the BCFG-F under AM1.5 illumination. A PCE of 0.47% was obtained
content, the surface morphology of the composites used as for the C60 : P3HT system, while the C60 -G : P3HT system
active layer was investigated. It was found that, in composite showed a PCE of 1.22%. The observed enhancement could
films containing 5 wt% of BCFG-F, only a few functionalized be attributed to the improved electron transport due to
graphene sheets could be seen embedded in the P3HT matrix. the presence of the C60 -grafted graphene. In the case of
Therefore, for low BCFG-F content, it cannot form enough the C60 : graphene device, the simple blending of C60 with
P3HT/BCFG-F interfaces, at which the separation of excitons the graphene cannot ensure a good interfacial contact to
occurs, and continuous pathways in the P3HT matrix for the facilitate strong electronic interactions for efficient electron
effective electron transport. In the composite film with 10 wt% transport between the two components. To make it even
BCFG-F, there were more graphene sheets than in the film worse, graphene sheets easily aggregated in the composite
with 5 wt% and they were well dispersed in the P3HT matrix, film, due to poor miscibility, to show a detrimental effect on
to form abundant P3HT/BCFG-F interfaces for charge the charge separation/transport. Therefore, the overall device
generation and interpenetrating networks. Finally, for the efficiency was not improved (0.44%) [62].
film of the composite with a 15 wt% content, the morphology Liu et al. [56] reported the fabrication and performance of
of the film demonstrated great agglomerated forms by devices with BHJ structure using an organic SPFGraphene as
aggregated graphene sheets, which had a deleterious effect electron-acceptor material and P3OT (poly(3-octylthiophene
on exciton separation and charge transport in the active layer 2,5 diyl)) and P3HT as donor material. Devices with SPF-
[60]. Graphene content of 1 wt%, 5 wt%, and 15 wt% (ratio to
Liu et al. [61] designed an organic photovoltaic device P3OT) were fabricated. The authors indicated that the
based on an acceptor of solution-processable functionalized functionalized graphene material could be dispersed into
graphene (SPFGraphene). The tested devices were based organic solvent to form a homogeneous solution. Controlled
on heterostructure polymer- (P3HT-) graphene composite annealing improved the device performance, and the best
layers as active layer. Different active layers were synthetized PCE of 1.4% (5 wt% SPFGraphene) was obtained using
by means of spin-coating from a solution of 15 mg/mL simulated 100 mW/cm2 AM1.5G illumination after annealing
P3HT in chlorobenzene with SPFGraphene content of 0 wt%, during 20 min at 160∘ C. Although the reported PCE is
1 wt%, 2.5 wt%, 5 wt%, 10 wt%, 12.5 wt%, and 15 wt%. Doping moderate, it is comparable with most of the best devices
of graphene into P3HT resulted in appropriate energetic using materials other than fullerenes as electron acceptors.
distance between HOMO and LUMO of the donor/acceptor Furthermore, there is much room for improvement, such as
for a high open circuit voltage and provided higher exciton optimizing the graphene content, annealing temperature, and
dissociation volume mobility of carrier transport for a large time further controlling the size and functionalized degree
short-circuit current density. The device containing only of graphene sheets and the device fabrication and structure
10 wt% of graphene showed the best PCE (0.88%), an open [56].
Wang et al. [63] studied the role of graphene (rGO) as the addition of the SPFGraphene oxide, stating that there is
atomic and structural scaffold in the nucleation and assembly an obvious charge transfer from the P3HT donor to the SPF-
of organic nanostructures. The photovoltaic properties of Graphene oxide acceptor. To recover the conjugated structure
the PDI (N,N 󸀠 -dioctyl-3,4,9,10-perylenedicarboximide) and and conductivity of the graphene sheet through removing
graphene hybrids were investigated to determine whether the organic functional groups from the SPFGraphene oxide
they offer enhanced performances over those of the indi- sheet, a thermal annealing process was carried out at 160∘ C
vidual constituents like PDI and G. PDI-G hybrids were at different times. The best PCE was obtained for a device
prepared by the hydrothermal treatment of GO and PDI containing 10 wt% of SPFGraphene annealed during 10 min
in DMF. The authors also investigated the performance of (1.046%) [66].
physically mixed PDI + G composites made of PDI and G; Liu et al. [67] tested a SPFGraphene in P3HT/PCBM
this system was used as a control to compare with the PDI-G photovoltaic devices. Tested devices took advantage of the
hybrid wires in order to find out if the coating of G around the electron-accepting feature of fullerenes and the high electron
PDI wires offers any enhanced performance. Using BHJ cells transport capability of graphene. The photovoltaic perfor-
tested under 100 mW/cm2 AM1.5 illumination, it was found mance was investigated for devices containing 0%, 1%, 2.5%,
that PDI-G hybrid wires based cells showed a PCE of 1.04%, 5%, 10%, 12.5%, and 15% of graphene. The best results were
while PDI cells presented a PCE of only 0.064% [63]. obtained with P3HT : PCBM (1 : 1) mixture with 10 wt% of
Liu et al. [64] studied a BHJ device with an active graphene with a PCE of 1.4% at illumination at 100 mW/cm2
layer consisting of P3HT and SPFGraphene. According to AM1.5. Results indicated that the addition of graphene
their results, adding graphene to the P3HT induced a great enhanced the performance of polymer photovoltaic devices
quenching of the photoluminescence of the P3HT, indicating [67].
a strong electron/energy transfer from the P3HT to the Different methods to obtain graphene-based materials
graphene. The device containing only 10 wt% of graphene have been developed (e.g., adhesive tape, epitaxial growth,
showed the best performance with a PCE of 1.1% under sim- and micromechanical cleavage). However, most of these
ulated AM1.5G conditions at 100 mW/cm2 after an annealing methods are not suitable for low-cost, large-area optoelec-
treatment at 160∘ C for 10 min. The annealing treatment at tronics. In this tenor, organic solution-processable materials
160∘ C greatly improved the device performance. However, are preferred for electronic applications due to their solubility
overgenerous conditions such as those at 210∘ C resulted in a using common solvents, which allow them to be used in
decrease in the device efficiency (0.57%) [64]. polymer-composite based materials preparation. Solution-
Wang et al. [65] reported on the fabrication of BHJ processable functionalized graphene (SPFGraphene) is by
devices based on P3HT : SPFGraphene doped with poly-2- far the most used functionalized graphene-based (Figure 4)
methoxy-5-(30,70-dimethyloctyloxy)-1,4-phenyleneviny- material employed in the development of BHJ devices.
lene (MDMO-PPV) and P3OT. In this work, the amount Although the performance of the cells using this material
of MDMO-PPV incorporated to the P3HT : SPFGraphene is lower than the most efficient BHJ cells tested, it is clear
active layer was varied from 0 to 2 mg, while the amount of that the use of graphene significantly increases the efficiency
P3OT varied in the range from 0 to 3 mg. For further charac- compared to the reference devices (i.e., without graphene)
terization, the solar cells were illuminated through the side reported in each experiment. The key to improve the PCE
of the ITO-coated glass plate. AM1.5G standard operating of SPFGraphene based materials seems to be related to the
with an illuminated intensity of 100 mW xenon lamp was improvement of its miscibility, which will assure a good
used as a broadband light source. The authors pointed out dispersion of the graphene in the polymer matrix. A better
that nondoped P3HT : SPFGraphene showed an efficiency miscibility will also avoid agglomeration and its detrimental
of 1.046%. By incorporating different amounts of P3OT, the effects on charge separation/transport. Thus, in this way, the
best efficiency obtained was of 1.12% when 1 mg of P3OT hole mobility and the number of extracted carriers will be
was added. On the other hand, a top efficiency of 1.506% was increased. An improved solubility will also ensure a good
registered when 1.5 mg of MDMO-PPV was used [65]. interfacial contact to facilitate strong electronic interactions
Wang et al. [66] fabricated solar cell devices based on for a better charge generation. Another important factor
SPFGraphene oxide and P3HT with different contents of to be considered is the graphene content that needs to be
SPFGraphene oxide (0%, 2.5%, 5%, 7.5%, 10%, 12.5%, and enough to form a continuous donor/acceptor interface and
15%). The 𝜋-conjugation of graphene enables the polymers to an efficient transport pathway for the active layer. Finally,
be used as an active material for various functional devices, annealing has proved to be an efficient treatment to increase
including photovoltaic devices. The pure P3HT thin film power conversion efficiency since it considerably increases
showed strong photoluminescence between 600 and 800 nm the 𝑉oc of the device.
with excitation at 450 nm; however, the photoluminescence
is remarkably reduced after doping of SPFGraphene oxide,
4. Transport/Extraction Layer Material
showing that efficient energy transfer occurred along the
P3HT/SPFGraphene oxide interface. The overall perfor- The interfaces between active layer and anode and cathode
mance of the P3HT/SPFGraphene oxide based devices was play an essential role in determining the overall device
much higher than that of the pristine P3HT-based one. performance of organic electronics [68]. In a simple BHJ
The improved photovoltaic performance was attributed to device, both the donor and acceptor phases are in direct
Table 4: PCE of BHJ OSCs using graphene as HTLs and EELs.
Material Function Device conformation Highest PCE Reference

GO HTLs ITO/GO/P3HT : PCBM/Al 3.50% [78]
GO HTLs ITO/PEDOT : PSS : GO/P3HT : PCBM/LiF/Al 3.80% [86]
GO HTLs ITO/GO : NiO𝑥 /P3HT : PCBM/LiF/Al 3.48% [79]
FLGs HTLs Glass/ITO/FLGs-PEDOT : PSS/P3HT : PCBM/Ca/Al 3.70% [85]
mrGO HTLs Glass/ITO/mrGO/P3HT : PCBM/LiF/Al 3.98% [81]
GO-OSO3 H HTLs ITO/GO-OSO3 H/P3HT : PCBM/Ca/Al 4.37% [82]
GO HTLs ITO/GO/P3HT : PCBM/LiF/Al 3.25%
GO-Cs EELs ITO/PEDOT : PSS/P3HT : PCBM/GO-Cs/Al 3.08% [83]
GO/GO-Cs HTLs/EELs ITO/GO/P3HT : PCBM/GO-Cs/Al 3.67%
UV/ozone-G HTLs ITO/UV/ozone-G/P3HT : PCBM/LiF/Al 3.00% [80]
rGO EELs Glass/ITO/PEDOT : PSS/P3HT : PCBM/rGO-pyrene : PCBM/Al 3.89% [84]
On the other hand, certain metal fluorides, n-type semi-

conductors (e.g., TiO2 , TiO𝑥 , and ZnO), n-type organic
semiconductors (e.g., 2,9-dimethyl-4,7-diphenyl-1,10-phe-
nanthroline, BCP), and conjugated polymer electrolytes have
been used as the EELs [74–77]. Materials used as EELs need
to have a low work function for electrons to be efficiently
transported to the cathode.
Thus, several research groups, motivated by the need to
overcome the limitations of PEDOT : PSS as the conventional
HTLs by finding a suitable solution-processable alternative
that is compatible with OSCs materials and fabrication
techniques and by the need to find new materials to serve
2 𝜇m as both HTLs and EELs that could not only simplify the
materials design and device fabrication but also allow for a
precise control of the energy barrier for electron and hole
Figure 4: SEM micrograph of SPFGraphene.
extraction by tuning its work function via, for example,
controlled functionalization, have reported their findings,
which are summarized in the following section and in Table 4.
electrical contact with the cathode and anode electrodes, Li et al. [78] used graphene oxide thin films as the
leading to recombination of carriers and current leakage. hole transport and electron extraction layer in OSCs. To
To minimize such detrimental effects, hole transport layers evaluate the performance of GO devices, a set of two other
(HTLs) and electron extraction layers (EELs) are used. devices was fabricated for comparison. One set was ITO-
HTLs must be wide band gap p-type materials; in this only control devices, and the other was the conventional
respect, several inorganic transition metal oxides such as OSCs incorporating PEDOT : PSS as the hole transport layer.
molybdenum, nickel, rhenium, vanadium, or tungsten oxides The photovoltaic characteristics of the fabricated devices
(V2 O5 , ReO3 , WO3 , and MoO3 with NiO being the most were characterized under simulated AM1.5 illumination at
effective) have been reported yielding efficiencies greater than 100 mW/cm2 . ITO-only device exhibited an average PCE of
5%. In a detrimental manner, inorganic HTLs are deposited 1.8%. The insertion of a 2 nm thick GO thin film between
using vacuum deposition methods that are incompatible with ITO and P3HT : PCBM led to an enhancement in the PCE to
solution-processable printable electronic techniques used to 3.5%, while the typical PEDOT : PSS typical device had shown
fabricate photovoltaic devices [69–71]. a 3.6% PCE. Thus, the incorporation of GO deposited from
The most commonly employed material used as HTLs neutral solutions between the photoactive P3HT : PCBM
in polymer solar cells is semiconducting PEDOT : PSS, layer and the transparent and conducting ITO led to a
which is used between the ITO anode and the active layer. decrease in recombination of electrons and holes and leakage
PEDOT : PSS has the advantages of being deposited from currents, resulting in a dramatic increase in the device PCE
solution and serve to minimize the detrimental effects of ITO to values that are comparable to devices fabricated with
roughness and to align the work function of P3HT and ITO PEDOT : PSS as the hole transport layer. [78].
for more efficient collection of holes. However, it is usually Ryu and Jang [79] reported a solution processed GO,
deposited from highly acidic aqueous suspensions that are NiO𝑥 , and GO/NiO𝑥 bilayer used as an anode interfacial layer
known to corrode ITO at elevated temperatures and can also in a BHJ device. In order to obtain the optimized thickness
introduce water into the active layer, degrading the device of GO layer, cells with different numbers of GO layers were
performance [68, 72, 73]. fabricated by spin-coating. The best cell performance was
achieved for the cell with 3 GO layers, exhibiting a PCE –COOH groups to be used as HTLs. Different devices
of 2.75%, which was superior to that of the cell without based on GO and GO-OSO3 H were fabricated varying the
HTL (2.33%). On the other hand, the device with a solution thickness of the HTLs from 2 to 6 nm. The best results were
processed NiO𝑥 layer showed an improved PCE of 3.10%. To obtained when using 2 nm thick HTLs. Because of the poor
further enhance cell performance of the device with GO and conductivity of GO, an increase in the GO thickness from
NiO𝑥 , devices with GO/NiO𝑥 and NiO𝑥 /GO were fabricated. 2 to 6 nm increased the series from 3.1 to 6.4 Ω cm2 and
Cell performance of the OSC with NiO𝑥 /GO as HTLs was hence decreased the PCE. By contrast, the performance of
similar to the device with a NiO𝑥 . However, the device with the GO-OSO3 H-based devices is nearly independent of the
a GO/NiO𝑥 layer showed an enhanced cell performance, HTLs thickness over the range from 2 to 6 nm. Compared
indicating a 15% increase in PCE, compared to the cell to that of GO, the better conductivity of GO-OSO3 H led to
without HTL. These results indicated that the NiO𝑥 functions an improved PCE of 4.37% versus 3.34% of GO. The control
both as a hole transport and an electron extraction layer. The devices based on PEDOT : PSS exhibited a PCE of 4.39%. The
device with a GO/NiO𝑥 showed a PCE of 3.48%. The cell relatively poor photovoltaic performance observed for the
efficiency is correlated with the matching of energy levels GO device can be attributed to high series resistance associ-
between ITO, hole transport layer, and P3HT and thus a well- ated with the insulating GO. Compared with the GO-based
matched GO/NiO𝑥 showed the best PCE [79]. devices, their GO-OSO3 H counterparts exhibited a much
Kwon et al. [80] fabricated organic devices using UV/ lower series resistance and hence a significantly improved
ozone-treated graphene sheets as HTLs. A PEDOT : PSS- PCE [82].
coated ITO device was used as reference and, in the case of Liu et al. [83] reported on the functionalization of GO to
the UV/ozone-treated graphene devices, the graphene was produce both hole and electron extraction materials for BHJ
transferred onto the ITO glass following exposure to UV- solar cells. GO was tested as HTLs and GO-Cs, in which the
ozone with a power of 30 mW/cm2 for 1, 3, 5, 7, and 9 min. periphery –COOH groups in GO were replaced by –COOCs,
Cells were tested under AM1.5G 100 mW/cm2 illumination. as EELs. GO itself has a work function of 4.7 eV, which
In the best case (UV-ozone treated device for 9 min), the matches the HOMO level of P3HT for hole extraction. By
sheet resistance increased from 1.1 kΩ/sq to infinity and the replacing the periphery –COOH with the –COOCs groups
transmittance at 550 nm decreased from 95.2% to 93.8% through charge neutralization, the work function of the GO-
due to the formation of carbon-oxygen functionalization Cs can be reduced to 4.0 eV, which matches the LUMO level
layers. Although the device with 9 min treated graphene was of PCBM for efficient electron extraction. To investigate the
expected to show the best efficiency (PCE of 1.46%) due hole extraction ability of GO, three different devices with the
to its highest work function (4.85 eV), the best PCE was same active layer, cathode, and EELs were compared. The
obtained from the cell with 5 min treated graphene (3.00%) device with GO as HTLs showed a PCE of 3.25%, which was
probably because the graphene sheet was damaged by UV- superior to that of the device using PEDOT : PSS (3.15%),
ozone exposure after 7 min, which roughened the surface implying that GO is an excellent hole extraction material for
creating defects [80]. BHJ solar cells. Similarly, to evaluate the ability of GO-Cs
Jeon et al. [81] used moderately reduced graphene oxide as the electron extraction layer, four devices were fabricated
(mrGO) as an alternative to the PEDOT : PSS HTL in BHJ with the same anode, hole extraction layer, active layer, and
OSCs. mrGO films were fabricated by simple and fast thermal cathode. In this case, the device using LiF showed the best
treatment of solution processed mrGO. Spin-coated mrGO PCE (3.15%). However, the cell based on GO-Cs exhibited a
layers were thermally treated at 150, 250, and 350∘ C for 10 min fairly comparable PCE (3.08%) showing the great capability
in air. Devices without and with thermal treatment at 150 and of GO-Cs as electron extraction material in BHJ solar cells.
250∘ C showed a well-formed 2-dimensional nanosheet. On Finally, based on the excellent capabilities demonstrated for
the other hand, in the case of mrGO films thermally treated GO and GO-Cs, a pair of BHJ devices with both materials was
at 350∘ C, some aggregation of nanosheets and relatively fabricated. For this purpose, both the normal and inverted
nonuniform morphologies were observed. The thicknesses configurations were investigated. In both cases, the devices
of nanosheets of mrGO without and with thermal treatment exhibited a better performance (3.67% and 2.97%, resp.) than
at 150, 250, and 350∘ C were estimated to 1.18, 1.07, 0.87, and that of the control device (1.20%) based on Cs2 CO3 and
0.85 nm, respectively. The decrease in the thickness of single PEDOT : PSS [83].
sheet resulted from the removal of oxygen groups, indicating Qu et al. [84] reported a graphene fullerene compos-
that solution processed mfGO films were reduced by simple ite (rGO-pyrene-PCBM), in which PCBM was attached
thermal treatment. Devices with thermally treated mrGO at onto rGO via the noncovalent functionalization approach.
250∘ C exhibited the best PCE (3.98%) compared to devices rGO-pyrene-PCBM was successfully applied as EELs for
containing conventional PEDOT : PSS HTLs, which showed P3HT : PCBM BHJ devices, affording a PCE of 3.89%, which
3.85%. Furthermore, mrGO-based cells showed superior is enhanced by ∼15% compared to that of the reference
stability compared to conventional devices under atmosphere device without EELs (3.39%). Additionally, the comparative
condition without any encapsulation process [81]. devices incorporating the rGO or pyrene-PCBM component
Liu et al. [82] developed a sulfated graphene oxide (GO- as EELs showed dramatically decreased PCE, 2.53% and
OSO3 H) with –OSO3 H groups attached to the carbon basal 2.18%, respectively, which are much lower than that of the
plane of reduced GO surrounded with edge-functionalized reference device, indicating the importance of composite
formation between rGO and pyrene-PCBM components for 5. Conclusions

its electron extraction property [84].
Nguyen et al. [85] demonstrated the use of a few-layered In this report, the various applications of graphene as a
graphene nanosheets- (FLGs-) PEDOT : PSS composite as constituent of BHJ OSCs were discussed focusing on the PCE
an effective HTL that improves the hole transporting ability achieved by the graphene-based devices. Results indicate that
in an organic device, with which the PCE was enhanced there is a great room and need for the improvement of BHJ
from 3.10% to 3.70%. FLGs are considered to be a class devices to compete with inorganic cells. However, there is also
of graphene materials, namely, 2D graphitic crystals, with evidence that graphene and its derivatives can be successfully
extraordinary electronic transport properties varied sys- used as a main component of the different layers that consti-
tematically by the number of graphene layers. FLGs were tute OSCs, giving the possibility to reduce the dependence on
synthetized via exfoliation from expanded graphite, since this the materials traditionally employed. As for transparent elec-
method produces a low defects material with an excellent trode material, graphene has demonstrated great potential
conductivity. To demonstrate the application of the FLGs- without the detrimental aspects of its traditional analogues;
PEDOT : PSS composite as HTLs, FLGs and PEDOT : PSS the main key to achieve a better performance relies on
were mixed at different volume ratios (1/1, 2/1,) as a part increasing the transparency and decreasing the sheet resis-
of a BHJ device based on P3HT : PCBM. All samples were tance of the graphene films. As for cathode material, the main
measured under light illumination of AM1.5 (100 mW/cm2 ). aim is to control the work function mainly using interfacial
By increasing the v/v ratio of FLGs and PEDOT : PSS, PCE layers or doping graphene films. Furthermore, its outstanding
increased to 3.47% (1/1) and 3.70% (2/1). Due to partially properties such as its band structure and dispersion ability
containing oxygen groups on the graphene edges of FLGs, have made it also adequate to be used as an acceptor material.
it was expected that the work function of the FLGs was The improvement of graphene miscibility to assure a good
in the range of 4.4 eV (graphite) to 5.1 eV (acid-oxidized dispersion represents an important issue in order to increase
MWCNTs), therefore possessing an energy level close to the performance of the devices using graphene as a main
that of P3HT. Furthermore, no significant differences were constituent of the active layer. Additionally, its excellent
found in surface roughness between the pure PEDOT : PSS charge extraction performance has made it viable to be used
and the FLGs-PEDOT : PSS composite films, indicating that as transport/extraction material in BHJ cells. The main goal
the contact resistance between the active layer and the hole in this area is to obtain HTL-materials that can be deposited
transport layer was unchanged in all devices. As a result, the from neutral aqueous suspensions and highly conductive
significant improvement of current density is attributed to EEL-materials using different functionalization agents.
higher hole mobility of FLGs as compared with PEDOT : PSS
[85]. Conflict of Interests
Yin et al. [86] reported a high-efficiency device made with
hydrophilic GO doped in PEDOT : PSS composites used as The authors declare that there is no conflict of interests
HTLs. The PCE of the nondoped composites was of 2.1% and regarding the publication of this paper.
increased to 3.8% for the doped composites under AM1.5G
100 mW/cm2 illumination in air. Preannealing of GO made References
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Alejandro Manzano-Ramírez,1 Edgar J. López-Naranjo,2

Correspondence should be addressed to Alejandro Manzano-Ramı́rez; [email protected]

Received 19 May 2015; Revised 30 August 2015; Accepted 31 August 2015

Academic Editor: Michal Otyepka

(a) (b) (c) (d)

Based on the simple consideration that low band gap

Table 1: PCE of BHJ OSCs using graphene as anode.

Material Device conformation Highest PCE Reference

Table 2: PCE of BHJ OSCs using graphene as cathode.

Material Device conformation Highest PCE Reference

Table 3: PCE of BHJ OSCs using graphene as acceptor material.

Material Device conformation Highest PCE Reference

Table 4: PCE of BHJ OSCs using graphene as HTLs and EELs.

Material Function Device conformation Highest PCE Reference

On the other hand, certain metal fluorides, n-type semi-

formation between rGO and pyrene-PCBM components for 5. Conclusions

Advances in The Scientific International Journal of

Journal of Journal of Journal of Journal of Journal of

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