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Graphene-Based Materials for Solar Cell Applications
Zongyou Yin, Jixin Zhu, Qiyuan He, Xiehong Cao, Chaoliang Tan, Hongyu Chen,
Qingyu Yan, and Hua Zhang*
Graphene has attracted increasing attention due to its unique electrical,
optical, optoelectronic, and mechanical properties, which have opened up
huge numbers of opportunities for applications. An overview of the recent
research on graphene and its derivatives is presented, with a particular focus
on synthesis, properties, and applications in solar cells.
1. Introduction
In the past decade, graphene, a 2D sheet composed of sp2-
bonded single-layer carbon atoms with the honeycomb lat-
tice structure, has attracted great research interest in physics,
chemistry, materials science, etc.[117] Until now, the electrical,
optical, mechanical, thermoelectric, and magnetic properties
of graphene have been intensively studied.[1834] In order to
mass produce high-quality 2D graphene nanosheets for poten-
tial applications, various strategies have been developed.[3540]
More importantly, graphene has been used in various applica-
tions. For example, its extremely high room-temperature carrier
mobility (20 000 cm2 v1 s1)[41] makes graphene a promising
candidate to replace the conventional semiconductor materials
in the electric circuit.[18,4246] Moreover, the high optical trans-
parency of graphene (only 2.3% of incident light absorbed in
the range from near-infrared to violet)[47] makes it promising
for next-generation transparent conductive electrodes, which
may replace traditional indium tin oxide (ITO) in optoelec-
tronics, displays, and photovoltaics.[4853] In addition, it is worth
mentioning that the large 2D basal plane with huge surface
area (2600 m2g1)[54] and high chemical/thermal stability of
graphene has been used as a template to synthesize versatile
functional composites used for sensors,[24,55,56] catalysts,[5760]
optical modulators,[10,61,62] antibacterial activities,[6365] sur-
face enhanced Raman scattering (SERS) platforms,[6668]
electrochemical devices,[6972] and energy storage.[7376] Fur-
thermore, the high flexibility makes graphene one of the
most promising materials for flexible and rollable electronics
applications.[49,51,7782]
Dr. Z. Yin, Dr. J. Zhu, Dr. Q. He, Dr. X. Cao, C. Tan,
Prof. Q. Yan, Prof. H. Zhang
School of Materials Science and Engineering
Nanyang Technological University
50 Nanyang Avenue, Singapore, 639798, Singapore
E-mail: hzhang@ntu.edu.sg
H. Chen
Division of Chemistry and Biological Chemistry
Nanyang Technological University
Singapore, 637371, Singapore
DOI: 10.1002/aenm.201300574
Adv. Energy Mater. 2014, 4, 1300574 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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The increasing demand for energy con-
sumption and the limited energy resources
are the two main driving forces for the
exploration of new energy-harvesting
processes, among which new materials,
especially nanomaterials, have been inves-
tigated in clean energy applications such
as solar cells,[8390] solar fuels,[9196] and
lithium-ion batteries (LIBs)[97104] and
supercapacitors.[ 105111 ] Here, we focus on the recent advances
of graphene-based materials for solar cell applications.
2. Various Applications in Solar Cells
With the unique properties, i.e., highly optical transparence,
highly electrical conduction, and mechanical flexibility, gra-
phene and its derivatives have been investigated extensively
in the field of solar cells. Lots of impressive results have been
reported, where graphene was used as the electrodes, i.e., trans-
parent anodes,[4951,82,112117] non-transparent anodes,[118,119]
transparent cathodes,[52,120122] and catalytic counter elec-
trodes,[117,123127] as well as where graphene was used as the
active layer, i.e., light harvesting material,[128130] Schottky
junction,[131135] electron transport layer,[136140] hole transport
layer,[141145] both hole and electron transport layer,[143] and inter-
facial layer in the tandem configuration.[146148] Table 1 summa-
rizes the previous work using graphene as the electrodes.
2.1. Conductive Electrodes
2.1.1. Transparent Conducive Anodes
Recently, graphene has been successfully used as the trans-
parent conductive anode for the flexible organic photovoltaic
(OPV) cell with the configuration graphene/poly(3,4-ethylene
dioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/copper
phthalocyanine (CuPc)/C60/bathocuproine(BCP)/Al
(Figure 1a).[82] Graphene was first deposited onto the Si/SiO2/
Ni film by chemical vapor deposition (CVD) and then trans-
ferred onto the transparent glass or polyethylene terephthalate
(PET) substrates (Figure 1b). The obtained graphene/PET film
showed its sheet resistance down to 230 /sq with transpar-
ency of 72%. The solar cell incorporating CVD-grown graphene
(referred to here as CVD-graphene) as the transparent conduc-
tive anode exhibited a power conversion efficiency () of 1.8%,
which is comparable to the performance (1.27%) obtained in
the device with the commonly used ITO electrode. Obviously,
the flexibility of CVD-graphene device surpasses that of the ITO
device because the former device can operate under bending
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up to 138 (Figure 1c), whereas the latter one degraded rapidly
and irreversibly even under bending of 60 (Figure 1d). Con-
sistently, the decay/decrease rate of the initial fill factor in the
CVD-graphene device was much slower than that in the ITO
one as the bending angle increased, and the fill factor of the
ITO device rapidly decayed to 0 when it was bent to around 60
(Figure 1e). The lower performance under bending, i.e., lower
flexibility, of the ITO device was caused by the generation of
microcracks in the ITO film under mechanical stress, while no
such microcracks were observed on the CVD graphene device
(Figure 1f).
In the area of flexible OPV devices, our group has used
chemically reduced graphene oxide (rGO) as the transparent
conductive anode in the device with configuration of rGO/
PEDOT:PSS/poly(3-hexylthiophene):phenyl-C61-butyric acid
methyl ester (P3HT:PCBM)/TiO2/Al. The performance of the
OPV devices mainly depends on the charge transport efficiency
and the transparency of the rGO electrodes, when the optical
transmittance of rGO is above and below 65%, respectively.
Impressively, the fabricated OPV device on rGO can sustain a
thousand bending cycles at 2.9% tensile strain.[51]
Iijima and co-workers reported a roll-to-roll method to
transfer the 30-inch CVD-graphene monolayer film from the
copper foil onto a flexible substrate, such as PET.[49] The gra-
phene film exhibited 97.4% optical transmittance with sheet
resistance as low as 125 /sq. After a four-layer graphene
film was achieved by layer-by-layer stacking, it was doped
with HNO3, showing the further decreased sheet resist-
ance (30 /sq at 90% transparency), which is superior
to the commercial transparent ITO electrode. Furthermore,
such graphene electrode was capable of withstanding high
strain.[49]
All of the aforementioned reports have demonstrated the
highly flexible nature of graphene, which shows its potential
application as the transparent conductive anode electrode for
flexible solar panels, since both CVD-graphene and solution-
processed rGO have exhibited superior mechanical perfor-
mance over ITO. For the flexible CVD-graphene based thin
film, which is compatible with the roll-to-roll fabrication pro-
cess developed by Iijima and co-workers,[80] it possesses not
only better mechanical properties than ITO, but also superior
sheet resistance and transparency compared to ITO when used
as a transparent electrode.
In addition to the OPV devices, graphene also shows poten-
tial as the transparent anode electrode for dye sensitized solar
cells (DSSCs). In a recent report,[50] the graphene thin film,
prepared by dip coating aqueous graphene oxide (GO) solution
on quartz followed by temperature-controlled film drying and
subsequent thermal reduction, exhibited a high conductivity of
550 S cm1 and transparency of more than 70% in the wave-
length range of 10003000 nm. A solid-state DSSC with con-
figuration of graphene/TiO2/dye/spiro-OMeTAD/Au has been
fabricated using the graphene film as the transparent anode
(Figure 2a). The corresponding energy level diagram of the
DSSC device is shown in Figure 2b. This is the first demonstra-
tion of a solid-state DSSC based on a graphene electrode with
the power conversion efficiency (PCE) of 0.26%, which is still
lower compared to the fluorine tin oxide (FTO)-based solid-state
DSSC (0.84%; Figure 2c).
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Zongyou Yin studied at Jilin
University in China for his
B.E. and M.S., and com-
pleted his Ph.D. at Nanyang
Technological University
in Singapore (2008). He
is currently working as a
postdoctoral fellow in Prof.
Hua Zhangs group. His
research interests include the
synthesis and application of
new functional nanomaterials
based on graphene and its inorganic analogues.
Hua Zhang studied at
Nanjing University (B.S.,
M.S.), and completed his
Ph.D. at Peking University
(with Zhongfan Liu) in 1998.
After postdoctoral work at
Katholieke Universiteit Leuven
(with Frans De Schryver) and
Northwestern University (with
Chad Mirkin), and working
at NanoInk Inc. and the
Institute of Bioengineering
and Nanotechnology (Singapore), he joined Nanyang
Technological University (2006). His current research
interests focus on synthesis of 2D and low-dimensional
nanomaterials and carbon materials (graphene and CNTs),
and their applications in nano- and biosensing, clean
energy, etc.
2.1.2. Transparent Conducive Cathodes
Graphene has also been developed as the transparent conduc-
tive cathode electrode for solar cells. Recently, our group has
reported that rGO was used as the working electrode for electro-
chemical deposition of functional materials, which was further
used as the cathode electrode for the hybrid solar cell applica-
tion.[52] Briefly, the rGO thin film on quartz was obtained by
two-step reduction of GO, i.e., using hydrazine vapor and then
thermal annealing. It exhibited a sheet resistance of 420 /sq at
61% transmittance. The n-type ZnO nanorods (NRs) were elec-
trochemically deposited on the obtained rGO electrode. Then,
the p-type poly(3-hexylthiophene) (P3HT) layer was spin-coated
on the top of ZnO NRs to form an inorganicorganic material
based hybrid solar cell. In addition, we found that the electro-
chemical deposition of ZnO strongly depends on the thickness,
i.e., the sheet resistance, of the rGO film. The thicker rGO film
with lower sheet resistance has advantages for the growth of
high quality crystalline ZnO nanorods. The device with a lay-
ered structure of quartz/rGO/ZnO NRs/P3HT/PEDOT:PSS/Au
was fabricated with a PCE of around 0.31% (Figure 3a).
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Table 1. Previous work on graphene or reduced graphene oxide (rGO) used as electrodes in solar cells.

Material Electrode (Rs: sheet resistance; Type and configuration of solar cells PCE [%] Ref.
T: transmittance)
rGO Transparent anode (Rs: 1.8 k/sq Solid-state DSSC: glass/rGO/TiO2/dye/ 0.26 [50]
at T: 70%) spiro-OMeTAD/Au
rGO Transparent anode (Rs: 3.2 k/sq OPV: PET/rGO/PEDOT:PSS/ 0.78 [51]
at T: 65%) P3HT:PCBM/TiO2/Al
CVD-graphene Transparent anode (Rs: 0.25 k/sq OPV: quartz/graphene/PEDOT:PSS/ 0.85 [115]
at T: 92%) CuPc:C60/BCP/Ag
rGO-CNT Transparent anode (Rs: 0.6 k/sq OPV: glass/rGO-CNT/PEDOT:PSS/ 0.85 [112]
at T: 87%) P3HT:PCBM/Ca:Al
CVD-graphene Transparent anode (Rs: 3.5 k/sq OPV: PET/graphene/PEDOT:PSS/ 1.18 [82]
at T: 89%) CuPc:C60/BCP/Al
CVD-graphene Transparent anode (Rs: 0.08 k/sq OPV: quartz/graphene/MoO3+ 2.5 [113]
at T: 90%) PEDOT:PSS/P3HT:PCBM/LiF/Al
Tetracyanoquinodimethane Transparent anode (Rs: 0.278 k/sq OPV: glass/TCNQ-graphene/PEDOT: 2.58 [116]
(TCNQ)-graphene at T: 92%) PSS/ P3HT:PCBM/Ca/Al
Au-doped graphene Transparent anode (Rs: 0.293 k/sq OPV: Au-graphene/PEDOT:PSS/ 3.04 [117]
at T: 90%) P3HT:PCBM/ZnO/ITO
rGO Transparent cathode (Rs: 0.42 k/sq Hybrid solar cell: quartz/rGO/ZnO/ 0.31 [52]
at T: 61%) P3HT/ PEDOT:PSS/Au
Al-TiO2 modified graphene Transparent cathode (Rs: 1.2 k/sq OPV: Au/graphene/Al-TiO2/P3HT: 2.58 [121]
at T: 96%) PCBM/MoO3/Ag
CVD-graphene Transparent cathode (Rs: 0.22 k/sq Thin film solar cell: glass/graphene/ 4.17 [120]
at T: 84%) ZnO/ CdS/CdTe/graphite paste
CVD-graphene Transparent cathode (Rs: 0.3 k/sq Hybrid solar cell: glass/graphene/ 4.2 (0.5) [122]
at T: 92%) PEDOT:PEG(PC)/ZnO/PbS QD(P3HT)/
MoO3/Au
Functiona-lized rGO Catalytic counter electrode Liquid DSSC: FTO/TiO2/dye/I3 /I1 4.99 [124]
mediated electrolyte/rGO
CVD-graphene Catalytic counter electrode Liquid DSSC: FTO/TiO2/dye/I3 /I1 5.73 [125]
mediated electrolyte/graphene
TiN-rGO Catalytic counter electrode Liquid DSSC: FTO/TiO2/dye/I3 /I1 5.78 [127]
mediated electrolyte/TiN-rGO
CNT-rGO paper Catalytic counter electrode Liquid DSSC: FTO/TiO2/dye/I3 /I1 6.05 [117]
mediated electrolyte/CNT-rGO
Graphene platelets Catalytic counter electrode Liquid DSSC: FTO/TiO2/dye/Co(III)/(II) 9.3 [126]
mediated electrolyte/graphene

As another example, Jiang and co-workers have successfully
demonstrated the CdTe thin film solar cell using CVD-gra-
phene as the front transparent electrode.[120] The graphene film
used in their work was grown on Cu foil by the low-cost CVD
at ambient pressure and then it was transferred onto the glass
substrate. Importantly, the layer number of graphene was well
controlled by the inlet H2 flow rate during the CVD growth.
The sheet resistance of the obtained graphene film is 220 /sq
at the transparency of 84%. As a proof of concept, the prototype
device with configuration of glass/graphene/ZnO/CdS/CdTe/
(graphite paste) has been fabricated (Figure 3b), with PCE of as
high as 4.17% (Figure 3c).
CVD-graphene normally is hydrophobic, which hampers
the direct growth of functional semiconductors on top through
the hydrothermal synthesis method. Using the conductive
polymer modification of CVD-graphene, Park and co-workers
successfully grew crystalline ZnO nanowires on a graphene
substrate via the hydrothermal method.[122] The obtained gra-
phene layer on glass after transferred from Cu foil exhibited
the sheet resistance of 300 /sq with transparency of 92%.
Based on the obtained graphene/polymer/ZnO structures, a
graphene-cathode based hybrid solar cell using PbS QDs and
P3HT as the p-type active material and ZnO as n-type mate-
rial has been developed (Figure 3d). The JV characteristics of
PbS QD and P3HT based hybrid solar cells are presented in
Figure 3e,f, respectively. The obtained PCEs of PbS QD-based
devices on ITO/ZnO, graphene/PEDOT:PEG(PC)/ZnO and
graphene/RG-1200/ZnO were 5.1%, 4.2%, and 3.9%, respec-
tively. The obtained PCEs of P3HT-based devices ITO/ZnO,
graphene/PEDOT:PEG(PC)/ZnO, and graphene/RG-1200/ZnO
were 0.4%, 0.3%, and 0.5%, respectively. It shows that the gra-
phene electrode is comparable with ITO in these devices.

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Figure 1. a) Schematic representation of the energy level alignment (top) and the construction of heterojunction organic solar cell fabricated with
graphene as anodic electrode: graphene/PEDOT/CuPc/C60/BCP/Al. b) Schematic illustration of the transfer process of CVD-graphene onto transparent
substrate. c,d) The plots of current density vs voltage for c) graphene and d) ITO devices under 100 mW cm2 AM1.5G spectral illumination at different
bending angles. Insets show the experimental setup used in the experiments. e) The plot of fill factor vs bending angle for the graphene and ITO devices.
f) Scanning electron microscopy (SEM) images of the surface structure of CVD-graphene (top) and ITO (bottom) devices after being subjected to the
bending angles described in panels (c,d). Reproduced with permission.[82] Copyright 2010, American Chemical Society.

The sheet resistance and transparency of graphene used as
the transparent electrode are two main factors that influence
the performance of graphene-based solar cells. For example,
the quartz/graphene/RG-1200/ZnO nanowires/P3HT/MoO3/
Au device exhibits a PCE of 0.5%,[122] enhanced by 61%
compared to the device of quartz/rGO/ZnO nanorods/P3HT/
PEDOT:PSS/Au with PCE of 0.31%.[52] The main reason is that
the CVD-graphene prepared in the former work has a much
better sheet resistance of 300 /sq at transparency of 92% com-
pared to the sheet resistance of 420 /sq at transparency of

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Figure 2. Illustration and performance of DSSC based on graphene electrodes. a) Schematic illustration of DSSC using graphene film as electrode. The
four layers from bottom to top are Au, dye-sensitized heterojunction, compact TiO2, and graphene film. b) The energy level diagram of the DSSC with
the configuration of graphene/TiO2/dye/spiro-OMeTAD/Au. c) Current densityvoltage curves of the graphene-based cell (black) and FTO-based cell
(red) illuminated under AM solar light (1 sun). Reproduced with permission.[50] Copyright 2008, American Chemical Society.

61% from the solution-processed rGO in the latter work. This
indicates the crystal quality of CVD-graphene is higher than the
solution-processed rGO since there are still oxygen functional
groups in rGO.[149] Importantly, the CVD-graphene based ZnO-
P3HT hybrid solar cells exhibited higher PCE compared to the
ITO electrode.[122,150] All the aforementioned results indicate
the great potential of graphene as a new transparent conductive
cathode material to replace the traditional ITO for the hybrid
solar cell applications.
2.1.3. Catalytic Counter Electrodes
As discussed above, graphene with its highly transparent con-
ductive characteristics has been used as efficient transparent
conductive electrodes in various photovoltaic devices. Much
beyond that, graphene has also been used for the catalytic
counter electrode in DSSCs with the prospect to replace the
traditional expensive platinum (Pt) counter electrode. To date,
much related research has been published, as listed in the
Table 1. Some typical work will be reviewed in the discussion
that follows.
Aksay and co-workers use the functionalized graphene sheet
(FGS) as a stand-alone catalyst in a DSSC to replace Pt.[124] The
FGS-based cell gave a high efficiency of 5%, which is only 10%
lower compared to the corresponding Pt-based cell (Figure 4c).
The catalytic activity from FGS is attributed to its comparable
charge-transfer resistance with platinum at an applied bias,
and the introduced oxygen-containing functional groups on
FGS (Figure 4a,b). Finally, they demonstrated that the FGS
ink-casted plastic substrate can be used as an efficient counter
electrode, eliminating the requirement for the common FTO
substrate. Tailoring the functionalization or morphology of the
FGS electrodes could decrease the charge-transfer resistance
and also facilitate the low-cost production of the catalytic, flex-
ible, and conductive counter electrodes for DSSCs.
Graphene nanoplatelets (GNPs) as a counter electrode mate-
rial have been demonstrated with high electrocatalytic activity
for the redox of Co(L)2 (L = 6-(1H-pyrazol-1-yl)-2,2-bipyridine)
by Grtzel and co-workers.[126] They observed that the exchange
current density for the Co2+/3+(L)2 redox was 1 to 2 orders of
magnitude larger than those for the conventional I3/I redox
couple on the same electrode. In the Co2+/3+(L)2 redox system,
the electrocatalytic activity of GNP-film cathode with optical
transmission below 88% outperformed the activity of the Pt
electrode. DSSCs with Y123 dye adsorbed on TiO2 photoanode
achieved the energy conversion efficiency of 810% for both
GNP and Pt-based cathodes. Importantly, the cell with GNP
cathode is superior to that with Pt cathode particularly in the
fill factor and the efficiency at higher illumination intensity
(Figure 4d,e).
In addition to pure graphene, graphene-based composites
with controlled functionalization have also been developed for
the catalytic counter electrodes. Chen et al. first realized the
direct growth of vertically aligned carbon nanotubes (VACNTs)
on 3 m thick graphene paper (GP) by a thermal CVD
method.[117] The as-prepared freestanding VACNT/GP film pos-
sesses superb flexibility and durability, which is attributed to the
highly flexible GP (Figure 5a). When employed as the counter
electrode in a DSSC, it displayed superior overall performance
over the GP or the tangled CNT/GP film and only slightly lower
efficiency compared to the Pt electrode (Figure 5b).
A facile and versatile route has been developed to synthe-
size nanohybrids of titanium nitride (TiN) nanoparticles deco-
rated on nitrogen-doped graphene (NG).[127] The resulting TiN/
NG hybrids exhibited comparable catalytic performance to the
platinum (Pt), which is widely used as the counter electrode

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Figure 3. a) Current densityvoltage (JV) characteristics of ZnO/P3HT hybrid solar cells with rGO film as electrode. Inset: schematic illustration of the
fabricated solar cell. Reproduced with permission.[52] b) Schematic diagram and c) JV characteristics of the glass/graphene/ZnO/CdS/CdTe/(graphite
paste) solar cell. Reproduced with permission.[120] d) Schematic illustration of glass/graphene/conductive polymer (PEDOT:PEG(PC) or Plexcore OC
RG-1200)/ZnO/PbS QD(P3HT)/MoO3/Au hybrid solar cells with PbS QD or P3HT as the photoactive material. e) JV characteristics of PbS QD based
device with different polymer interlayers, demonstrating their performance comparable to that of a reference solar cell on ITO substrate. f) JV char-
acteristics of P3HT based device with different polymer interlayers, compared with a reference device on ITO. Insets in (e,f) show the cross-sectional
SEM images of the device. Reproduced with permission.[122] Copyright 2012, American Chemical Society.

in DSSCs (Figure 5c,d). This work demonstrated that the TiN/
NG nanohybrids can be used as a low-cost counter electrode
to replace the traditional Pt in DSSCs. Furthermore, the den-
sity functional theory (DFT) calculation indicated that the high
catalytic performance of TiN/NG originates from the synergetic
effect between TiN and NG.
Based on the aforementioned promising results achieved
from graphene and graphene-based composites, we can antici-
pate the great potential of graphene-based materials to replace
the traditional expensive Pt electrode as a low-cost catalytic
counter electrode in DSSCs.
2.2. Active Layers
The facile chemical functionalization enables graphene as a
new candidate for active material in photovoltaic device appli-
cations.[128130] Moreover, the work function of graphene can
be adjustable by doping with another semiconductor to form a
Schottky junction if their energy band structures match.[131135]
With high charge mobility, graphene and rGO are good can-
didates for the electron transport layer,[136140] hole transport
layer,[141,142,144,145] both hole and electron transport layer,[143]
and interfacial layer for tandem solar cells in the photovoltaic

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Figure 4. a) Schematic illustration of functional groups and lattice defects on an FGS. Epoxides and hydroxyls are on both sides of the graphene plane,
while carbonyl and hydroxyl groups are at the edges. A 585 defect (green), and a 5775 (Stone-Wales) defect (yellow) are also shown. Carbon,
oxygen, and hydrogen atoms are gray, red, and white, respectively. b) Side view emphasizing the topography of the FGS. These schematics are rep-
resentative of the functionalities on FGS but not an actual sheet, which would measure on the order of 1 m across. c) JV characteristics of DSSCs
using thermally decomposed chloroplatinic acid and FGS counter electrodes. Active area is 0.39 cm2. Reproduced with permission.[124] Copyright 2010,
American Chemical Society. d) JV characteristics of DSSCs with Pt counter electrode. e) JV characteristics of DSSCs with GNP counter electrode.
Reproduced with permission.[126] Copyright 2011, American Chemical Society.

field.[146148] The previously reported photovoltaic devices that
use graphene or graphene-based composites in active layers
have been summarized in Table 2. Some typical researches will
be reviewed as follows.
2.2.1. Light-Harvesting Materials
GO is easy to be functionalized based on various requirements
since it has various functional groups. For example, Chen and
co-workers functionalized GO sheets with phenyl isocyanate,
which changed hydrophilic GO surface to hydrophobic one.[128]
The resultant solution-processed functionalized graphene (SPF-
Graphene) was mixed with poly(3-octylthiophene) (P3OT) to
form the P3OT/SPFGraphene composites, which were then
used as the active layer material in the bulk heterojunction
(BHJ) OPV device (Figure 6ad). The annealing conditions are
critical for better performance of the device, since annealing
can remove the functional groups from graphene sheets and
enhance the crystallinity of P3OT. Based on their result, the
optimized annealing condition, 160 C for 20 min, was applied
for fabrication of the OPV device, which achieved the best
power conversion efficiency of 1.4%. This work indicated that
the functional graphene can serve as a competitive alternative
to [6,6]-phenyl C61-butyric acid methyl ester (PCBM) as the elec-
tron acceptor for high-performance OPV devices.
Importantly, the effect of graphene with different lateral size
in OPV devices was studied.[130] In this work, the active layer of
OPV device was composed of aniline-functionalized graphene

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Figure 5. a) Flexible GP. b) Currentvoltage characteristics of four DSSCs using the Pt, GP, TCNT/GP film, and VACNT/GP film as counter electrodes.
Reproduced with permission.[117] c) Schematic illustration of a DSSC using TiN/NG as the counter electrode. d) Characteristic JV curves of DSSCs
with TiN/NG or Pt counter electrodes measured under simulated sunlight 100 mW cm2 (AM 1.5). Inset table: photovoltaic parameters of DSSCs with
different counter electrodes. Reproduced with permission.[127]

(used as electron acceptor) and P3HT (used as electron donor).
It was found that after optimization, the device with aniline-
functionalized graphene quantum dots (ANI-GQDs) and P3HT
showed enhanced efficiency as compared to the one with
aniline-functionalized graphene sheets (ANI-GS) and P3HT.
The corresponding current density versus voltage curves of
ANI-GQDs-P3HT and optimized ANI-GS-P3HT based devices
are plotted in Figure 7a. The maximum power conversion effi-
ciency is 1.14% obtained from ANI-GQDs with 1 wt% of ANI-
GQD and P3HT, which is much higher than 0.65% obtained
from the optimized ANI-GS devices with 10 wt% ANI-GSs and
P3HT. This is attributed to the improved morphological and the
optical characteristics in ANI-GQDs. The performance of GQD-
based devices is expected to be further improved by choosing
other proper functionalization systems.
In addition, Li and co-workers presented a novel solubiliza-
tion strategy for synthesis of graphene nanostructures through
a bottom-up method instead of the common top-down method
based on the exfoliation of graphite.[129] Solution-processable
black GQDs with uniform size were synthesized through solu-
tion chemistry, which were then used as a sensitizer for solar
cells (Figure 7b). However, a much low current density was
observed, which was attributed to the low affinity of GQDs on
TiO2 surface due to the physical adsorption, and the conse-
quent poor charge injection. In the future, synthesis of hydro-
philic graphene nanostructures or realization of the chemical
bonding between graphene nanostructures and TiO2 surface is
expected to improve the device performance.
2.2.2. Schottky Junctions
The metallic graphene can form the Schottky junction with
semiconductor and employed as the active layer for solar cells.
Qin and co-workers have developed a simple and scalable pat-
terning method for graphene using electron-beam or ultraviolet
lithography followed by a lift-off process.[152] The patterned
graphene was used for fabrication of CdSe nanobelt (NB)/gra-
phene Schottky junction solar cells. An ideal Schottky junction
was formed between metallic graphene and semiconducting
CdSe NB, which facilitates the electron-hole separation and
diffusion driven by the built-in potential between graphene
and CdSe. Accordingly, an excellent photovoltaic with an
open-circuit voltage of 0.51 V, a short-circuit current density
of 5.75 mA cm2 and an overall solar energy conversion effi-
ciency of 1.25% has been obtained.
Similarly, solar cells based on Schottky junctions between
graphene sheets (GSs) and n-type doped Si (n-Si) have been
developed (Figure 8a).[133] In these examples, the GS film not
only serves as a transparent electrode for light transmittance,
but also is used as the Schottky junction layer for the electron
hole separation and hole transport. This means that the pho-
togenerated carriers are separated by the built-in field, while
the electrons and holes are diffused to GS and n-Si, respectively
(Figure 8b). The solar energy conversion efficiency is 1.65%
and 1.34% for the devices with junction areas of 0.1 cm2 and
0.5 cm2, respectively (Figure 8c). Although the efficiency of
such GS/n-Si Schottky junction devices is still far lower than

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Table 2. Summary of graphene and graphene-based composites used in active layers for solar cells.

Materials Function Configuration of solar cells PCE [%] Ref.

Graphene QDs Sensitizer of dye Liquid DSSC: FTO/TiO2/graphene QD dye/ I3/I1 mediated <0.1 [129]
electrolyte/Pt
Aniline-modified GO QDs Electron acceptor OPV: ITO/P3HT/ANI-GQDs/Al 1.14 [130]
rGO (called graphene in the cited paper) Electron acceptor OPV: ITO/PEDOT:PSS/P3OT:graphene/ LiF/Al 1.4 [128]
GrapheneCdSe nanobelts Schottky junction layer Schottky junction solar cell: Si/SiO2/graphene-CdSe 1.25 [134]
nanobelt/In-Au
Graphene/n-Si Schottky junction layer Schottky junction solar cell: Ti/Pb/Ag/n-Si/graphene/Au 1.65 [133]
HNO3-modified-graphene/Si pillar array Schottky junction layer Schottky junction solar cell: Ti/Pb/Ag/Si pillar array/ 7.7 [135]
graphene/Ti/Au
Graphene-TiO2 Schottky junction layer Liquid DSSC: FTO/TiO2-graphene/dye/I3 /I1 mediated 6.06 [132]
electrolyte/Pt
TFSA-doped graphene/n-Si Schottky junction layer Schottky junction solar cell: In/Ga eutectic/n-Si/TFSA doped 8.6 [131]
graphene/Cr/Au
rGO (called graphene in the cited paper) Electron transport layer OPV: ITO/PEDOT:PSS/P3HT:PDIa)-graphene/LiF/Al 1.04 [136]
rGO Electron transport layer Liquid DSSC: FTO/rGO/TiO2/dye/I3/I1 mediated 1.68 [140]
electrolyte/Pt
rGO Electron transport layer Liquid DSSC: FTO/rGO/TiO2/dye/ electrolyte/Pt 6.97 [139]
HNO3 oxidized CVD-graphene Electron transport layer OPV: ITO/PEDOT:PSS/PCDTBTb)/PC71BMc)/GO/TiOx/Al 7.5 [151]
rGO-P3HT Hole transport layer OPV: ITO/PEDOT:PSS/rGO-P3HT/C60/Al 0.61 [144]
GO Hole transport layer OPV: ITO/GO/P3HT:PCBM/Al 3.5 [141]
p-TosNHNH2 reduced GO (pr-GO) Hole transport layer OPV: ITO/pr-GO/P3HT:PCBM/Ca/Al 3.7 [142]
GO-SWCNT Hole transport layer OPV: ITO/GO-SWCNT/P3HT:PCBM /Ca/Al 4.1 [145]
GO and cesium-neutralized GO (GOCs) Hole and electron OPV: ITO/GO/P3HT:PCBM/GOCs/Al 3.67 [143]
transport layer
MoO3-graphene Interfacial layer Series tandem solar cell: ITO/PEDOT:PSS/ P3HT:PCBM/ 2.3 [146]
graphene-MoO3/ZnPc:C60/LiF/Al
Parallel tandem solar cell: ITO/ZnO/P3HT: PCBM/ 2.9
MoO3-graphene-MoO3/ZnPc:C60/LiF/Al
ZnO-GO-PEDOT:PSS Interfacial layer Series tandem solar cell: ITO/PEDOT:PSS/ P3HT:PCBM/ 4.14 [148]
ZnO-GO-PEDOT:PSS/ P3HT:PCBM/Ca/Al
GO-SWCNTs Interfacial layer Regular series tandem solar cell: ITO/GO: SWCNTs/ 4.1 [147]
P3HT:PCBM/ZnO-GO:SWCNTs /P3HT:PCBM/Ca /Al
Inverted series tandem solar cell: ITO/ZnO/P3HT:PCBM/ 3.5
GO:SWCNTs/ZnO/P3HT:PCBM/GO:SWCNTs/Al

a)PDI:
N,N-dioctyl-3,4,9,10-perylenedicarboximide; b)PCDTBT:poly[N-9-heptadecanyl-2,7-carbazole-alt-5,5-(4,7-di-2-thienyl-2,1,3-benzothiadiazole)]; c)PC71BM: [6,6]-
phenyl C71 butyric acid methyl ester

that of pure silicon thin-film solar cells (12%),[153155] it pro-
vides an improved understanding of the effects on solar cell
performance from the electronic coupling, surface passivation,
doping, and junction formation. Therefore, more advanced and
efficient graphene/silicon-based architectures with improved
solar cell performance are possible.
Furthermore, Hebard and co-workers reported that the
performance of Schottky solar cells based on the graphene-Si
system can be greatly enhanced after proper doping of gra-
phene.[131] Figure 9a shows the schematic illustration of the
Schottky solar cell composed of doped graphene/n-Si. The gra-
phene sheet was first doped with bis(trifluoromethanesulfonyl)-
amide[((CF3SO2)2NH)] (TFSA). This TFSA doped (p-type
doping) graphene exhibited lower sheet resistance.
Importantly, the TFSA doping further increased the work func-
tion of graphene, thus increasing the built-in potential between
the doped-graphene and n-Si in solar cells (Figure 9b). As
shown in the JV characteristics before and after doping of the
graphene sheets with TFSA (Figure 9c), Jsc, Voc, and fill factor
(FF) increase from 14.2 to 25.3 mA cm2, 0.43 to 0.54 V, and
0.32 to 0.63, respectively. The increases in Jsc and Voc boost the
power conversion efficiency from 1.9% to 8.6% (Figure 9c),
which is the highest power conversion efficiency reported for
graphene-based solar cells to date. Additional characterization
of this device is presented in Figure 9d, showing the external
quantum efficiency (EQE) before and after doping of graphene.
The pristine device shows an EQE near 50% in the wavelength
range of 400850 nm, indicating the significant electronhole

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Figure 6. a) The idealized chemical structures of graphene and P3OT. b) Schematic illustration of the device with P3OT/graphene thin film as the active
layer and the structure ITO (ca. 17 /sq)/PEDOT:PSS (40 nm)/P3OT:graphene (100 nm)/LiF (1 nm)/Al (70 nm). c) Energy level diagram of P3OT
and SPFGraphene. d) Schematic representation of the reaction of phenyl isocyanate with GO to form SPFGraphene. Reproduced with permission.[128]

pair generation and the subsequent facile collection of elec-
trons and holes by the corresponding electrodes. After the
TFSA doping, the EQE was significantly increased to a value of
65% in the abovementioned wavelength range, which is due
to the more efficient charge separation and charge collection
as a result of the increased built-in potential and reduced sheet
resistance.
Based on the aforementioned discussion, graphene,
which works as the electron acceptor after being functional-
ized with organic materials or as the Schottky junction metal
layer combined with the inorganic semiconductors, has pre-
sented promising performance in solar harvesting. Since the
performance is still low compared to the current equivalent
solar cells without graphene, lots of work should be done
for the improvement of performance, such as the design of
graphene-based architectures with specific
physical properties at heterojunctions, the
chemistry at interface of the graphene-based
hybrids, and the exploration of advanced
materials and processing technologies.
Combining low cost, mass production,
high electron mobility with efficient charge
transport, and 2D features with facile func-
tionability, graphene is expected to play an
increasingly important role in both research
and industry for sustainable clean energy by
partially or even fully replacing organic and/
or Si in photovoltaic cells in the future.

Figure 7. a) JV characteristics of the photovoltaic devices based on ANI-GQDs with different

2.2.3. Charge Transport Layers
amount of GQDs in ANI and ANI-GS with 10 wt% GS in ANI (under optimized condition)
annealed at 160 C for 10 min. Reproduced with permission.[130] Copyright 2011, American
Chemical Society. b) JV characteristics of a typical nanocrystalline TiO2 solar cell sensitized 2.2.3.1. Electron Transport Layer. Taking
by GQDs, in the dark and under illumination, respectively. Reproduced with permission.[129] the advantage of high electron mobility of
Copyright 2010, American Chemical Society. graphene, Jiang and co-workers reported

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Figure 8. a) Schematic illustration, b) energy diagram, and c) room-temperature JV characteristics of a GS/n-Si Schottky junction solar cell. In (b,e),
G and n-Si are the work functions of graphene and n-Si, respectively; V0 is the built-in potential. Vbias is the applied voltage for solar cells. b is the
barrier height. is the electron affinity. EC, EV, and EF correspond to the conduction band edge, valence band edge, and Fermi level, respectively, and
Eg is the bandgap. Reproduced with permission.[133]
that rGO can be used as the 2D electron transport channel
in rGO-TiO2 nanocomposite based DSSCs, showing better
performance than 1D CNT-TiO2 composite based DSSCs
(Figure 10 ad). In graphene composite electrodes, the particles
can anchor onto graphene better, and the photogenerated elec-
trons can be easily captured and transferred by the graphene.
However, when the composite of TiO2 with 1D CNT is formed,
there is less contact/connection between them. Therefore, the
transfer barrier is large, resulting in the severe recombination
of electrons and holes. Based on the operational principle of
the device (Figure 10e), the introduced 2D graphene performs
as an electron transport layer, i.e., accepts electrons from TiO2
and then transfers them quickly to the FTO electrode. There-
fore, the recombination of electrons and holes is suppressed. In
Figure 10f, the photocurrentvoltage characteristics of DSSCs
with different electrodes are presented. The best performance
is demonstrated by the device with the photoanode layer of
TiO2 with loading of 0.4% rGO (i.e., 0.6% GO loading since
GO will lose weight after reduction).[139] It means there is an
optimal rGO loading window in terms of the PCE of the devices
because too little graphene loading weakens its electron trans-
porting effect, while too much graphene loading reduces the
dye adsorption onto TiO2. Moreover, the excessive graphene can
act as a kind of recombination center instead of providing an
electron pathway, thus easily triggering the short circuit.
As another example, graphene as the electron transport layer
(ETL) in OPV has been reported by Heeger and co-workers.[151]
Instead of the usual solution-processed coating to prepare
graphene film, they developed a novel facile stamping process
to directly transfer graphene onto the bulk heterojunction (BHJ)
layer prior to the top Al cathode deposition. Such stamping
nanotechnology is able to transfer large-area, single-layer
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CVD-graphene onto specific regions of a substrate. In this
work, the graphene was first doped/oxidized by HNO3, which is
also called graphene oxide (GO). In order to compare with the
traditional TiOx ETL used in OPV, the pure GO, pure TiOx, and
GO/TiO2 double layer used as the ETL in OPV and the device
without the ETL were all studied. Consistently, the OPV with
ETL has much higher power conversion efficiency (PCE) than
that without the ETL. Importantly, the PCE of a device based on
a GO/TiO2 ETL was increased by 6.8% compared to the pure
TiO2 ETL based device. The improved BHJ device performance
is attributed to the fact that introduction of the GO/TiO2 ETL
layer, as compared to the pure TiO2 or GO ETL layer, increases
the hole blocking barrier (h) and simultaneously shifts Evac
downwards, thereby decreasing the electron injection barrier in
the BHJ device. The larger hole blocking barrier facilitates the
photogenerated hole to transport towards the ITO anode. The
smaller electron injection barrier enables the photogenerated
electron to transport efficiently towards the Al cathode. Hence,
such a synergistic effect enhances the short-circuit current den-
sity (Jsc) and thus the PCE of GO/TiO2 ETL-based BHJ devices.
2.2.3.2 Hole Transport Layer. Different from graphene, which
is a highly efficient electron transporter, the functionalized
GO and GO-based composites showed excellent hole trans-
port properties in photovoltaic devices. Huang and co-workers
have combined GO and SWCNTs as the hole transport layer
for P3HT:PCBM-based polymer solar cells (Figure 11a). They
found that the addition of the proper amount of SWCNTs into
GO can significantly improve the conductivity of the GO film
as the hole transport layer. Such GO:SWCNT composite films
reduce the hole transport resistance and facilitate the hole
transport from the active layer to the anode. The results shown
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Figure 9. a) Schematic illustration of graphene/n-Si (left) and TFSA doped graphene/n-Si (right) Schottky solar cells. b) The band diagram at the
graphene/n-Si interface before (left) and after (right) the doping. c) JV curves of graphene/n-Si (blue curve) and doped-graphene/n-Si (red curve)
Schottky solar cells under the AM 1.5 G illumination. The green curve is the JV curve for doped-graphene/n-Si device in dark. d) The plot of external
quantum efficiency (EQE) vs wavelength (, nm) for the pristine and TFSA-doped graphene/n-Si solar cells. Reproduced with permission.[131] Copyright
2012, American Chemical Society.

in Figure 11b demonstrate that the GO:SWCNTs composite
film based device exhibits higher performance than the pure
GO film based one. Note that the GO:SWCNT composite can
offer comparable performance to the conventional PEDOT:PSS-
based devices.[145] At the same time, Chhowalla and co-workers
also reported that the thin GO film with thickness of 2 nm on
ITO can work as an effective hole transport layer in polymer
solar cells (Figure 11c), showing the comparable values of effi-
ciency to devices fabricated with PEDOT:PSS. They also found
a clear trend of decreasing PCE with increasing GO film thick-
ness (Figure 11d). As a result, the thinnest GO film yielded the
best performance. This is mainly attributed to the increased
serial resistance in the thicker GO film, which decreases Jsc and
FF and also slightly lowers its transmittance.
In order to lower the resistance of the GO film as the hole
transport layer in the polymer solar cell, rGO was used as the hole
transport layer.[142] In this work, hydrazine was used to reduce GO
(referred to as r-GO). However, since hydrazine is highly toxic, a
new reductant, p-toluenesulfonyl hydrazide (p-TosNHNH2), was
developed to reduce GO. The obtained pr-GO not only exhibited
comparable reduction degree as that of r-GO, but also gave much
smoother thin-film morphology. The obtained highest PCE
(3.7%) is from the pr-GO based device, which is even higher
than that obtained from the traditional PEDOT:PSS based device
(3.6%).[142] In terms of the device stability after exposure to the
air, the device with pr-GO shows a much longer life time than
those with PEDOT:PSS. The aforementioned results clearly dem-
onstrate that the chemically reduced GO using p-TosNHNH2 as
a novel reductant is a promising interfacial material and a prac-
tical replacement for the conventional PEDOT:PSS. It promises
the realization of highly efficient, highly stable, and low-cost
polymer solar cells by using an environmentally friendly, high-
throughput, roll-to-roll manufacturing.
2.2.3.3. Hole and Electron Transport Layer. The work function of
GO can be easily tuned by simple chemical modification. Dai
and co-workers recently reported GO and modified GO as hole
and electron transport layers, respectively, in the single solar
cell configuration.[143] As shown in Figure 12a,b, by replacing
the periphery COOH groups with COOCs groups, the work

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Figure 10. Schematic illustrations of a,c) 1D and b,d) 2D nanomaterial composite electrodes. e) Operational principle of the device in term of charge
transfer behavior in the DSSC. f) Photocurrentvoltage characteristics of different electrodes. The sensitizer is N3 (ruthenium dye). The cell active area
is 0.20 cm2. The light intensity is 100 mW cm2. Electrodes 14 are pure TiO2, TiO2 with loading of 0.6% GO, TiO2 loading of with 2.5% GO, and TiO2
loading of with 8.5% GO, respectively. Reproduced with permission.[139] Copyright 2012, American Chemical Society.

function of the cesium-neutralized GO (GO-Cs) can be reduced
to 3.94.1 eV from 4.64.8 eV for pure GO. As a result, the work
function of GO matches both the ITO anode and the HOMO
level of P3HT for efficient hole extraction, while the work func-
tion of GO-Cs matches both Al and the LUMO level of PCBM
for efficient electron extraction (Figure 12b).
Excellent hole/electron extraction capabilities have been
demonstrated for GO/GO-Cs based polymer solar cells. Both
the normal device with the configuration of ITO(anode)/
GO/P3HT:PCBM/GO-Cs/Al(cathode) and inverted device of
ITO(cathode)/GOCs/P3HT:PCBM/GO/Al(anode) were investi-
gated (Figure 12c). The observed good performance for both the
normal and inverted devices containing GO and GOCs dem-
onstrates the capability of hole and electron extraction from GO
and GOCs, respectively. The slightly lower performance from
the inverted device, compared with the normal device, is mainly
due to its smaller open-circuit voltage (Voc) (Figure 12d). This
study implies that the chemically engineered GO is promising
for both hole and electron transport materials in solar cells.
2.2.3.4. Interfacial Layer in Tandem Solar Cells. Huang and co-
workers found that the mixed solution of GO and PEDOT:PSS
exhibits a one to two order of magnitude increase in viscosity
compared to either pure GO or PEDOT:PSS.[148] Although GO
is electrically insulating, the thin film made from the mixture
of GO and PEDOT:PSS possesses one order of magnitude
improvement in conductivity as compared to the PEDOT:PSS
film. Therefore, the GO/PEDOT:PSS composite based thin film
is adhesive, transparent, and conducting, which is well suited
for the mechanically and electrically connecting part, i.e., the
interfacial layer, in tandem solar cells. As a proof of concept,
such a composite thin film has been used as the sticky inter-
connect to increase the charge transport and the adhesion
between the two subcells in the tandem solar cell configura-
tion (Figure 13a). As shown in Figure 13b, the Voc values of
separately prepared front and back subcells are 0.59 and 0.53 V,
respectively. The Voc of the tandem cell is 0.94 V, i.e., 84% of
the total Voc of the subcells. This proves that two subcells have
been successfully connected in series by using GO/PEDOT as
the interfacial layer. The PCE of the final tandem cell with GO/
PEDOT is calculated to be 4.14%, which is higher than that
of the single rear and front cells (2.92% and 3.75%, respec-
tively). Importantly, it is much higher than that of the tandem
cell with only PEDOT:PSS as the interfacial layer (see the blue

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cell and holes from top cell. As for three-

Figure 11. a) Schematic illustration and b) current densityvoltage characteristics of ITO/GO/
P3HT:PCBM/Ca/Al device based on unmodified ITO (inverted triangle), GO layer (open circle,
spin coated from 0.15 wt% dispersion), PEDOT:PSS layer (diamond), and GO:SWCNT layer
(solid circle, spin coated from 0.15 wt% GO dispersion, GO:SWCNTs = 1:0.2, w/w). Repro-
duced with permission.[145] c) Schematic illustration and d) current densityvoltage charac- fiability in electrical properties, transfer-
teristics of ITO/GO/P3HT:PCBM/Al devices with different GO thickness. Reproduced with ability between substrates, and chemical/
permission.[141] Copyright 2010, American Chemical Society.
solid-triangle curve in Figure 13b).[148] This study proves the
importance of the composite film, with both enhanced viscosity
and conductivity characteristics, used for the interfacial layer in
tandem cells.
In addition, the same research group also demonstrated
that the water-processable GO:SWCNT thin film can be used
as an effective interfacial layer to construct tandem polymer
solar cells in both regular and inverted geometry by all-solu-
tion processing routes.[147] Although the same polymer is used
in both subcells, the significantly improved PCEs from the
subcell (3.41%) to the serially connected regular tandem cell
(4.1%) and from the subcell (2.9%) to the inverted tandem cell
(3.5%) show that the GO:SWCNT thin film serves as the good
mechanical separator and electrical interconnect of the two
subcells. Because of its high transparency in the near infrared
(NIR) region, the GO:SWCNT-based interconnect should work
well with the complementary tandem cell if a low bandgap
polymer is used. By using p- or n-doped SWCNTs with GO, the
charge recombination in the interconnect layer is expected to
be further improved.
In addition to GO, the CVD-graphene can also be employed
as an interfacial layer in tandem organic solar cells. Loh and co-
workers reported that the work function of graphene (4.2 eV)
can be increased by coating MoO3 with a bulk work function
of 6.76 eV. [ 146 ]
By using such MoO3/graphene as the interfacial
layer in series/parallel tandem solar cells (Figure 14a), the per-
formance can be effectively improved. For two-terminal series-
connected tandem cells, MoO3/graphene acts as a recombi-
nation center for the extraction of electrons from the bottom
terminal parallel connected tandem cells, the
sandwiched MoO3/graphene/MoO3 interfa-
cial layer only extracts the holes from the two
end ITO and LiF/Al cathodes (Figure 14b).
Finally, the MoO3/graphene thin film was
demonstrated as interfacial layer in tandem
solar cells, which harvest wide spectral solar
energy by stacking different bandgap pho-
toactive materials. A high Voc of 1 V and a
high Jsc of 11.6 mA cm-2 were obtained in
series and parallel connection, respectively
(Figure 14c,d). The values of Voc and Jsc in
the tandem cell are very close to the sum
values of Voc and Jsc from two single subcells
in series and parallel connections, respec-
tively, further confirming the good ohmic
contact at the active layer/MoO3-modified
graphene interface. In this case, the gra-
phene interfacial layer is capable of multi-
plying the open circuit voltage and short cir-
cuit current density by linking the subcells
properly. The performance of tandem cells
could be further enhanced if the efficiency of
two subcells could be improved.
With their solution processability, modi-
thermal stability, graphene and graphene-
based nanomaterials have been successfully
demonstrated in the feasibility of ultrathin films ranged from
single-layer to few-layer thickness, which were then utilized
as charge (electron/hole) transport layers in single and/or
tandem OPV solar cells as discussed above. Either using low
work-function graphene based nanomaterials as the ETL or
high work-function graphene-based materials as the HTL, or
even both functions in one tandem solar cells, graphene-based
nanomaterials have exhibited obvious advantages in device
performance enhancement over the traditional ETL materials
of ZnO or TiO2 and HTL materials of MoO3 or PEDOT:PSS.
In this aspect, the role of graphene-based materials is expected
to play an important role in the configuration of OPV solar
cells, aiming for higher performance devices in future.
3. Conclusions and Outlook
It is promising that graphene, as the transparent electrode
material, has exhibited superiority in that it is highly flexible,
an abundant carbon source, and has high thermal/chemical
stability, compared to the traditional ITO. In particular, the flex-
ible transparent electrodes show applications not only in solar
cells, but also in flexible touch screens, displays, printable elec-
tronics, flexible transistors, memories, etc.[4951,79,156158]
In addition to working as transparent electrodes, graphene,
GO, and their derivatives show many other important appli-
cations that include being electron/hole transporters and
serving as interfacial layers and Schottky junction layers in
photovoltaics devices. 2D GO is capable of stacking and

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Figure 12. a) Chemical structures and synthetic route of GO and GO-Cs. b) Energy level diagrams and c) device structures of the normal device and
the inverted device with GO as hole-extraction layer and GOCs as the electron-extraction layer. d) Current density-voltage curves of the normal device
(left) and inverted device (right) with GO as the hole-extraction layer and GOCs as the electron-extraction layer. Reproduced with permission.[143]

hydrogen bonding. This makes it possible to use such a 2D
scaffold as the template to self-assemble GO-based novel inor-
ganic, organic, and inorganic-organic hybrids with multifunc-
tionalities[54,159164] for applications in photovoltaics. On the
other hand, to enrich the application of graphene, processes
on bandgap opening have always attracted the attention of
scientists. To date, many methods have been investigated to
engineer the band structure of graphene, including inducing
a quantum confinement effect by reduction of graphene lat-
eral size to form nanoribbons[165169] or nanomesh,[170175]

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Figure 13. a) Cross-sectionalal SEM image of the fabricated tandem device. The two subcells and the interconnect layer can be clearly distinguished.
Scale bar = 150 nm. b) JV curves of separately prepared front cell (black), rear cell (red), tandem cells with PEDOT:PSS (blue) and GO/PEDOT:PSS
gel (green) as the sticky interfacial layer, respectively. Reproduced with permission.[148] Copyright 2011, American Chemical Society.

Figure 14. a) Schematic illustration of the structure of photovoltaic device. b) Energy level diagram of the tandem photovoltaic cell connected in series
and parallel configuration. c) JV characteristics of the reference single cell (ITO/PEDOT:PSS/P3HT:PCBM/LiF/Al (bottom cell), ITO/MoO3/ZnPc:C60/
LiF/Al (top cell)) and series connected tandem cell under light illumination. d) JV characteristics of the reference single cells (characterized individu-
ally from the parallel connected tandem cell) and parallel connected tandem cell under light illumination. The theoretical JV curve of the tandem cell
is also constructed by summing the JV curves of the single cells (the line with hollow squares). Inset graphs show the optimized thickness of MoO3
in the tandem device. Reproduced with permission.[146]

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introducing foreign elements,[176178] and employing a strain

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