Journal of

Materials Chemistry A
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FEATURE ARTICLE View Journal

Graphene in photovoltaic applications: organic

photovoltaic cells (OPVs) and dye-sensitized solar
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Cite this: DOI: 10.1039/c4ta01047g

cells (DSSCs)
Dong Wook Chang,*a Hyun-Jung Choi,b Alan Filerb and Jong-Beom Baek*b

Received 1st March 2014
Accepted 10th April 2014
DOI: 10.1039/c4ta01047g
www.rsc.org/MaterialsA
Graphene, a one-atom thick layer of graphite with a two-dimensional sp2-hybridized carbon network, has
recently attracted tremendous research interest due to its peculiar properties such as good mechanical
strength, high thermal conductivity, superior transparency, large specific surface area and exceptional
charge transport properties. To take advantage of its unusual properties, graphene has been widely
studied in various energy conversion and storage applications such as supercapacitors, fuel cells,
batteries and solar cells. Amongst these applications, the development of efficient solar cells, which can
convert sunlight into electricity is in high demand in order to solve up-coming energy-related and global
warming issues. So far, significant effort has been devoted to using graphene for improving the overall
performance of photovoltaic devices such as organic photovoltaic cells (OPVs) and dye sensitized solar
cells (DSSCs). It has been reported that graphene can play diverse, but positive roles such as an
electrode, an active layer, an interfacial layer and an electron acceptor in photovoltaic cells. Herein, we
summarize the recent progress and general aspects of graphene in various photovoltaic cells including
the synthesis, structure, properties and performance. In addition, challenges and future perspectives in
this field are also discussed.

a
Department of Chemical Systematic Engineering, Catholic University of Daegu,
13-13, Hayang, Gyeongbuk 712-702, South Korea. E-mail: dwchang@cu.ac.kr
b
School of Energy and Chemical Engineering/Low-Dimensional Carbon Materials
Center, Ulsan National University of Science and Technology (UNIST), 100,
Banyeon, Ulsan 689-798, South Korea. E-mail: jbbaek@unist.ac.kr

Dong Wook Chang is an Assis- Jong-Beom Baek is a Professor at

tant Professor and Department
Chair of Chemical Systematic
Engineering at the Catholic
University of Daegu, South
Korea. He obtained his PhD in
Materials Engineering at the
University of Dayton in 2007.
Prior to taking up his current
position, he worked for two
years as a senior researcher at
Samsung Total Petrochemicals
Company and another two years
as a Research Assistant Professor of the Interdisciplinary School of
Green Energy at the Ulsan National University of Science and
Technology (UNIST). Currently, he is working on the synthesis and
functionalization of organic materials and carbon-based nano-
materials for optoelectronic and renewable-energy applications.
the School of Energy and
Chemical Engineering and
Director of the Low-Dimensional
Carbon Materials Center at the
Ulsan National Institute of
Science and Technology
(UNIST), South Korea. Aer
receiving his PhD in Polymer
Science from the University of
Akron (USA) in 1998, he joined
the Wright-Patterson Air Force
Research Laboratory (AFRL).
Aer four years at the AFRL, he returned to his home country to
take up a position as an Assistant Professor of Chemical Engi-
neering at Chungbuk National University (Korea) in 2003, before
moving to UNIST in 2008. His current research interests include
the syntheses of high-performance two-dimensional (2D) network
polymers and the chemical modications of carbon-based mate-
rials for multifunctional applications.

This journal is © The Royal Society of Chemistry 2014 J. Mater. Chem. A


Journal of Materials Chemistry A
1. Introduction
Humanity is currently facing serious threats, e.g., energy-related
issues and global warming problems, due to the huge increase
in world population, rapid economic expansion and large
emission of greenhouse gases from fossil fuels. To solve these
problems, the development of clean and renewable energy
resources has attracted a great deal of interest in both academia
and industry. Above all, solar energy is in the limelight owing to
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its great potential as an unlimited and cheap renewable energy
resource. Although most solar cells (
90%) currently available
in the market are composed of silicon-based materials,1 the
development of promising alternative solar cells, for example,
organic photovoltaic cells (OPVs)2,3 and dye sensitized solar cells
(DSSCs),4,5 is gaining traction due to their unique advantages
such as exibility and low manufacturing costs. As a result of
the recent progress during the last decade, the power conver-
sion efficiency (PCE) of OPVs and DSSCs has greatly improved
with the current state-of-the-art devices exceeding 9% 6 and
15%,7 respectively. However, further improvements of the PCE,
costs and long-term stability of OPVs and DSSCs are still greatly
required for practical applications. In addition, it is well known
that the overall performance of these solar cells strongly
depends not only on the structure of the devices, but also on the
properties of the materials. Therefore, the development of new
materials, which are useable as the various parts of solar cells
such as the electrodes, active layers and interfacial layers, as
well as the related device fabrication techniques, are of great
importance.
Since the breakthrough discovery by Novoselov et al.,8
graphene, a single layer of graphite with a two-dimensional
carbon network structure, has attracted great attention for
use in various applications. Specically, graphene has been
widely used for emerging energy conversion and storage
applications such as supercapacitors, fuel cells, batteries and
solar cells,9–11 owing to its fascinating properties, such as its
huge mechanical strength (Young's modulus of 1.0 TPa), high
thermal conductivity (
5000 Wm1 K1), superior trans-
parency (>97%), large specic surface area (2630 m2 g1), and
exceptional charge transport properties (200 000 cm2 V1
S1).8,12,13
Much attention has been devoted to the application of
graphene in the particularly interesting eld of OPVs and
DSSCs due to its versatility and unique properties.10,14–17 For
example, it has been reported that graphene can be success-
fully employed in most parts of OPVs including the electrode,
the active layer and the interfacial layer. The results that have
been obtained from graphene in OPVs are promising
compared with its counterparts. Similarly, graphene has also
shown great potential in DSSCs as a transparent electrode,
photoanode, and counter electrode. Although graphene and
graphene-based materials have demonstrated a broad range of
applications, we will focus on recent advances in OPVs and
DSSCs. In addition, the remaining challenges for newly-
developed graphene materials in photovoltaic applications
will be discussed.
J. Mater. Chem. A
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Feature Article
2. Synthesis and functionalization of
graphene for solar cells
Although there are a numerous methods to produce graphene,
they can be categorized into two representative approaches. The
rst method is a top-down approach, in which single and a few
layer graphene can be prepared by exfoliation of natural or
synthetic graphite. The two-dimensional graphene can be
exfoliated from graphite using the Scotch tape method8 as well
as consecutive oxidation–exfoliation–reduction reactions of
graphite,18 the so-called graphene oxide (GO) method, are the
most widely used methods for top-down approaches. In addi-
tion, liquid-phase exfoliation,19 graphite intercalation
compounds (GICs)20 and electrochemical exfoliation21 can be
regarded as other examples of top-down approaches. The other
method is a bottom-up approach. Graphene can be directly
synthesized from a carbon feedstock using various synthetic
protocols, such as chemical vapor deposition (CVD)22,23 and
epitaxial growth.24 This second method is better for producing
graphene with high-quality and large-area lms, although it has
signicant drawbacks, such as high manufacturing costs,
tedious optimization, and tight control of the process
conditions.
Due to large area p–p interaction among graphitic layers,
pristine graphite is difficult to exfoliate into single and a few-
layer graphene sheets in matrices such as solvents and poly-
mers, which limits not only the scalability of production for
practical applications, but also the realization of unique prop-
erties. In addition, further tailoring and/or altering the prop-
erties of graphene is oen necessary to meet requirements for
specic applications. To solve these problems, various chemical
and/or physical methods for modifying graphene have been
developed. Fig. 1A summarizes the most important methods for
the functionalization of graphene, including edge-functionali-
zation (Fig. 1A(a)), basal-plane functionalization (Fig. 1A(b)),
non-covalent adsorption on the basal plane (Fig. 1A(c)), asym-
metric functionalization (Fig. 1A(d)), and the self-assembly of
graphene (Fig. 1A(e)).25 Due to its good dispersibility and reac-
tive functional groups such as carboxylic acids, epoxides,
carbonyl and hydroxyl groups, graphene oxide (GO), which is
produced from the oxidation of graphite using strong oxidizing
reagents (e.g., H2SO4 and KMnO4), is widely used as a starting
material for the further modication of graphene (Fig. 1B).25
Furthermore, chemical doping of graphene by incorporation of
heteroatoms such as boron and nitrogen has attracted signi-
cant attention. The electronic properties of graphene, for
example, its band structure and charge carrier mobility (of holes
and electrons), are greatly modulated aer chemical doping of
carbon-based graphene structures (Fig. 1C).26
Recently, Baek et al. reported a simple, cost-effective and eco-
friendly method using ball-milling (Fig. 2A)27 and a direct
Friedel–Cras acylation (Fig. 2B)28 for the large-scale production
of edge-selectively functionalized graphene (EFG). These
methods can efficiently introduce various organic molecular
wedges such as 4-substituted benzoyl groups at the edges of
graphene, due to the versatility of the mechanochemical
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Feature Article
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Fig. 1 (A) Functionalization possibilities for graphene: (a) edge-functionalization, (b) basal-plane functionalization, (c) noncovalent adsorption on
the basal plane, (d) asymmetric functionalization and (e) the self-assembly of graphene. (B) Chemical structure of graphene oxide. Reproduced
from ref. 25 with permission from the American Chemical Society. (C) Process for boron- and nitrogen-doping of graphene. Reproduced from
ref. 34 with permission from the American Chemical Society.
ball-milling and the Friedel–Cras acylation in PPA/P2O5.29
Unlike in GO, the EFG produced by ball-milling and the Friedel–
Cras acylation largely preserved the highly crystalline graphitic
structure of its basal plane. In addition, the efficient exfoliation
of graphite into graphene could be easily obtained due to the
strong repulsive forces between the edge-selectively attached
functional groups. As a result, EFG has been used in many
applications, such as highly conductive large-area lms, metal-
free electrocatalysts for oxygen reduction reaction (ORR),28,30,31
and electrodes in DSSCs32,33 with signicantly enhanced
properties.
3. Graphene in organic photovoltaic
cells (OPVs)
During the last few decades, organic photovoltaic cells (OPVs)
have attracted a great deal of interest due to their advantages
such as low-cost manufacturing, light weight, the versatility of
their components and exibility.2,3 Various p-conjugated poly-
mers and/or small molecules have been used as the light-
absorbing active layers in OPVs.34–36 Incessant and creative
efforts by many researchers have led to a signicant enhance-
ment in power conversion efficiency (PCE). However, further
improvement in PCE and lowering the device cost are still
required for commercialization. In this regard, much attention
has been focused on the application of graphene in the eld of
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OPVs, because of its outstanding mechanical, optical, and
electronic properties with relatively high cost-effectiveness.
3.1. Transparent electrodes
Firstly, graphene has been widely investigated as a transparent
electrode in OPVs to replace conventional indium tin oxide
(ITO) electrodes. Currently, ITO plays a pivotal role as trans-
parent electrodes for OPVs, but it has several drawbacks such as
high cost, poor exibility, low stability, and a complicated
manufacturing process.15,37 Although many alternatives
including conducting polymers,38 carbon nanotubes (CNTs),39
and metal oxides40,41 have been extensively developed, it has
been reported that graphene can offer several potential advan-
tages over these other candidates. For example, the trans-
mittance of single layer graphene can reach more than 97% in
the visible region. In addition, a low sheet resistance (a few
hundred U to kU/square), which is necessary to meet the
requirements for replacing ITO, can also be easily achieved.42
Recently, Choi et al. reported the device fabrication of OPVs
using CVD grown graphene lms on glass substrates as trans-
parent electrodes.43 The CVD grown graphene lms showed
high transparency (
84%) in conjunction with low sheet resis-
tance (
374  3U/square). For the preparation of OPVs, a thin
layer of CVD grown graphene lm was rst transferred to a glass
substrate with the aid of a poly(methyl methacrylate) (PMMA)
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Fig. 2 (A) Schematic of the ball milling procedure. Reproduced from ref. 27 with permission from National Academy of Sciences. (B) Schematic
representation of the direct Freidel–Crafts acylation in PPA/P2O5. Reproduced from ref. 28 with permission from the American Chemical Society.

supporting layer (Fig. 3a). Aer consecutive spin-coatings of a acid methyl ester (P3HT/PCBM) onto the graphene lm, the
PEDOT:PSS lm and a bulk heterojunction active layer cathode of Ca(20 nm)/Al(100 nm) was nally evaporated
composed of poly(3-hexylthiophene)/[6,6]-phenyl C61-butyric (Fig. 3b). The resultant graphene-based OPVs are shown in

Fig. 3 (a) Schematic illustration of the synthesis and transfer of CVD grown graphene onto glass substrates. (b) Schematic diagram of the bulk-
heterojunction OPVs comprising a CVD-grown graphene electrode with Al:Ca cathode. (c) A photograph of the OPVs. Reproduced from ref. 43
with permission from Elsevier.

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Fig. 3c. Although the PCE of the OPVs with the graphene elec-
trode (
1.17%) was still not comparable to that of devices with a
standard ITO electrode (
3.43%), these yet to be optimized
results indicate that graphene lms are a promising and
economic substitute material for replacing conventional ITO
electrodes. Due to the higher carrier concentration and
improved compatibility, a further enhancement in PCE has
been reported using a doped CVD-grown graphene electrode
containing various dopants such as Au,44,45 acids,46,47 and
organic molecules.48,49 Moreover, Zhou et al. obtained a nearly
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transparency was compromised. Unfortunately, the PCE of the
optimized devices with an rGO lm as the transparent electrode
was limited to 0.4%, which was much lower than that of ITO-
based devices (
0.8%) with the same conguration.51 This low
PCE likely originated from the higher sheet resistance of the
rGO lm as well as its poor compatibility with the PEDOT:PSS
layer. Although the PCEs of OPVs with rGO electrodes are still
inferior to those of devices with ITO electrodes, they can offer
the unique advantage of outstanding exibility. Recently, Zhang
et al. demonstrated highly exible OPVs using an rGO lm on a

equivalent PCE (
1.18%) to that of an ITO-based OPV device
(
1.27%)50 using highly exible OPVs with a smooth, large
surface area, few-layer CVD-grown graphene lm as the trans-
parent electrode.
Apart from CVD-grown graphene, chemically or thermally
reduced graphene oxide (rGO) derived from graphene oxide
(GO) has been also widely investigated as a transparent elec-
trode material for OPVs. This top-down approach is more
desirable than a bottom-up approach like CVD from the view-
point of mass production potential. Chen et al. reported the
possibility of using rGO as a transparent electrode for OPVs.51
Aer an insulating GO lm is deposited by spin-coating,
annealing at high temperature combined with hydrazine vapor
can be used to produce a conductive rGO lm. It was also found
that the transparency and conductivity, two key properties of
transparent electrodes, are strongly dependent on the thickness
of the rGO lm. For example, the conductivity was signicantly
improved by increasing the lm thickness, whereas the
polyethylene terephthalate (PET) substrate as the transparent
electrode (Fig. 4).52 The rGO lm was obtained by the thermal
annealing of a spin-coated GO lm under a H2/Ar atmosphere at
1100  C for 2 h. A higher PCE of 0.78% was obtained using rGO
lms with a thickness of 16 nm, sheet resistance of 3.2 kU/
square and transmittance of 65%. Interestingly, the overall
performance of the OPVs with an rGO on PET electrode was able
to withstand up to 1200 bending cycles (Fig. 4D). The applied
tensile strain for the bending–relaxing experiments was esti-
mated to be 2.9%. It is worth noting that ITO-based OPVs with
the same device structure easily crack upon bending and their
device performance dramatically degrades due to the brittle
nature of ITO. This result clearly paves the way to develop
various exible optoelectronic devices using graphene as a
transparent electrode. Similarly, several promising results using
OPVs with a graphene-based transparent electrode have also
been reported.15,52,53 Consequently, graphene made either by
top-down approaches like CVD or bottom-up approaches

Fig. 4 (A) A photograph of rGO on PET. (B) Schematic representation of the layer structure of OPVs, i.e., rGO/PEDOT:PSS/P3HT:PCBM/TiO2/Al,
with rGO as the transparent electrode. (C) J–V curves of OPVs using a rGO/PET electrode under 100 mW cm2 AM 1.5G illumination with a rGO
film thickness of 21 nm. (D) J–V curves of OPVs with a 4 nm thickness rGO film on PET as the transparent electrode after applying (i) 400, (ii) 800,
and (iii) 1200 cycles of bending. Reproduced from ref. 52 with permission from the American Chemical Society.

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starting from GO has high potential as a transparent electrode

in OPV applications.

3.2. Electron acceptors

Among the various device congurations of OPVs, the most
successful have adopted bulk heterojunction structures with an
electron donor (D) and an electron acceptor (A). In bulk heter-
ojunctions, a bicontinuous, nanometer-scale, interpenetrating
network of donor and accepter with large interfacial area is
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efficiently generated. Under these conditions, excitons are

mostly located at the D/A interfacial area within their limited
diffusion length, which is benecial for improving the device
performance through efficient charge separation.54,55 In
contrast to the intensive development of a huge number of
electron donors for OPVs including polymers and small mole-
cules with low band gaps,35,36 C60 derivatives, specically [6,6]-
phenyl C61-butyric acid methyl ester (PCBM), have been
predominantly used as electron acceptors for OPVs. However,
C60 derivatives have signicant drawbacks such as very weak
light absorption in the visible range and low energy levels for
their lowest unoccupied molecular orbital (LUMO).56,57 There-
fore, the development of new electron acceptors has been
required for the practical application of OPVs. In this regard,
graphene, as a carbon allotrope, is a good candidate for an
alternative electron accepting material, due to the unique
advantages of its two-dimensional structure, high carrier
mobility and versatile functionalization. Chen et al. have
reported the solution-processable fabrication and character-
ization of OPVs with bulk heterojunction structures that have
conjugated polymers as the electron donor and graphene as the
electron acceptor.58 The structure of the materials used as well
as a schematic representation and energy level diagram of the
device are shown in Fig. 5. The device has a typical structure of
ITO/PEDOT:PSS/P3OT:SPFGraphene/LiF/Al (Fig. 5b) and the
energy levels of each component in the device are appropriate
for successful operation (Fig. 5c). In order to enhance the
hydrophobic nature of graphene, a reaction was carried out
between GO and phenyl isocyanate to produce functionalized
graphene known as SPFGraphene (Fig. 5d). Under 100 mW
cm2 AM 1.5G illumination, a limited PCE of 0.4% was obtained
from OPVs with a bulk heterojunction structure using P3OT and
SPFGraphene as the donor and acceptor, respectively. However,
the PCE was greatly increased up to 1.4% aer thermal
annealing of the devices. Morphological improvement of the
active layer and further reduction of the SPFGraphene during
the annealing process contributed to this signicant enhance-
ment in PCE.58 In addition, this relatively high value of PCE is
comparable to most OPVs with new electron acceptors, except
C60 derivatives.
Dai et al. fabricated bulk heterojunction OPVs with a gra-
phene–C60 hybrid material used as an electron acceptor
(Fig. 6).59 In order to produce the graphene–C60 hybrid material,
C60 was graed onto the surface of GO using a lithiation reac-
tion. A 2.5 fold increase in PCE (
1.22%) was observed for OPVs
using the graphene–C60 hybrid material as an electron acceptor
compared to a device with only C60 as an acceptor (
0.47%).
Fig. 5 (a) The idealized chemical structures of graphene and P3OT. (b)
Schematic of a device with P3OT/graphene thin film as the active layer.
(c) Energy level diagram of P3OT and SPFGraphene. (d) Schematic
representation of the reaction of phenyl isocyanate with graphene
oxide to form SPFGraphene. Reproduced from ref. 58 with permission
from the Wiley-VCH.
This enhancement in the PCE of the devices with the graphene–
C60 hybrid acceptor was clearly attributable to an improvement
of the electron transport properties because the introduction of
the graphene–C60 hybrid into the active layer of the device could
promote the formation of a direct electron conduction pathway
through percolation of the highly conducting two-dimensional
graphene sheets. As shown in Fig. 6A, the photo-generated
electrons from C60 are readily transferred to the graphene and
nally reach the Al cathode. So far, while several investigations
on graphene-based acceptors for OPVs have been reported, the
overall performance of the devices is still poorer than that of
OPVs with C60-based acceptors. To overcome this problem,
further studies are currently being undertaken on OPVs with
graphene-based electron acceptors including studies on
controlling the grain size and layer structure of the graphene
acceptor, matching the band structures between the donor–
acceptor pairs and optimization of the device fabrication
processes.
3.3. Interfacial layers
As discussed above, pristine or functionalized graphene can
serve as a transparent electrode and electron acceptor in bulk
heterojunction OPVs. However, there are still additional appli-
cations of graphene in OPVs. Interfacial layers such as the hole
extraction layer (HELs) and electron extraction layer (EEL) are
good examples.14,25 For high performance OPVs, these addi-
tional layers are oen fabricated into OPVs to minimize the
energy barriers between the active materials and electrodes. The

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Fig. 6 (A) Schematic representation of C60-grafted graphene (C60-G) facilitating electron transfer and transport in a P3HT-based PSC. (B) (a)
Absorption spectra of the C60-G:P3HT (1 : 1 wt/wt) film before and after annealing (130  C, 10 min) and the C60:P3HT (1 : 1 wt/wt) film spin-cast
onto quartz plates. (b) Schematic diagram of a PSC with the C60-G:P3HT composite used as the active layer. (c) J–V curves of the photovoltaic
devices with the C60-G:P3HT (1 : 1 wt/wt), C60:P3HT (1 : 1 wt/wt), or C60/G mixture (10 wt%):P3HT (1 : 1 wt/wt) used as the active layers after
annealing. (d) Energy level diagram for the photovoltaic device with the C60-G:P3HT composite as the active layer. Reproduced from ref. 59 with
permission from the American Chemical Society.

HEL and EEL are benecial for matching the energy levels
between the work function of the anode and HOMO level of the
electron donor, as well as the work function of the cathode and
the LUMO level of electron acceptor, respectively. Poly(3,4-eth-
ylenedioxythiophene) doped with poly(styrene sulfonate)
(PEDOT:PSS) is the most widely used HEL, but it has drawbacks
such as etching of the ITO electrode and a strong hygroscopic
nature, which are detrimental to device efficiency and life-
time.60,61 On the other hand, various materials such as low work
function metals or their related salts (e.g., Ca, LiF), metal oxide
semiconductors (e.g., TiO2, ZnO), and conjugated polymer
electrolytes have been reported as EELs.62–64 Recently, graphene
oxide and its derivatives have been emerging as promising
candidates for use as interfacial layers in OPVs, due to their
high electrical conductivity, tunable optoelectronic properties,
low cost, and extraordinary stability. For example, there are
several advantages when thin lm of graphene oxide is applied
as a HEL in OPVs rather than PEDOT:PSS, including less
corrosion of the ITO electrode, a better band structure for more
efficient hole extraction and higher transparency.
Li et al. reported a graphene based HEL in OPVs. They
fabricated OPVs with a simple structure of ITO/GO/
P3HT:PCBM/Al (Fig. 7a).65 The work function of the GO HEL
(4.9 eV) matched well with that of ITO and the LUMO of the

Fig. 7 (a) Schematic representation of the OPV device structure with GO as a HEL. (b) Energy level diagrams of all of the components in the
OPVs. (c) An AFM height image of a GO thin film with an approximate thickness of 2 nm. (d) J–V characteristics of the devices with no HEL, with a
30 nm PEDOT:PSS film and with a 2 nm GO film. (e) J–V characteristics of ITO/GO/P3HT:PCBM/Al devices with different thickness of GO film.
Reproduced from ref. 65 with permission from the American Chemical Society.

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P3HT donor (Fig. 7b). In addition, the GO lm exhibited a

smooth surface with a root mean square (rms) value of 0.7 nm,
which is even lower than that of a pristine glass/ITO electrode
(rms ¼ 3 nm) (Fig. 7c). Without HEL, the device showed a
limited PCE of 1.8%. However, an improved PCE (
3.5%) was
obtained when GO was used as a HEL, which is highly compa-
rable to conventional OPVs using a PEDOT:PSS counterpart
(
3.6%) (Fig. 7d). Furthermore, the device with GO as a HEL
demonstrated signicantly improved long-term stability,
possibly due to effective suppression of the leakage current and
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separation of the carriers. It was also found that the thickness of

the GO lm is critical for device performance. Increasing the
thickness of the GO lm gradually decreases the PCEs of OPVs
(Fig. 7e). The higher sheet resistance of the thicker lm resulted
in a lower short circuit current (Jsc), ll factor (FF) and optical
transmittance for the device.
Dai et al. also reported the utilization of sulfonated GO (GO- Fig. 8 (a) Schematic structure and synthesis scheme for GO-Cs. (b)
Energy level diagram of all of the components in the OPV devices. (c)
SO3H), as a HEL in OPVs.66 They introduced the strongly acidic
J–V characteristics of the devices (device structure: ITO/PEDOT:PSS/
moiety SO3H into the carbon basal plane of GO resulting in an P3HT:PCBM/EEL/Al) with none, LiF, Cs2CO3 and GO-Cs as the EEL.
enhancement of the interfacial doping of the electron-donor as Reproduced from ref. 71 with permission from Wiley-VCH.
well as affording solution-processability. In addition, the
conductivity of the GO-SO3H was greatly enhanced during the
reaction, due to the dehydration effect of the fuming sulfuric
acid used as a reactant. As a result, a greatly improved PCE of
4. Graphene in dye sensitized solar
4.37% was obtained along with an FF of 0.71, open-circuit cells (DSSCs)
voltage (Voc) of 0.61 V, and Jsc of 0.15 mA cm2 from the OPVs
Since the pioneering work on dye sensitized solar cells (DSSCs)
with GO-SO3H as a HEL. There are also several other reports on
conducted by Grätzel et al.4 these devices have attracted
the development of graphene oxide derivatives as HELs for high
tremendous attention in both academia and industry, owing to
performance OPVs.67–70 So far, graphene-based materials have
their high efficiency and low manufacturing costs. DSSCs are
displayed promising performance as HELs compared with
typically composed of a nanocrystalline TiO2 lm combined
PEDOT:PSS and other candidates like metal oxides.14 Further
with sensitizers on a transparent electrode, an electrolyte
optimization of the structure and manufacturing process of
usually containing an I/I3 redox couple, and a counter elec-
graphene-based HELs in OPVs should lead to great improve-
trode. Highly conductive oxides such as ITO or uorine tin oxide
ments in overall device performance.
(FTO) are generally used as the transparent electrode, while
In principle, if the energy level of graphene can be properly
platinum (Pt) is used as the counter electrode. The generation of
tuned it can be used as both a HEL and EEL in OPVs. Dai et al.
electricity in DSSCs involves the following steps: (i) excitation of
reported the preparation of edge-functionalized GO for use as
the sensitizers under light irradiation, (ii) an electron-injection
the EEL in OPVs. They used a simple charge neutralization
into the conduction band of the semiconducting TiO2 lm, (iii)
reaction of the –COOH groups at the edge of GO with cesium
regeneration of the sensitizers by the I/I3 redox couple, and
(–COOCs) to modify the work function of GO (Fig. 8a).71 The GO
(iv) reduction of the oxidized species of the redox couple at the
itself has a work function of 4.7 eV, which is suitable for the HEL
counter electrode.72 Although recent progress in DSSCs has led
in OPVs. However, the work function of the cesium neutralized
to a relatively high PCE of 15%,7 there are still many challenges
GO (GO-Cs) shied to 4.0 eV. This value is appropriate for an
for the further development of DSSCs. For example, the
EEL, because it matches well with the LUMO level of PCBM,
replacement of high cost transparent and counter electrodes,
which acts as an electron acceptor (Fig. 8c). Well-designed OPV
the suppression of charge recombination, and the enhance-
device structures, i.e., normal and inverted congurations, were
ment of long-term stability. In this regard, graphene-based
successfully fabricated with a high PCE of 3.67%, using GO and
nanomaterials have been intensively explored as replacements
GO-Cs as the HEL and EEL, respectively, Furthermore, both the
for the various components of DSSCs including the transparent
normal and inverted devices with GO-based interfacial layers
electrode, counter electrode, light absorber and so forth, to
outperformed the corresponding OPVs with a standard HELs
produce cost-effective devices with promising performance.
and EELs, such as PEDOT:PSS and LiF, respectively.71 Therefore,
the work function of graphene can be efficiently tuned by
controlled chemical modications, which open up new 4.1. Transparent electrodes
avenues for the development of functionalized graphene with As discussed above, due to their unique electrical, mechanical
tailor-made chemical structures and electronic properties and optical properties, graphene-based materials have been
like GO-Cs. regarded as promising alternatives to ITO and FTO transparent
electrodes. Wang et al. reported a simple approach for the

J. Mater. Chem. A This journal is © The Royal Society of Chemistry 2014


Feature Article
fabrication of a conductive rGO lm for use as a transparent
electrode in DSSCs.73 Once the GO lm was deposited onto a
hydrophilic quartz substrate by dip coating the GO dispersion,
it was thermally reduced under Ar and/or H2 gas to yield a nal
rGO lm. A high electrical conductivity of 550 S cm1 and
transparency of over 70% in the range of 1000–3000 nm were
obtained from the resultant rGO lm. The related device
structures and energy level diagram for these DSSCs are shown
Fig. 9A and B, respectively. In this study, 2,20 ,7,70 -tetrakis(N,N0 -
di-p-methoxyphenylamine)-9,90 -spirobiuorene (spiro-OMe-
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TAD) was used as the hole transport material to build solid state
devices. Unfortunately, the solid state DSSCs with rGO as a
transparent electrode exhibited a PCE of 0.26%, which was
lower than that of the device with a standard FTO electrode
(0.84%). This signicant reduction of PCE in these graphene-
based DSSCs can be attributed to the high sheet resistance and
low transmittance of the rGO lm as well as electronic interfa-
cial change. However, it is believed that there is still room for
further improvement of device performance using graphene-
based transparent electrodes. As a cheap, abundant and easily
processable resource, graphene possesses several advantages
such as excellent conductivity, good optical transparency in
both the visible and near-infrared region, high chemical
stability and superior exibility, all of which are highly bene-
cial for its use as a transparent electrode in DSSCs. To maximize
Fig. 9 (A) Illustration of a dye-sensitized solar cell using a rGO film as a
transparent electrode. The four layers from bottom to top are: Au, dye-
sensitized heterojunction, compact TiO2, and rGO film. (B) The energy
level diagram for the rGO/TiO2/dye/spiro-OMeTAD/Au device. (C) I–V
curve of the graphene-based cell (black) and FTO-based cell (red),
illuminated under AM solar light (1 sun). Reproduced from ref. 73 with
permission from the American Chemical Society.
This journal is © The Royal Society of Chemistry 2014
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Journal of Materials Chemistry A
these advantages, the development of production methods for
high-quality graphene as well as further optimization of device
structures and fabrication techniques should be preferentially
considered.42
4.2. Electron transport and absorption in photoanodes
A layer of a nanocrystalline semiconductor such as TiO2 is
indispensable for DSSCs, because it can provide not only an
anchoring surface for sensitizers, but also perform the key
functions of charge collection and diffusion.10 In general, a
porous, nanostructured TiO2 lm with a typical thickness of 10–
15 mm and a porosity of 50% is fabricated on a transparent
electrode to enhance the internal surface area of the lm. In this
conguration, large amounts of sensitizer can be successfully
anchored onto the semiconductor lm, which is greatly bene-
cial for obtaining higher PCE values in DSSCs. However, one of
the main drawbacks of semiconductor lms in DSSCs is the
limited transport of collected electrons across the layer.1 It is
reported that this electron transport process in the photoanode
competes with undesirable charge recombination. Among the
several approaches that have been used to improve electron
transport (i.e., suppressing charge recombination), the incor-
poration of carbon-based nanomaterials into the photoanode
has been widely investigated due to the huge potential of these
materials in optoelectronics.74–77 Yang et al. reported that the
introduction of two dimensional (2D) graphene sheets into a
TiO2 nanostructured photoanode as 2D bridges could signi-
cantly increase the short-circuit current density (Jsc) and PCE of
DSSCs by 45% and 39%, respectively, compared to a standard
device containing a TiO2 photoanode without graphene
(Fig. 10).78 Due to the unique advantages of graphene including
its high conductivity, good interfacial contact with TiO2 nano-
particles and suitable work function (4.4 eV), graphene sheets
can not only improve charge transport, but also the electron
accepting properties of the semiconductor layer. Furthermore,
Tang et al. have reported the in situ incorporation of graphene
sheets (GS) into a TiO2 lm using a molecular graing
Fig. 10 Differences between (a, c) 1D and (b, d) 2D nanomaterial
composite electrodes. In the 2D nanomaterial composite electrodes
(with graphene bridges), the TiO2 particles can anchor to the graphene
better and photoinduced electrons can be captured and transferred by
the graphene. However, in the 1D nanomaterial composite, there are
less intermolecular forces and connection between the TiO2 and the
1D nanomaterial. Therefore, the transfer barrier is larger and recom-
bination is much more likely to happen. Reproduced from ref. 78 with
permission from the American Chemical Society.
J. Mater. Chem. A

Journal of Materials Chemistry A
technique and their application of this lm in DSSCs as a
photoanode.79 Interestingly, the PCE for DSSCs with this newly
developed GS/TiO2 composite layer (1.68%) is more than
5 times higher than that based on a TiO2 layer (0.32%). Again,
the better performance of the GS/TiO2 based DSSCs is attrib-
utable to the enhanced electrical conductivity as well as better
dye loading levels for the GS/TiO2 lm compared to the bare
TiO2 lm.
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4.3. Counter electrode
One of the important components of DSSCs is the counter
electrode, from which electrons are injected into the electrolyte
for the reduction of the redox couple (from I3 to I). The
excellent catalytic activity and high conductivity of platinum (Pt)
on a conductive ITO or FTO substrate allows it to be used as a
counter electrode in DSSCs. However, Pt-based electrodes have
several drawbacks including high costs, limited resources in
nature and corrosion due to the redox couple.1,10,72 Recently,
signicant effort has been made to reduce or replace Pt-based
counter electrodes in DSSCs. In particular, graphene-based
materials have been widely studied as counter electrodes in
DSSCs, due to having the advantages of low cost, high
conductivity, transparency, and superior corrosion resistance.
Kavan et al. reported the fabrication of DSSCs with an optically
transparent graphene lm on FTO as a counter electrode.80
High electrocatalytic activity was obtained toward the I3/I
redox couple from the counter electrode, which was made of
commercially available graphene, particularly in ionic liquid
electrolytes (Z952). The same group also investigated graphene
on an FTO lm as a counter electrode in DSSCs using other
redox couples such as Co(bpy)33+/Co(bpy)32+, to overcome the
less efficient performance of Pt-based electrodes with Co
Fig. 11 (a) Preparation route of the N-GF counter electrode. (b) A DSSC with an N-GF counter electrode. (c) Triiodide reduction on the N-doped
graphene surface. Reproduced from ref. 85 with permission from Wiley-VCH.
J. Mater. Chem. A
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Feature Article
mediators.81 Recently, Co(bpy)33+/Co(bpy)32+ redox couples have
been preferred because great improvement in the PCE of DSSCs
can be achieved by using a Co(bpy)33+/Co(bpy)32+ redox couple.
This enhancement in PCE is closely related to an increase in the
open circuit voltage (Voc) of up to 0.9 V, which originates from
the higher redox potential of the Co(bpy)33+/Co(bpy)32+ couple
(0.56 V) compared with the conventional I3/I redox couple
(0.35 V).82,83 Interestingly, graphene could outperform Pt as a
counter electrode in cobalt mediated DSSCs from the view point
of efficiency and chemical stability.81
In general, the higher catalytic activity of graphene as a
counter electrode in DSSCs is due to the existence of a large
number of active sites on the material. Aksay et al. reported that
the content of oxygen containing moieties like hydroxyl, epoxy
and carbonyl groups is crucial to the catalytic activity of gra-
phene-based counter electrodes in DSSCs.84 The amount of
oxygen-containing groups on graphene can be controlled by a
high temperature thermal annealing process. Aer increasing
the population of functional groups, the catalytic activity was
also improved for graphene-based counter electrodes in DSSCs.
However, the introduction of oxygen-containing active sites on
graphene oen results in signicant damage to the conjugated
structure of the graphene network, which can lead to a sharp
decrease in electrical conductivity.85 In order to work as an
efficient counter electrode in DSSCs, it is important to balance
the electrical conductivity and electrocatalytic activity. One of
the most promising approaches for improving the catalytic
activity without decreasing the electrical conductivity is chem-
ical doping of graphene networks with heteroatoms like B, N
and P.86–89 For example, the introduction of nitrogen atoms into
graphene can enhance its electron transfer ability and electro-
catalytic activity by generating additional lone pairs electrons,
which can impart negative charge with respect to the
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Feature Article Journal of Materials Chemistry A

delocalized p-system of the sp2-hybridized carbon framework.32
Furthermore, it has been also demonstrated that heteroatom
doping can enhance the electrical conductivity and surface
hydrophilicity to promote charge transfer and electrolyte–elec-
trode interactions, respectively. Therefore, chemically doped
graphene can be regarded as a promising candidate for efficient
counter electrodes in DSSCs.
Dai et al. rst reported the application of nitrogen doped
graphene as a counter electrode in DSSCs.85 They developed a
three dimensional nitrogen-doped graphene foam (N-GF) with a
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activity of N-GF induced by heteroatom doping, coupled with
the unique three dimensional foam structure, which has a large
surface area, high porosity and good surface hydrophilicity.85
Recently, Baek et al. reported a simple, cost-effective and eco-
friendly method involving ball-milling33 or a direct Friedel–
Cras acylation32 for the large-scale production of edge-selec-
tively nitrogen doped graphene to be used as a metal-free
counter electrode in DSSCs. Firstly, a large quantity of edge-
nitrogenated graphene nanoplatelets (NGnPs) was produced by
ball-milling pristine graphite in the presence of nitrogen gas

high nitrogen content of 7.6%. This N-GF was manufactured by
annealing freeze-dried graphene oxide foam (GOFs) in
ammonia and the resulting N-GF was transferred onto a FTO
glass substrate for use as a counter electrode in DSSCs
(Fig. 11a). Schematic representations of the device structure and
triiodide reduction on N-GF are shown in Fig. 11b and c,
respectively. From the DSSC with a N-GF counter electrode, a
high PCE of 7.07% was obtained, which is comparable to that of
a DSSC with a Pt counter electrode (7.44%). The outstanding
performance of the DSSC with a N-GF counter electrode can be
attributed to the high electrical conductivity and catalytic
(N2).33 The facile formation of active carbon species occurs via
mechanochemical cracking of the graphitic C–C bonds during
the ball-milling process, which leads to direct nitrogen xation
at the broken edges of the graphite (Fig. 12a).33 An extremely
high nitrogen content of 14.84 wt% (equivalent to a carbon/
nitrogen atomic ratio of 5.6) was obtained via the mechano-
chemical reaction of graphite with inert nitrogen gas, which
reveals the effectiveness of the ball-milling process. Secondly, a
different type of NGnPs was also prepared by a simple two-step
reaction sequence (Fig. 12b).32 Briey, edge-selectively func-
tionalized graphene was made via the direct Friedel–Cras

Fig. 12 Schematic representation of (a) the synthesis of NGnPs via mechanochemical ball milling under nitrogen gas (N2) and (b) the synthesis of
NGnPs via edge-selective functionalization of pristine graphite with 4-aminobenzoic acid and subsequent heat treatment under a nitrogen
atmosphere at 900  C. Current–voltage characteristics of (c) the DSSCs with Pt and NGnP counter electrodes and (d) with Pt and different
thicknesses of NGnPs as the counter electrodes under one sun illumination (AM 1.5G). (a), (c) Reproduced from ref. 33 with permission from
Nature Publishing Group. (b), (d) Reproduced from the ref. 32 with permission From the American Chemical Society.

This journal is © The Royal Society of Chemistry 2014 J. Mater. Chem. A


Journal of Materials Chemistry A
acylation of pristine graphite and 4-aminobenzoic acid in a PPA/
P2O5 medium followed by an additional thermal treatment at
900  C for 2 h under nitrogen, which was applied to yield the
target product of NGnPs.28,32 In order to evaluate the perfor-
mance of the edge-nitrogenated graphene as a counter elec-
trode, DSSCs with O-alkylated-JK-225, HC-A and Co(bpy)33+/2+ as
a sensitizer, co-adsorbent, and redox couple, respectively, were
fabricated with graphene-based counter electrodes, i.e., NGnPs
(from ball-milling) or NGnPs (from direct Friedel–cras acyla-
tion), on FTO substrates using an electrostatic spray deposition
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technique. For comparison purposes, DSSCs with Pt as a
counter electrode were also fabricated. Interestingly, the DSSCs
with the two types of edge-nitrogenated graphene outperformed
their Pt counterpart (Fig. 12c and d). For example, the NGnP-
based DSSC exhibited a PCE of 9.05%, which is higher than that
of the Pt-based device (8.43%) by a factor of 1.07 (Fig. 12d).32
These results suggest that NGnPs produced either by ball-
milling or a direct Friedel–Cras acylation followed by thermal
treatment are promising candidates for metal-free counter
electrodes in DSSCs.
5. Conclusions and perspectives
In this feature article, the recent development of graphene for
various photovoltaic applications such as OPVs and DSSCs has
been discussed. Due to its unique properties and versatility,
graphene has quickly emerged as a new class of material
useable in a diverse range of device components including the
transparent electrode, active layer, interfacial layer and counter
electrodes. The great potential of graphene has been widely
demonstrated in high performance and cost-effective solar cells
with additional advantages suitable for exible, resilient, and
light-weight devices.
Despite notable progress, research in this eld is still in its
infancy. A large number of additional challenges still exist for
the use of graphene as a key component in OPVs and DSSCs.
First, the development of simple, large-scale, and cost-effective
protocols for the synthesis of graphene with controlled
morphological and electronic properties is quite essential,
because the performance of graphene-based solar cells is closely
related to the intrinsic nature of graphene such as its purity,
band-gap, structural uniformity and so on. In this regard,
recently developed preparation methods, such as edge-selec-
tively functionalized graphene (EFG) with minimal damage to
its basal plane and a large number of desired functional
moieties installed at its edges either by mechanochemical ball-
milling process27,33 or direct Friedel–Cras acylation,28,32 can be
considered as quite promising candidates for the scalable
production of high quality functionalized graphene for OPVs
and DSSCs. Secondly, the exploitation of optimized device
fabrication techniques with scalability and processability is also
of great importance for the practical application of graphene-
based OPVs and DSSCs. For example, a roll-to-roll process in
conjunction with CVD has been preferred for the mass
production of graphene-based transparent electrodes in various
optoelectronic devices.42 Finally, the development of new types
of graphene-based materials like graphene quantum dots
J. Mater. Chem. A
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Feature Article
(GQDs) can be also considered another important challenge.90,91
In this approach, more precise control of the structure–property
relationship in graphene-based materials for solar cells is
possible. Due to quantum connement and edge effects
induced by conversion of 2D graphene sheets into 0D quantum
dots, some unusual properties of graphene can be obtained
from GQDs, which could ideally allow the fabrication of all
graphene-based solar cells in the near future. Therefore, it is
believed that continuous ongoing and innovative efforts into
the development of graphene-based materials and device
fabrication techniques should make graphene quite promising
as a material for OPVs and DSSCs.
Acknowledgements
This research work was supported by Basic Science Research
(2013R1A1A2007716), BK21 Plus, Mid-Career Researcher (MCR)
and Basic Research Laboratory (BRL) programs through the
National Research Foundation (NRF) of Korea funded by the
Ministry of Education, Science and Technology (MEST), VPP
program supported by King Saud University and the U. S. Air
Force Office of Scientic Research (AFOSR).
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