Copyright © 2015 by American Scientific Publishers

All rights reserved.

Science of
Printed in the United States of America
Advanced Materials
Vol. 7, pp. 1863–1912, 2015
www.aspbs.com/sam

Graphene-Based Dye-Sensitized
Solar Cells: A Review
Eric Singh1, 2 and Hari Singh Nalwa2, ∗
1
William S. Hart High School, 24825 North Newhall Avenue, Santa Clarita, California 91321, USA
2
Advanced Technology Research, 26650 The Old Road, Valencia, California 91381, USA

ABSTRACT
Current research in photovoltaic solar cells is intended to find appropriate organic materials as alternatives to
critically important metals (such as platinum and indium) in the fabrication of solar cell devices. Graphene-based
materials are receiving attention for areas from nanoelectronics to biomedical engineering, and also show sig-
nificant potential for solar energy applications. This article selectively focuses on the recent developments made
in applications of graphene-based materials as counter electrodes, photoanodes, electrolytes, and photosensi-
tizers in the fabrication of dye-sensitized solar cells (DSSCs). DSSCs consisting of graphene composites with
carbon nanotubes (CNTs), titanium dioxide (TiO2 ), platinum (Pt), zinc oxide (ZnO), nickel oxide (NiO), polypyr-
role, polyaniline, semiconductors, ionic liquids, metals, upconversion nanoparticles, and halide perovskites are
discussed in detail and their photovoltaic performance is compared with standard reference solar cells. One of

REVIEW
the interesting developments is that graphene–TiO2 nanocomposites exhibit superior photovoltaic properties to
those of the pure TiO2 commonly used as a photoanode in DSSCs. Overall PCE of graphene-based DSSCs
fluctuates in a wide range, and is significantly affected by a number of factors, including the materials used
for electrodes, electrolytes, photosensitizers, and solar cell configuration; it currently remains at a high of 13%
for push–pull porphyrin dyes. Additionally, the nanofabrication and processing of graphene-based materials
into quantum dots, nanofoams, nanoplatelets, aerogels, multilayers, fibers, paper, sheets, nanoparticles, and
nanoflakes, in addition to chemical functionalization, heteroatomic doping, thermal annealing, and molecular
interactions between semiconductor electrodes and dyes also significantly influence the photovoltaic perfor-
mance of DSSCs. Finally, we discuss the current status of graphene-based DSSCs and current challenges in
environmental stability, toxicity, and cost-effective production for commercial applications.
KEYWORDS: Graphene, Dye-Sensitized Solar Cells, Counter Electrodes, Photoanodes, Redox Electrolytes,
Photosensitizers, Graphene-Metal Composites, Graphene-Carbon Nanotube Composites, Graphene-Polymer
Composites, Graphene–TiO2 Composites, Graphene-Perovskite Composites, Chemical Functionalization,
Graphene Molecules, Heteroatom Doping, Photovoltaic Properties.

CONTENTS 6. Graphene-Based Electrolytes . . . . . . . . . . . . . . . . . . . . . . 1897

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1863 7. Graphene-Based Photosensitizers . . . . . . . . . . . . . . . . . . . 1901
2. Need of Graphene in Solar Cell Industry . . . . . . . . . . . . . . 1865 8. Conclusion and Perspective . . . . . . . . . . . . . . . . . . . . . . . 1903
3. Graphene and Dye-Sensitized Solar Cells . . . . . . . . . . . . . . 1866 Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1904
3.1. Graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1866 References and Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . 1904
3.2. Dye-Sensitized Solar Cells (DSSCs) . . . . . . . . . . . . . . 1867
4. Graphene-Based Counter Electrodes (CEs) for DSSCs . . . . . . 1870
4.1. Graphene Materials for CEs . . . . . . . . . . . . . . . . . . . 1870 1. INTRODUCTION
4.2. Graphene-Metal Composites for CEs . . . . . . . . . . . . . . 1876 Energy is one the most important social problems the
4.3. Graphene-Carbon Nanotubes Composites for CEs . . . . . . 1883 world faces today, because we need energy in every aspect
4.4. Graphene-Polymer Composites for CEs . . . . . . . . . . . . 1886
of our daily life. Therefore, many different sources of
4.5. Effect of Heteroatom Doping on
Graphene-Based CEs . . . . . . . . . . . . . . . . . . . . . . . . 1890 energy, including fossil, thermal, nuclear, hydroelectric,
5. Graphene-Based Photoanodes . . . . . . . . . . . . . . . . . . . . . . 1893 wind, natural gas, and solar1–5 are used to fulfill our grow-
ing demand. Solar energy is of great interest because it
∗
provides clean energy harvested from the Sun. New mate-
Author to whom correspondence should be addressed.
Email: nalwa@mindspring.com rials, technology, and fabrication processes have therefore
Received: 26 June 2015 been explored and continue to be. Several concepts of solar
Accepted: 2 August 2015 cells have been developed and studied over recent decades

Sci. Adv. Mater. 2015, Vol. 7, No. 10 1947-2935/2015/7/1863/050 doi:10.1166/sam.2015.2438 1863

 Graphene-Based Dye-Sensitized Solar Cells: A Review Singh and Nalwa

Eric Singh is a senior at William S. Hart High School in Los Angeles, California, USA.
He ranks number 1 among 537 students and has a GPA of 4.82 (w) vs 4.0/4.0 (uw). He
has received scores of 800 in both SAT Math I and SAT Mathematics Level II and 790
in Physics. Eric scored 5s in AP Physics B, AP Calculus BC with 5 AB subscore, AP
Computer Science, AP Physics C: Mechanics, AP Physics C: Electricity and Magnetism,
AP Statistics, and AP English Language and Composition and 4s in AP Biology and AP
Human Geography. Eric received the “National AP Scholar” award in 2015 and the “AP
Scholar with Distinction” award in 2014 and 2015 from the College Board. As a junior, Eric
also completed university-level Linear Algebra and Calculus III. Eric did a summer research
internship in science and engineering on plasma-jet printing of nanomaterials under the
auspices of Dr. M. Meyyappan, Director of the Center for Nanotechnology at NASA Ames
Research Center in California and on solar cells at Massachusetts Institute of Technology (MIT). Eric has two research
articles, “Graphene-based bulk-heterojunction solar cells: A review,” and “Stability of graphene-based heterojunction
solar cells,” to his credit, completed under the guidance of Dr. Hari Singh Nalwa.
Hari Singh Nalwa is an independent distinguished scientist and scholar working in
the fields of nanotechnology and materials science. He is the Founder, President, and
Chief Executive Officer (CEO) of American Scientific Publishers (www.aspbs.com), which
he established in 2000. Working for over 30 years, Dr. Nalwa has authored over 160
scientific articles, 25 book chapters, 18 patents, and 114 volumes of scientific books
in cross-disciplinary research areas of nanotechnology, materials science, polymer sci-
ence, chemistry, physics, and biosciences. He has played a critical role in the promo-
tion of the field of nanotechnology, as well as in cutting-edge scientific research in
REVIEW

materials science. Dr. Nalwa is an international authority who has written and edited/
co-edited 114 volumes of scientific books for the scientific community, and he is also one
of the most cited scientists in the world. Dr. Nalwa received a Bachelor of Science (B.Sc.)
degree in Biosciences (Chemistry, Zoology, and Botany) from Meerut University in 1974, a Master of Science (M.Sc.)
in Organic Chemistry from the Indian Institute of Technology (IIT) at Roorkee in 1977, and a Ph.D. in Polymer Sci-
ence/Physical Organic Chemistry from the Indian Institute of Technology (IIT) at Delhi in 1983. He started his career
as a guest scientist at the Hahn Meitner Institute (HMI, now part of Helmholtz-Zentrum Berlin für Materialien und
Energie) in West Berlin, West Germany (1983–1984), and thereafter moved to the University of Southern California
(USC) in Los Angeles, California (1984–1987) as a research associate. After a 3-year stay at USC, he moved to the
State University of New York at Buffalo (1987–1988) to work in the field of nonlinear optics. In 1988, he joined the
Tokyo University of Agriculture and Technology in Koganei, Tokyo, Japan, where he researched conducting polymers
and organic materials for second-order nonlinear optics and taught classes (1988–1990). In October 1990, he joined
Hitachi Research Laboratory (Omika-cho, Hitachi City, Ibaraki), Hitachi Ltd, Japan (1990–1999), as a staff scientist,
and while working at Hitachi Ltd, he was concurrently an honorary visiting professor at IIT Delhi. Dr. Nalwa returned
to the United States in 1999 and then became the head of department and R&D manager at Ciba Specialty Chemical
Corporation (Ciba-Geigy, Switzerland) in Los Angeles, California (1999–2000) where he worked for a year and there-
after, he established American Scientific Publishers (www.aspbs.com) in 2000, exclusively focused on nanotechnology.
Dr. Nalwa has been awarded a number of prestigious fellowships and awards including a National Merit Scholarship, an
Indian Space Research Organization (ISRO) Fellowship, a Council of Scientific and Industrial Research (CSIR) Senior
Fellowship, an NEC Fellowship–Japan (1988–1990), and a Japanese Government Science and Technology Agency Fel-
lowship. Dr. Nalwa was the founder and Editor-in-Chief of the Journal of Porphyrins and Phthalocyanines published
by John Wiley (1997–2000). He is the founder and Editor-in-Chief of the Journal of Nanoscience and Nanotechnology
(2001–present), published by American Scientific Publishers. Dr. Nalwa is well-known throughout the scientific com-
munity for his monumental major reference work on the Handbook of Nanostructured Materials and Nanotechnology,
5-volume set (Academic Press, 2000), which received the “Award of Excellence’ from the Association of American
Publishers, and the Encyclopedia of Nanoscience and Nanotechnology, 25-volume set (American Scientific Publishers,
2004/2011), which received the prestigious “Best Reference Work Award’ in 2005 from the American Society for Engi-
neering Education, and was selected as the 2005 “Outstanding Academic Title” by CHOICE magazine from the American
Library Association. Dr. Nalwa’s research experience includes organic electronic and photonic materials focused on ferro-
electric polymers, electrically conducting polymers, polymer electrets, metallophthalocyanines, nonlinear optical materials
for integrated optics, electroluminescent materials, low- and high-dielectric constant materials for microelectronics pack-
aging, organic semiconductors, nanocrystalline and nanostructured materials, Langmuir-Blodgett films, high-temperature
resistant polymer composites, epoxy-based photopolymers, rapid modeling, and stereolithography.

1864 Sci. Adv. Mater., 7, 1863–1912, 2015

Singh and Nalwa
including: (1) crystalline silicon (Si)-based solar cells based
on the p–n junction concept,6–8 (2) thin-film solar cells9–11
of cadmium telluride (CdTe), copper indium gallium
selenide (CuInGaSe), gallium arsenide (GaAs), (3) mul-
tijunction quantum dot solar cells,12 13 and (4) organic
polymer-based solar cells.14–16 The fastest growing groups
are the inorganic–organic halide perovskite–based solar
cells exhibiting power conversion efficiencies (PCEs) of
up to 20.1%.17 Still, one of the quests is to find other
solar energy materials as alternatives to the conventional
semiconductors used in solar cells, for low-cost production
and viability for commercial applications in future tech-
nologies. High-technology industries such as those pro-
ducing computers, cellular phones, light-emitting diodes
(LEDs), liquid-crystal displays (LCDs), integrated cir-
cuits, coatings, catalysts, batteries, energy storage devices,
aerospace, medical imaging, pharmaceuticals, and others,
depend upon the availability of energy sources.
2. NEED OF GRAPHENE IN SOLAR
CELL INDUSTRY
An important source of materials, critical to energy
generation, are metals found in our earth’s crust. Cur-
rent semiconductor electronic industries are based on sil-
icon technology. Graedel et al.18 have rightly pointed
out the criticality of 62 metals and metalloids in the
coming decades, because an imbalance exists between
increasing demands of many metals (including platinum
(Pt), gallium (Ga), germanium (Ge), selenium (Se), tel-
lurium (Te), gold (Au), chromium (Cr), tungsten (W), and
molybdenum (Mo)) in electronic and optoelectronic indus-
tries, which are affected by the lack of available metal
resources, supply risks, environmental implications, and
cost-effectiveness of production. Even though these metals
are used in a tiny quantity, current and emerging high-
technology industries may face risks due to the unavail-
ability of these critically important minerals. Once fossil
fuel–based energy resources become depleted, high-tech
industries and our daily life will be more dependent upon
other sources, including renewable energy sources such
as solar energy. The U.S. National Research Council19
evaluates the criticality of all types of minerals and
mineral-based materials for U.S. economic growth and
increasing demand in manufacturing industries. The criti-
cality of 11 minerals, including copper, gallium, indium,
lithium, manganese, niobium, some platinum group met-
als, and some rare-earth elements, as assessed by a criti-
cality matrix, is shown in Figure 1.19 For the growth of the
solar cell industry, minerals such as silicon, gallium, plat-
inum, selenium, tellurium, and indium are critically impor-
tant. Among these 11 critical minerals, conventionally used
platinum and indium were found to be the most critical
minerals from the viewpoint of their future availability due
to such factors (some unpredictable) as exhaustion of nat-
ural resources, economic and environmental acceptability,
Sci. Adv. Mater., 7, 1863–1912, 2015
Graphene-Based Dye-Sensitized Solar Cells: A Review
Fig. 1. Criticality assessments for 11 minerals or mineral-based materi-
als for U.S. economic growth. Reprinted with permission from [19], Min-
erals, Critical Minerals, and the U.S. Economy. U.S. National Research
Council, Washington D.C.: National Academies Press. © 2007, The
National Academy of Sciences.
and geopolitical concerns. It has therefore become a pri-
ority to find appropriate low-cost organic substitutes for
solar energy industries as well as other emerging future
REVIEW
technologies. For example, indium tin oxide (ITO) has
been traditionally used in the semiconductor industry in
the manufacturing of electronic components as well as
the fabrication of solar cells, and indium is an expensive
and critically important metal. Another important metal
is platinum, which is even more expensive than gold but
is valuable for electronic components manufacturing, cat-
alytic technologies, and chemotherapy. In fact, indium and
platinum are the most important metals currently used
in solar energy research as electrode materials for both
dye-sensitized solar cells (DSSCs) and bulk-heterojunction
(BHJ) solar cells.
Current research activity in solar cells is aimed at find-
ing appropriate substitute organic materials to prepare
metal-free transparent counter electrodes for cost-effective
DSSCs. Graphene is easily derived and processed from
graphite, which is copiously available in nature, whereas
the critically important metals are not. Therefore, graphene
has emerged as potentially important for not only replacing
critical minerals in semiconductor industries but to replace
both platinum and ITO in solar cell devices. Graphene-
based materials also offer high catalytic activity similar to
platinum and >90% optical transparency. Graphene and
graphene-based materials offer the flexibility to fabricate
devices over large areas; additionally, their low-cost pro-
duction and low weight are also attractive features for
tapping their potential in organic solar cells. Graphene
or graphene oxide can be used in transparent electrodes
in solar cells to replace ITO thin films. Like organic
polymeric materials, graphene offers several advantages,
including tunability of its work function, ease of process-
ing and fabrication into thin films, and inexpensive pro-
duction on a large scale. In addition to other components,
1865
 Graphene-Based Dye-Sensitized Solar Cells: A Review
the counter electrode is an important part of DSSCs, and
where graphene can play important roles for both photoan-
odes and transparent electrodes.
The harvesting of energy from the Sun using inorganic
semiconductors has been studied for decades. Graphene
has emerged as a potential new material to replace inor-
ganic semiconductors in solar cell fabrication, and thus
has drawn the attention of the scientific community. A few
review articles about graphene-based solar cells have been
published, but scientific data on bulk-heterojunction solar
cells and dye-sensitized solar cells are mixed together,
sometimes even with data on other energy storage devices
such as supercapacitors, batteries, and fuel cells. This has
motivated the authors to cautiously diverge the field into
two research areas: (i) graphene-based bulk-heterojunction
(BHJ) solar cells, and (ii) graphene-based dye-sensitized
solar cells (DSSCs). Recently, Singh and Nalwa20 pub-
lished an informative state-of-the-art review exclusively
focused on graphene-based BHJ solar cells. In the review
article, they cover graphene-containing perovskite and tan-
dem solar cell devices, and the role of layer thickness,
post-fabrication thermal annealing, hetero-atom doping,
REVIEW
mechanical bending, perovskites, and tandem solar cell
structure on the photovoltaic performance of graphene-
based solar cells. In another article, the stability and
degradation of graphene BHJ solar cells under atmo-
spheric conditions are analyzed and compared to organic
solar cells.21 A separate, complementary review article
is needed, to summarize data that are focused solely on
graphene-based DSSCs, with a new perspective to appeal
to the very broad scientific community working in the
fields of materials science, nanotechnology, physics, elec-
trical engineering, chemical engineering, chemistry and
device design, and engineering.
This review is rather selective and summarizes the
progress made in graphene-based DSSCs, where graphene
has been used, from electrode materials (photoan-
ode/counter electrode), to additive components (elec-
trolyte/sensitizer), in DSSCs for solar-energy harvesting
applications. The introduction outlines the importance of
metals in solar cells and research searching for alternative
organic materials where graphene shows a potential to fill
such demands. The first part of this review article focuses
on graphene and graphene-based materials. The second
part discusses DSSC structure and different components
including photosensitizers, electrolytes, and electrodes that
are used in the fabrication of DSSC devices. The third part
summarizes DSSCs based on graphene materials in dif-
ferent forms such as layers, foams, aerogels, sheet, films,
nanoplatelets, and their nanocomposites in combination
with carbon nanotubes (CNTs), polymers, ionic liquids,
metals, perovskites, and titanium dioxide (TiO2 . The sep-
arate sections are devoted to DSSCs based on graphene
composites with CNTs and TiO2 . The effect of elec-
trode materials, electrolytes, and dyes on the photovoltaic
1866
Singh and Nalwa
performance of graphene-based DSSCs is discussed. In the
conclusion, important challenges in commercial develop-
ment of DSSCs from graphene-based materials are out-
lined. This review outlines details from easily accessible
research articles on graphene-based DSSCs.
3. GRAPHENE AND DYE-SENSITIZED
SOLAR CELLS
3.1. Graphene
New materials play an important role in developing solar
energy technologies. Graphene, one of the allotropes
of abundantly available carbon, has emerged as one of
the most promising materials for applications in solar
cells since its discovery in 2004 after Novoselov et al.22
reported an electric field effect in a few-atoms-thick layer
of graphene. Geim and Konstantin of the University of
Manchester received the 2010 Nobel Prize in Physics for
their pioneering research on graphene.22 Graphene is a
1-atom-thick transparent layer of sp2 -hybridized carbon
atoms packed into a 2D nanostructure. Room temperature
carrier mobilities of 10,000 cm2 /Vs have been reported for
few-layer graphene (FLG).22 Nair et al.23 measured 97.7%
optical transparency for a single layer of graphene that
decreases as the number of graphene layers increase, and
where each additional graphene layer adds 2.3% opacity.
A sheet resistance of 2.1 k/sq for a single graphene layer
and 350 /sq for 4-layer graphene with ∼90% optical
transparency at a wavelength of 550 nm was reported by
Li et al.24 Therefore, both optical transparency and the
resistance of graphene decrease with an increasing num-
ber of graphene layers. High carrier mobility, low sheet
resistance, and high optical transparency are important cri-
teria when considering a material for solar cell applica-
tions; graphene fits perfectly as a transparent conductive
electrode (TCE) material. Lee et al.25 reported a Young’s
modulus of 1.02 terapascals (TPa) for bulk graphite, estab-
lishing graphene as the strongest material. Zhang et al.26
demonstrated by thermogravimetric analysis (TGA) that
the initial reduction of graphene oxide (GO) occurs at
100  C with the removal of absorbed water molecules,
and thereafter a 30% weight loss in 110–230  C takes
place due to the decomposition and removal of thermal-
liable oxygen functional groups from the GO surface.
Shen et al.27 conducted a TGA of reduced graphene oxide
(rGO) and indicated that the removal of oxygen functional
groups increases thermal stability for rGO, which has
only 2% weight loss at 700  C in a nitrogen atmosphere.
As discussed above, graphene shows unique electrical,
mechanical, thermal, chemical, and optical properties due
to its 2D characteristics, which can be further tailored via
processing into different forms. The 2D graphene struc-
ture can be transformed into large-area stretchable ultra-
thin films,28–30 nanoribbons,31–33 foams,34 35 and large-area
graphene paper36 and sheets.37–41 Pristine graphene has no
Sci. Adv. Mater., 7, 1863–1912, 2015
Singh and Nalwa
bandgap; therefore, it acts as a semimetal. Scientists are
exploring new chemical and physical ways to create an
artificial bandgap in graphene, which is one of the require-
ments for the fabrication of electronic devices. Zero-
bandgap graphene can be transformed into a wide-bandgap
semiconductor through hydrogenation via sp3 C–H bond
formation.42 Balog et al.43 reported a bandgap opening in
graphene by the patterned adsorption of atomic hydrogen
onto the Moiré superlattice positions of graphene when
graphene grown on an Ir(111) substrate was exposed to a
dose of atomic hydrogen. Fully or partially hydrogenated
graphene exhibits different structural, thermopower, elec-
tronic, magnetic, and transport properties from pristine
graphene.44 45
Because graphene is an atom-thick layer, it is a per-
fect nanoscale material and, therefore, has great poten-
tial in a very wide range of applications in the field
of nanotechnology. Nanoscale carbon materials such as
fullerenes, CNTs, diamonds, amorphous carbon, and their
composites have been widely studied for nanotechno-
logical applications,46–71 including nanoelectronics, nano-
optics, display devices, LEDs, computer data storage,
energy, membranes, nanofilters for water purification,
sensors, nanomedicine, stem cells, and energy conver-
sion devices.72–76 The emergence of nanotechnology has
significantly impacted high-tech industries and research,
where metal and metal oxide nanoparticles, nanotubes,
nanowires, and quantum dots can now replace con-
ventional semiconductor materials in solar cell devices.
Graphene is a 2D carbon-based material having a single
layer of carbon atoms; therefore, it is a simple nanos-
tructured material. Because of this, graphene has been
extensively studied for nanotechnological applications in
field-effect transistors, solar cells, fuel cells, supercapac-
itors, rechargeable batteries, optical modulators, chemi-
cal sensors, drug delivery, and biomedical applications, in
addition to other areas.77–90
Graphite oxide or graphene oxide (GO) contains
hydroxyl (–OH) and epoxide (–C–O–C–) functional
groups on the basal planes, and carbonyl (–COH) and car-
boxyl (–COOH) functional groups at the edges.91–92 Gao
et al. reported the presence of 5- and 6-membered-ring
lactols in a graphite oxide structure.93 Therefore, graphite
oxide has a heterogeneous electronic structure due to its
mixed sp2 and sp3 hybridizations.94–97 These functional
groups can be partially removed either by thermal anneal-
ing or by chemical treatment from graphite oxide,98 99
however, a few of these oxygen groups are still retained
in graphene sheets. A systematic study on the reduction
of GO was conducted by Mathkar et al.100 to tailor the
bandgap. By a controlled reduction process, the optical
bandgap of GO was found to change from 3.5 eV to
1.0 eV. The structural changes from GO to rGO and then
to graphene are accompanied by gradual changes in optical
Sci. Adv. Mater., 7, 1863–1912, 2015
Graphene-Based Dye-Sensitized Solar Cells: A Review
bandgap, electrical conductivity, carrier mobility, and ther-
mal stability. These parameters significantly affect the pho-
tovoltaic properties and stability of graphene-based solar
cells. GO is hydrophilic in nature, while graphene attains a
hydrophobic characteristic after a complete removal of all
oxygen functional groups from the GO surface. Oxygen
functional groups on the GO surface offer tremendous pos-
sibilities for chemical functionalization of the GO surface,
from small molecules to macrocyclic structures, to be used
in drug delivery, electronics, solar cells, and other applica-
tions. GO, rGO, and graphene have been extensively stud-
ied for both DSSC devices as well as bulk-heterojunction
solar cells. This review focuses solely on applications of
graphene-based materials in fabricating DSSC devices.
3.2. Dye-Sensitized Solar Cells (DSSCs)
In 1991, O’Regan and Grätzel101a proposed the DSSC
as a low-cost approach to producing solar energy, as
well as an alternative to silicon-based solar cells. Their
solar cell device was based on optically transparent thin-
film electrodes of nanocrystalline TiO2 with a porous
structure and ruthenium(II)–bipyridyl complex as a
REVIEW
photosensitizer (dye), which exhibited light-to-electric
energy conversion efficiencies of up to 7.9%, with great
stability. In 1993, Nazeeruddin et al.101b developed a
series of cis-X2 -bis(2,2-bipyridyl-4,4-dicarboxylate)-
ruthenium(II) complexes (where X = C1− , Br− , I− ,
CN− , or SCN− , where cis-di(thiocyanato)-bis(2,2-
bipyridyl-4,4-dicarboxylate)ruthenium(II) (RuL2 (NCS)2
complex), known as N3 dye, that can absorb up to
800 nm, proved to be the most interesting photosensitizer,
with a PCE of 10% with lithium iodide/triiodide as a
redox couple. Nazeeruddin et al.102 developed N749 dye,
trithiocyanato-4,44 -tricarboxy-2,2:6 ,2 -terpyridine-
ruthenium(II) [RuL’(NCS)3 complex], commonly known
as black dye, where ruthenium has 3 thiocyanato ligands
and 3 tetrabutyl ammonium cations. Black dye absorbs
sunlight in the near-IR region up to 920 nm. One of
the criteria for achieving a high PCE from a DSSC is
that the sensitizing dye should absorb as much sunlight
as possible. N3 dye has for this reason become one of
the reference dyes for DSSCs. DSSCs are thin film–
based, using a different photovoltaic mechanism from
that of standard p–n inorganic semiconductor–based solar
cells.
A number of reviews and book chapters on DSSCs
have been published in the literature103–139 since 1991. The
electrochemistry, physics, materials science, and technol-
ogy behind DSSCs have been extensively reviewed therein
by leading professionals working in this field. DSSCs
are also known as Grätzel solar cells, honoring their
invention and the pioneering work performed by Michael
Grätzel at the Swiss Federal Institute of Technology in
Switzerland.105 106 109 110 Figure 2 shows a schematic rep-
resentation of a DSSC, which basically mimics natural
1867
 Graphene-Based Dye-Sensitized Solar Cells: A Review Singh and Nalwa

Load also was made, using a DSSC as a top cell and a cop-
per indium gallium diselenide (Cu(In,Ga)Se2, or CIGS)
Dye thin film as a bottom cell, where the tandem device struc-

Fluorine-doped SnO2 (FTO)

Reduction ture DSSC/CIGS yielded >15% PCE.138 139 The operat-
Indium Tin Oxide (ITO)

3I–
ing principle of DSSCs has broadly been described in
Glass Substrate

Glass Substrate
the literature.108 113 121–123 The DSSC operating principle
Light

Platinum
e– Electrolyte as explained by Hara and Arakawa113 is outlined below.
(I-/I3-) e–
The key electrochemical process in DSSCs is photosen-
sitization. The photosensitizing dye molecules absorbed
I3– on the TiO2 photoanode–nanostructured surface absorb
Oxidation photons from incoming visible light, which excites the
TiO2 dye molecules from their ground state to an excited state
because of the metal-to-ligand charge transfer (MLCT)
transition. Electrons from photoexcited dye molecules are
Photoanode Counter
Electrode then injected into the conduction band of the TiO2 pho-
toanode, causing oxidation of the dye molecules. The
Fig. 2. Schematic representation of a common type of dye-sensitized injected electrons are transported between TiO2 meso-
solar cell (DSSC). The four critical components of a DSSC: (1) pho- porous nanoparticles flowing toward the transparent con-
toanode (here, mesoporous titanium dioxide [TiO2 ]); (2) light-absorbing
photosensitizing dye; (3) electrolyte (here, iodide/triiodide, [I− /I−3 ]) that
ductive oxide (back electron transfer), which then reach
regenerates the dye molecules; and (4) counter electrode (here, platinum), the Pt counter electrode via external loading. The oxidized
which facilitates catalysis. dye molecules attain a ground state after accepting elec-
trons from the iodide/triiodide redox couple, and then the
photosynthesis for light-harvesting from the Sun. A DSSC iodide (I−  gets oxidized to the triiodide (I− 3  oxidized
REVIEW

has four essential components: state. The oxidized triiodide (I− 3  ions flow toward the
(1) a photoelectrode (a semiconductor charge collector Pt counter electrode and are then reduced to iodide (I− 
ions. No permanent chemical transformation is involved
e.g., a thin-layer mesoporous oxide photoelectrode such as
in the generation of electric power in this electrochemi-
TiO2 ,
cal process. Considering the merits and challenges of the
(2) a photosensitizer (a light-absorbing photosensitive
DSSC system, the main disadvantages include the corro-
dye molecule, such as N3 dye, adsorbed onto the
sive nature of liquid redox electrolytes, which can dissolve
photoelectrode),
and degrade sealants and other connector metals over a
(3) an electrolyte (a reduction–oxidation [redox] elec-
period of time; the stability of electrolytes at high and low
trolyte in an organic solvent [e.g., iodide/triiodide redox
temperatures; and their toxicity. The advantages of DSSCs
couple] or a solid electrolyte), and
include ease in fabricating solar cell devices with readily
(4) a counter electrode (a high-catalytic-activity cathode
accessible component materials (electrodes, photosensitiz-
for performing the electrochemical redox reactions). ITO
ing dyes, electrolytes), low toxicity and low environmental
or fluorine-doped tin oxide (FTO) coated on a transparent pollution, high PCE, recyclability, and stability. In the past
glass substrate has generally been used as an anode, while few years, there have been significant advances in improv-
platinum-coated FTO glass has been used as the standard ing the PCE of DSSCs. The progress made in the research
transparent counter electrode for DSSCs. and development of electrode materials for photoanodes
The PCE of a DSSC is impacted by many variables, and counter electrodes, electrolytes, and sensitizing dyes
including photocurrent density. Therefore, new materials used for DSSCs are briefly discussed next.
such as photosensitizers (dyes) and electrolytes have been
sought in order to improve the photovoltaic performance 3.2.1. Electrode Materials (Photoanode and
of DSSCs. Hara and Arakawa113 outlined different com- Counter Electrode)
ponents, operating principles, and charge transfer kinetics Titanium dioxide (TiO2  is a naturally occurring min-
of a DSSC. Four energy levels are involved in the mecha- eral abundantly available around the world, therefore, it
nism of a DSSC, all of which contribute to performance: is commonly used for applications from photocatalysts
the excited state, or lowest occupied molecular orbital to pigments for sunscreen. Platinum (Pt) is the tradi-
(LUMO); the ground state, or highest occupied molecular tional counter electrode material used in DSSCs due to its
orbital (HOMO) of the dye (photosensitizer); the Fermi high electrical conductivity, stability, and desirable elec-
level of the TiO2 electrode; and the redox potential of the trochemistry with iodide/triiodide redox electrolytes. Here,
iodide/triiodide (I− /I−
3  mediator in the electrolyte. Pho- the charge transfer resistance (RCT  is one of the impor-
tocurrent is related to light-harvesting efficiency (LHE), tant parameters that determine the ability of a cathode
and to the balance between charge collection, regeneration, material in a DSSC device because it controls the elec-
and injection yields; A multijunction solar cell structure tron transfer process at the electrode-electrolyte interface.

1868 Sci. Adv. Mater., 7, 1863–1912, 2015

Singh and Nalwa
The RCT corresponds to the transfer resistance of elec-
trons at the interface of the counter electrode and the
electrolyte. The counter electrode plays the important role
of collecting electrons from the photoanode and acts as
a catalyst for the regeneration of the redox couple in
the electrolyte. Research activities have been focused on
finding alternative, new materials for fabricating Pt-free
counter electrodes for DSSCs because Pt is one of the
most expensive metals. A wide variety of counter elec-
trode materials having good stability have been devel-
oped and used to enhance PCEs in DSSCs. Hao et al.,140
Thomas et al.,141 and Wu and Ma142 summarized differ-
ent counter electrode materials used in DSSCs, includ-
ing Pt-based bulk, nanoparticles and composite materials,
carbon materials such as carbon black, amorphous car-
bon, mesoporous carbon, nanostructured carbons (CNTs,
graphene, nanofibers) and their composites, polymers-
based composites, transition metal-based carbides, nitrides,
oxides, sulfides, phosphides, selenides, tellurides, their
alloys, and organic conducting polymers such as polypyr-
role, polythiophene, polyaniline, and polystyrenesulfonate
(PSS)-doped poly(3,4-ethylenedioxythiophene) (PEDOT)
(PEDOT:PSS). Zhang and Cao124 reviewed different types
of nanostructured photoelectrode materials, which include
nanoparticles, nanowires, and nanotubes made of TiO2 ,
zinc oxide (ZnO), hybrid nanomaterials, core–shell nano-
structures, aggregates, etc., used in DSSCs. The PCE
of DSSCs varies depending on these electrode materials,
which include TiO2 , ZnO, SnO2 , TiO2 /ZnO, SnO2 /ZnO,
Nb2 O5 /TiO2 , TiN, TiC, CoS, NiS, MoS, MoP, carbons,
conjugated polymers, etc. In addition to other carbon-
based materials, graphene has emerged as a new counter
electrode material that can replace Pt electrodes in DSSCs.
Maçaira et al.144 reviewed nanostructured photoelectrodes,
including nanoparticles, nanotubes, nanowires, 3D hier-
archically ordered photoelectrodes, and graphene/TiO2
hybrids for fabricating high-performance DSSCs.
3.2.2. Electrolytes
The electrolyte influences the photovoltaic parameters
of a DSSC, in addition to others of its characteristics.
An electrolyte performs several functions, including the
regeneration of photosensitizer (dye), electrochemical
reactions, and interactions with the electrode interfaces,
the ultimate role of a charge transport carrier between
a photoelectrode and a counter electrode in a DSSC
device. The counter electrode should be of high cat-
alytic activity because it plays a very important role in
reducing triiodide to iodide, and consequently helps in
regenerating dye molecules. The electrolyte acts as a con-
ducting medium, which can be either a liquid or a solid
electrolyte. Boschloo and Hagfeldt122 discussed the role
of a iodide/triiodide redox couple in DSSCs, including
energetics, working mechanism, and kinetics as well as
alternative redox electrolytes such as a bromide/tribromide
Sci. Adv. Mater., 7, 1863–1912, 2015
Graphene-Based Dye-Sensitized Solar Cells: A Review
(Br− /Br− 
3  redox couple, tris(2,2 -bipyridyl)cobalt(II/III)
complex [Co(bpy)3]2+/3+ , copper(I/II) coordination com-
plexes, and solid-state hole-transport materials (HTM)
of 2,2 ,7,7 -tetrakis-(N ,N -di-p-methoxyphenylamine)-9,9-
spirobifluorene (spiro-MeOTAD) developed by Bach
et al.143 Wu et al.137 published an excellent review
summarizing different types of electrolytes used in
fabricating DSSCs, including liquid electrolytes, quasi
solid-state electrolytes, and solid-state HTMs, such as
PEDOT, spiro-OMeTAD, P3HT, CuI, and CuSCN. Hao
et al.140 also summarized different iodine-free redox
electrolytes such as ferrocenes, pyridines, porphyrins, 5,5 -
dithiobis(1-methyltetrazole)/1-methyltetrazole-5-thiolate
(T2 /T− , copper bis-2,9-dimethyl-1,10-phenanthroline
(Cu(dmp)2, a Co(II/III)(2,2-bipyridine)3 redox com-
plex, etc.
3.2.3. Photosensitizers (Dyes)
In a DSSC, the sunlight harvesting process is performed
by the photosensitizing dye. It is very important that
the dye has a longer spectral absorption range so that
it can absorb as much sunlight as possible. Pioneering
work by Grätzel101 111 led to the research and develop-
REVIEW
ment of today’s DSSC-based technology. A large number
of ruthenium-based photosensitizers as well as ruthenium-
free organic dyes were designed and synthesized by
Grätzel’s group (Chen et al.104 and Grätzel105 ), including
a heteroleptic ruthenium complex containing an electron-
rich hexylthio-terminal chain, which exhibited a PCE of
11.5%. Yum et al.111 and Mishra et al.134 outlined all
types of metal-free organic dyes for DSSCs. Narayan114
reviewed the literature on different types of natural dyes
used as photosensitizers in DSSCs. Basically, DSSCs oper-
ate in a similar way to how photosynthesis takes place
in plants. Chlorophyll, found in the chloroplasts of plant
cells, acts as a light harvester similar to the organic dye
that acts as a photosensitizer in DSSCs. Although chloro-
phyll itself has no significant relevance to solar cells,
it is worth mentioning that from the chemistry point
of view, both chlorophyll and photosensitizing porphyrin
dyes share a common heterocyclic central ring struc-
ture, where four pyrrole units connected via methylyli-
dene bridges constitute a highly -conjugated system. Ye
et al.145 summarized photosensitizers based on ruthenium
polypyridyl dyes, porphyrin dyes, and quantum dot (QD)
sensitizers including CdS, CdSe, CdTe, PbS, PbSe, Sb2 S3
QDs, halide perovskite CH3 NH3 PbX3 (X = Cl, Br, or I)–
based sensitizers, and upconversion nanoparticles, among
others. Recent developments in photosensitizers in connec-
tion with graphene-based DSSCs are discussed in subse-
quent sections.
Figure 3 shows the chemical structures of a few com-
monly used redox electrolytes, solid-state electrolytes
(HTMs) and photosensitizers in the fabrication of DSSCs,
which will be discussed throughout this article. Here,
1869
 Graphene-Based Dye-Sensitized Solar Cells: A Review Singh and Nalwa

(1) Co(bpy)3 (2) PEDOT (3) PSS (4) P3HT

(5) Spiro-OMeTAD (6) Chlorophyll a

REVIEW

-
COO TBA+

HOOC S
N C
N N
Ru
N
N C
N
S
+ -
TBA OOC C

S
TBA = tetra butylammonium cation

(7) N3 Dye (8) N719 dye (9) N749 Dye (Black dye)

Fig. 3. Chemical structures of (1) Co(bpy)3 = tris(2,2 -bipyridyl)cobalt(II/III) redox electrolyte; solid-state hole-transport materials (HTM), including
(2) PEDOT = poly(3,4-ethylenedioxythiophene), (3) PSS = poly(styrenesulfonate), (4) P3HT = poly(3-hexylthiophene), (5) spiro-OMeTAD = 2,2 ,7,7 -
tetrakis(N ,N -p-dimethoxy-phenylamino)-9,9 -spirobifluorene; photosensitizers, including (6) the natural dye chlorophyll a, where M = Mg2+ and
R = phytol chain, (7) N3 dye = cis-bis(isothiocyanato)bis(2,2 -bipyridyl-4,4 -dicarboxylato)ruthenium(II), (8) N719 dye = di-tetrabutylammonium cis-
bis(isothiocyanato)bis(2,2 -bipyridyl-4,4 -dicarboxylato)ruthenium(II), where tetrabutylammonium cation = (C4 H9 4 N+ , (9) N749 dye or black dye =
triisothiocyanato-(2,2 :6 ,6 -terpyridyl-4,4 ,4 -tricarboxylato) ruthenium(II) tris(tetra-butylammonium), commonly used for DSSCs.

tris(2,2 -bipyridyl)cobalt(II/III) [Co(bpy)3] is a redox elec-
trolyte, and poly(3,4-ethylenedioxythiophene) (PEDOT),
poly(styrenesulfonate) (PSS), and poly(3-hexylthiophene)
(P3HT), and 2,2 ,7,7 -tetrakis(N ,N -p-dimethoxy-phenyl-
amino)-9,9-spirobifluorene (spiro-OMETAD) are solid-
state HTMs. Chlorophyll a, cis-bis(isothiocyanato)
bis(2,2 -bipyridyl-4,4-dicarboxylato) ruthenium(II) (N3 dye),
ditetrabutylammonium cis-bis(isothiocyanato)bis(2,2-

bipyridyl-4,4 -dicarboxylato)ruthenium(II), where tetra-
butyl-ammonium cation (C4 H9 4 N+  (N719 dye), and
triisothiocyanato-(2,2:6 ,6 -terpyridyl-4,4,4 -tricarboxy-
lato) ruthenium(II) tris(tetra-butylammonium) (N749
or black dye) are photosensitizers commonly used for
DSSCs. Carbon-based materials such as carbon nanotubes,
graphene, carbon nanofibers, microporous hard carbon
spherules, porphyrinic carbons as counter electrodes,
new photosensitive organic dyes such as ruthenium com-
plexes, porphyrins, phthalocyanines, cyanines, coumarins,
perylenes, squaraines, and new electrolytes have been
investigated as alternative components for DSSCs.
4. GRAPHENE-BASED COUNTER
ELECTRODES (CEs) FOR DSSCs
4.1. Graphene Materials for CEs
Graphene-based materials have shown significant poten-
tial in the field of solar cells, and extensive liter-
ature on their use exists. Graphene, GO, and their

1870 Sci. Adv. Mater., 7, 1863–1912, 2015

Singh and Nalwa
based blends, composites, and hybrids have been exten-
sively studied for fabricating solar cells in both DSSCs
and bulk-heterojunction (BHJ) structures.146–150 Singh
and Nalwa20 21 recently reviewed the current status of
graphene-based BHJ solar cells and the stability and
degradation of BHJ solar cells under air atmosphere
for commercial applications. Roy-Mayhew and Aksay147
summarized graphene-based materials and their applica-
tions in DSSCs as transparent electrode, semiconducting
layer, photosensitizer, additives in electrolytes, and counter
electrode. Kavan148 reviewed multiple types of carbon
nanomaterials, including fullerenes, CNTs, graphene, and
diamond for their applications in DSSCs as photoanode,
counter electrode, current collector, and light-absorbing
molecules.
Graphene-based materials have been explored as new
counter electrode materials in DSSCs because of their
interesting electrochemical catalytic activities, high con-
ductivities, high surface areas, corrosion resistance, low
weight, and low cost of production. This section is
devoted to graphene and GO–based CEs for DSSCs.
The PCEs of DSSCs under identical experimental condi-
tions also are listed for comparison, where a standard Pt
counter electrode was used in a reference cell. A num-
ber of factors influence the photovoltaic performance of
graphene-based DSSCs, including the materials used for
electrodes (photoanode and counter electrode), redox elec-
trolytes, and photosensitizing organic dyes; the solar cell
configuration; the nanofabrication process of graphene-
based materials into different physical forms such as
nanoparticles, nanoflakes, nanoplatelets, QDs, nanofoams,
aerogels, multilayers, fibers, paper, sheets, and their dop-
ing, as well as the molecular interactions between semi-
conductor electrodes (photoanode, cathode) and organic
dyes. Table I summarizes the photovoltaic performance
of DSSCs in terms of short-circuit photocurrent density
(JSC , open-circuit voltage (VOC  fill factor (FF), and
power conversion efficiency (PCE; , in addition to pho-
tosensitizing dye and redox couples for graphene and
GO–based materials, including different physical forms
such as nanoplatelets, nanofoams, QDs, aerogels, multi-
layers, fibers, paper, sheets, nanoparticles, nanoflakes, and
chemically functionalized materials.151–175
Graphene nanoplatelets have shown a significant
promise for DSSCs. Kavan et al.151 fabricated an optically
transparent cathode for DSSCs using graphene
nanoplatelets, where new electrolytes based on ionic liquids,
namely, Z946 consisting of 1 M 1,3-dimethylimidazolium
iodide + 0.15 M iodine + 0.5 M N -butylbenzoimidazole +
0.1 M guanidine thiocyanate in 3-methoxypropionitrile,
and Z952 consisting of 1,3-dimethylimidazolium
iodide + 1-ethyl-3-methylimidazolium iodide + 1-ethyl-3-
methylimidazolium tetracyanoborate + iodine + N -butyl-
benzoimidazole + guanidinium thiocyanate (molar ratio of
12/12/16/1.67/3.33/0.67), were used in an iodide/triiodide
Sci. Adv. Mater., 7, 1863–1912, 2015
Graphene-Based Dye-Sensitized Solar Cells: A Review
redox system. RCT was found to be in the range of
94–1183  cm2 for the Z946 electrolyte and 15–
205  cm2 for the Z952 electrolyte ionic liquid, showing
that RCT is 5–6 times larger for the Z952 electrolyte
ionic liquid than for the Z946 electrolyte. The films
of graphene nanoplatelets showed 85% transparency.
At 1 sun illumination, graphene nanoplatelets with the
Z946 electrolyte exhibited a PCE of 5% and FF of
0.52 compared to a PCE of 6.89% and FF of 0.74
for the reference Pt electrode. This study evidenced
the role of electrolyte ionic liquid in the efficiency
of DSSCs with graphene nanoplatelets (GNPs). Kavan
et al.152 fabricated DSSCs using GNP on a fluorine-doped
SnO2 (FTO) with a [Co(bpy)3]2+/3+ redox couple and
Y123 dye-sensitized TiO2 photoanodes. Here, the Y123
dye is 3-[6-[4-[bis(2 4 -dihexyloxybiphenyl-4-yl)amino-]
phenyl[-4,4-dihexylcyclopenta-[2,1-b:3,4-b]dithiphene-2-yl]-
2-cyanoacrylic acid. The loading of GNP on FTO was
between 1–10 g/cm2 and GNP films were labeled
according to an optical transparency of 550 nm. With GNP
(G100) loading of 0.3 g/cm2 , optical transparency was
equal to the FTO electrode, and a cell resistance (RCV 
of 200  cm2 , a sheet resistance (RSH  of 2.6  cm2 ,
REVIEW
and a RCT of 104  cm2 were recorded. At the 0.51 sun
illumination, GNP showed a PCE of 9.6% and a FF of
75%, which were superior compared to a Pt/FTO-based
cathode (PCE, 9.2%; FF, 71%).
In another study, Kavan et al.153 used GNP film on FTO
as a cathode, with a Co2+/3+ (L)2 redox couple where L
is 6-(1H-pyrazol-1-yl)-2,2-bipyridine, and with a Y123-
sensitized TiO2 photoanode. The chemical structures of
the Co2+/3+ (L)2 redox couple and Y123 dye are shown in
Figure 4. In the Y123 dye structure, the triphenylamine is
an electron donor, the dithiophene species is the -bridge,
while CN(COOH) is an electron acceptor. The current
densities of GNP film for the Co2+/3+ (L)2 redox reaction
were found to be 1–2 orders of magnitude higher com-
pared with the I− −
3 /I redox couple on the similar elec-
trode. The GNP films with <88% transparency showed
better performance than the Pt/FTO counter electrode for
the Co2+/3+ (L)2 redox reaction. With the Y123 dye on the
TiO2 photoanode, PCEs were between 8% and 10% for
both GNP and Pt-based cathodes, where the GNP cathode
outperformed the Pt/FTO cathode in terms of PCE and FF
at higher illumination intensities. At 0.5 sun illumination,
the GNP with a Co2+/3+ (L)2 redox couple showed a PCE
of 9.7% and FF of 0.73, compared to a PCE of 9.2% and
FF of 0.68 for the reference Pt electrode, because of the
higher electro-catalytic activity at the GNP cathode due to
its lower RCT .
Different physical forms of graphene have been
used for DSSCs. Ju et al.154 used nitrogen-doped
graphene nanoplatelets (N-GNP) as counter electrode in a
[Co(bpy)3]3+/2+ -based redox electrolyte for DSSCs, where
N-GNP was coated on an FTO surface using electro-
spray method. The N-GNP electrode showed a RCT of
1871
 Graphene-Based Dye-Sensitized Solar Cells: A Review Singh and Nalwa

Table I. Graphene-based counter electrodes used in DSSCs. Short-circuit photocurrent density (JSC , open-circuit voltage (VOC , fill factor (FF), and
power conversion efficiency (PCE, ), redox couples, and dye used in DSSCs containing graphene and graphene oxide. The PCE of a DSSC with a
standard Pt counter electrode is used as the reference electrode in a solar cell device.

Graphene-based counter electrodes in DSSC Redox couples Dye JSC (mA/cm2  VOC (V) FF (%) PCE (, %) Ref.
− − a
Graphene nanoplatelets I /I (Z946)
3 N719 134 0657 65 573 [151]
− −
Pt reference I /I (Z946)
3 N719 131 0627 77 633 [151]
− −
Graphene nanoplatelets I /I (Z952)b
3 N719 116 0610 73 516 [151]
− −
Pt reference I /I (Z952)
3 N719 118 0612 78 570 [151]
Graphene nanoplatelets [Co(bpy)3 ]2+/3+ Y123c 148 0878 72 94 [152]
Pt reference [Co(bpy)3 ]2+/3+ Y123 140 0904 65 82 [152]
Graphene nanoplatelets Co2+/3+ (L)2 Y123 127 1030 70 93 [153]
Pt reference Co2+/3+ (L)2 Y123 121 1047 63 81 [153]
Nitrogen-doped graphene nanoplatelets [Co(bpy)3 ]2+/3+ JK-225d 1383 0883 742 905 [154]
Pt reference [Co(bpy)3 ]2+/3+ JK-225 1348 0885 706 843 [154]
Graphene oxide (heated at 450  C in air) [Co(bpy)3 ]2+/3+ Y123 151 0892 66 88 [155]
Reduce graphene oxide (rGO) [Co(bpy)3 ]2+/3+ Y123 156 0891 61 84 [155]
GO (50%)/graphene nanoplatelets [Co(bpy)3 ]2+/3+ Y123 156 0885 67 93 [155]
Pt reference [Co(bpy)3 ]2+/3+ Y123 152 0901 66 90 [155]
Honeycomb-structured graphene (HSG) I− /I−3 N719 272 0773 371 780 [156]
Graphene (chemical exfoliation of graphite) I− /I−3 N719 648 0785 127 064 [156]
Graphene nano-foam (CVD grown) I− /I−3 N719 122 071 600 52 [157]
Pt reference I− /I−3 N719 121 07 692 57 [157]
Reduced graphene oxide (rGO) I− /I−3 N719 811 072 46 264 [158]
Pt reference I− /I−3 N719 803 074 61 350 [158]
Reduced graphene oxide (rGO) – – 1699 075 54 681 [159]
REVIEW

Reduced graphene oxide (rGO) I− /I−3 N719 1635 066 333 360 [160]
Pt reference I− /I−3 N719 1620 067 600 644 [160]
Graphene quantum dots I− /I−3 N3 558 0583 66 215 [161]
Functionalized graphene sheet (FGSs)/FTO I− /I−3 N3 1316 064 60 499 [162]
Platinum (Pt)/FTO I− /I−3 N3 789 073 72 416 [162]
Pt reference I− /I−3 N3 1303 064 67 548 [162]
Functionalized graphene sheet (FGS) I− /I−3 N719 134 0737 69 679 [163]
Pt reference I− /I−3 N719 134 0743 68 679 [163]
Functionalized graphene sheet (FGS) [Co(bpy)3 ]2+/3+ D35 849 0813 65 451 [163]
Functionalized graphene sheet (FGS) (T2 /T−  D35 950 0663 55 345 [163]
Graphene ribbons (few-layer) I− /I−3 N719 11852 0780 499 461 [164]
Pt reference I− /I−3 N719 13269 0790 622 693 [164]
Inverted graphene ribbons (few-layer) I− /I−3 N719 7983 0770 525 323 [164]
Inverted Pt reference I− /I−3 N719 8183 0760 745 463 [164]
Nitrogen-doped graphene film I− /I−3 N719 1175 073 49 420 [165]
Nitrogen-doped graphene foam (N-GF) I− /I−3 N719 1584 077 58 707 [165]
Reduced graphene oxide foams (rGOF) I− /I−3 N719 1434 075 45 484 [165]
Pt reference I− /I−3 N719 1427 079 66 744 [165]
Nitrogen-doped rGO [Co(bpy)3 ]2+/3+ N719 1001 0589 65 385 [166]
Sulfur-doped rGO [Co(bpy)3 ]2+/3+ N719 1095 0607 64 423 [166]
Nitrogen/sulfur-doped rGO [Co(bpy)3 ]2+/3+ N719 1170 0601 67 473 [166]
Reduced graphene oxide (rGO) [Co(bpy)3 ]2+/3+ N719 1045 0598 56 357 [166]
Pt reference [Co(bpy)3 ]2+/3+ N719 1022 0609 50 311 [166]
Graphene nanosheet/graphene foam – – 1521 076 77 770 [167]
Graphene nanoplatelets [Co(bpy)3 ]2+/3+ SM315 181 091 78 130 [168]
Graphene nanoplatelets – SM371 159 096 79 120 [168]
Graphene aerogels – – 1180 074 68 593 [170]
Pt reference 1188 073 71 620 [170]
CVD-3D graphene network I− /I−3 N719 172 0713 69 846 [171]
Pt reference I− /I−3 N719 163 0725 676 798 [171]
Edge-fluorinated graphene nanoplatelets [Co(bpy)3 ]2+/3+ JK-306e 1444 0970 715 101 [172]
Hydrogen-graphene nanoplatelets [Co(bpy)3 ]2+/3+ JK-306 1405 0925 458 596 [172]
Pt reference [Co(bpy)3 ]2+/3+ JK-306 1428 0965 698 961 [172]
Fluorinated graphene I− /I−3 – 1090 066 359 256 [173]
Edge-carboxylated graphene nanoplatelets [Co(bpy)3 ]2+/3+ JK-303 1407 – 744 931 [174]
Reduced graphene oxide (rGO) [Co(bpy)3 ]2+/3+ JK-303 1388 – 729 894 [174]
Pt reference [Co(bpy)3 ]2+/3+ JK-303 1369 – 716 867 [174]

1872 Sci. Adv. Mater., 7, 1863–1912, 2015

Singh and Nalwa Graphene-Based Dye-Sensitized Solar Cells: A Review

Table I. Continued.

Graphene-based counter electrodes in DSSC Redox couples Dye JSC (mA/cm2  VOC (V) FF (%) PCE (, %) Ref.
− −
Graphene nanosheet I /I 3 N719 1266 0752 572 545 [175]
Graphene nanosheet (400  C, 4 h) I− /I−
3 N719 1222 0812 697 693 [175]
Pt reference I− /I−
3 N719 1280 0828 681 723 [175]

Notes: a Z946 = electrolyte based on ionic liquids 1 M 1,3-dimethylimidazolium iodide + 0.15 M iodine + 0.5 M N -butylbenzoimidazole + 0.1 M guanidine
thiocyanate in 3-methoxypropionitrile (coded Z946); b Z952 = 1,3-dimethylimidazolium iodide + 1-ethyl-3-methylimidazolium iodide + 1-ethyl-3-methylimidazolium
tetracyanoborate+iodine+N -butylbenzoimidazole+guanidinium thiocyanate (molar ratio 12/12/16/1.67/3.33/0.67); c Y123 dye = 3-[6-[4-[bis(2  4 -dihexyloxybiphenyl-4-yl)
amino-]phenyl[-4,4-dihexylcyclopenta-[2,1-b:3,4-b]dithiphene-2-yl]-2-cyanoacrylic acid; d JK-225 = (E)-3-(5-(6-(Bis(9,9-dimethyl-9H-fluoren-2-yl)amino)-4,4-dimethyl- 4H-
indeno[1,2-b]thiophen-2-yl)thiophen-2-yl)-2-cyanoacrylic acid (JK-225); e JK-306 = (E)-3-{5 -{4-[bis(2 ,4 -dihexyloxybiphenyl-4-yl)amino]phenyl}-2,2 -bithioph-ene-5-yl}-2-
cyanoacrylic acid.

1.73  cm2 , much lower compared with a Pt electrode
(3.15  cm2 . The DSSC with N-GNP counter elec-
trode had a FF of 74.2% and PCE of 9.05%, outperform-
ing the Pt counter electrode, which had a FF of 70.6%
and PCE of 8.43% because of the decreased RCT at the
interface of the counter electrode and electrolyte solution.
Kavan et al.155 used single-layer GO films coated on an
FTO surface, either in its pure form or as a composite
with graphene nanoplatelets, for fabricating DSSC with a
[Co(bpy)3]3+/2+ redox couple in acetonitrile with a Y123-
PCE of 7.80%, twelve times higher than that of a counter
electrode made of graphene and prepared by chemical
exfoliation of graphite, which was comparable to an 8%
PCE of a Pt electrode–based DSSC device. Lee et al.157
fabricated 3D nano-foam of few-layer graphene (3D-NFG)
via chemical vapor deposition (CVD) method to use as a
counter electrode in DSSCs. The 3D-NFG offers a large
surface area and high electrical conductivity. The 3D-NFG
counter electrode showed a FF of 60% compared to 69.2%
for the Pt counter electrode, and both RSH and RCT of 3D-

sensitized TiO2 photoanode. At 0.095 sun illumination,
the PCEs of GO, rGO, GO (10%)/graphene nanoplatelets
composite, and Pt cathodes were almost the same (10%).
At 0.51 sun illumination, PCEs of 9.3% for rGO with
84% transmittance, 9.6% for GO/graphene nanoplatelets
with 10%, 20%, and 50% GO loading having 63%, 88%,
and 80% transmittance at 550 nm were measured, respec-
tively. Wang et al.156 prepared 3D-honeycomb-structured
graphene (HSG) to be used as a counter electrode for
DSSCs. The 20 m–thick HSG film prepared with 12-
hour reaction time showed a RSH of 3.4 k/square. A TiO2
photoanode on FTO substrate was used with N719 dye
in an iodide/triiodide electrolyte for DSSCs and showed a
REVIEW
NFG were also higher than that of the Pt electrode. The
PCE of a DSSC device fabricated with a 3D-NFG counter
electrode was found to be comparable to a Pt-based DSSC.
Cruz et al.158 used graphene films as counter electrodes in
DSSCs that were prepared by spray deposition of graphene
oxide (GO) or chemically reduced GO (RGO). The GO-
based DSSCs showed a PCE of 75% compared with
reference Pt counter electrodes. The RGO showed 95%
transparency at 550 nm, so it is more transparent than
the graphene with 85% transparency reported by Kavan
et al.,151 although PCEs of both types of graphene are simi-
lar. The annealed graphene oxide (AGO) counter electrode
exhibited slightly higher transparency (89% at 550 nm)

(Co2+/3+(L)2) (Y123 dye)

Fig. 4. Chemical structure of Co2+/3+ (L)2 redox couple where L is 6-(1H -pyrazol-1-yl)-2,2 -bipyridine and 3-[6-[4-[bis(2  4 -dihexyloxybiphenyl-4-
yl)amino-]phenyl[-4,4-dihexylcyclopenta-[2,1-b:3,4-b]dithiphene-2-yl]-2-cyanoacrylic acid (Y123 dye). Redrawn and adapted from [152], L. Kavan,
et al., Graphene nanoplatelets outperforming platinum as the electrocatalyst in co-bipyridine-mediated dye-sensitized solar cells. Nano Lett. 11, 5501–
5506 (2011). [153] L. Kavan, et al., Graphene nanoplatelet cathode for Co(III/II) mediated dye-sensitized solar cells. ACS Nano 5, 9171–9178 (2011).
© 2011, American Chemical Society.

Sci. Adv. Mater., 7, 1863–1912, 2015 1873

 Graphene-Based Dye-Sensitized Solar Cells: A Review Singh and Nalwa

and higher PCE (2.64%). Jang et al.160 used moderately

reduced GO films as a counter electrode in DSSCs. A PCE
of 0.5% was recorded for GO films with no thermal treat-
ment or which were thermally treated at 150  C. When GO
films were thermally treated at 350  C, the PCE increased
to 3.60%, which may result from the improvement in elec-
trical conductivity as well as from higher catalytic activity
from the reduction of GO. Wei et al.161 prepared three-
dimensional cauliflower fungus–like graphene (3D CFG)
from CO2 , which exhibited high electrical conductivity.
The 3D CFG, Pt, and graphene prepared via chemical
exfoliation of graphite were used as counter electrodes in
DSSCs. The 3D CFG electrode showed a PCE of 8.1%, ten
times higher compared to graphene from chemical exfoli-
ation of graphite (PCE, 0.7%), and also higher than a Pt
counter electrode (PCE, 7.5%).
Chemically functionalized graphene has been used
for DSSCs. Roy-Mayhew et al.162 compared the energy
conversion efficiency of functionalized graphene sheets
(FGSs) with Pt, where different dyes and electrolytes were
also used for comparison. FGSs contain oxygen-rich func-
tional groups such as hydroxyls, carbonyls, and epoxides,
and therefore have a large surface area, up to 2630 m2 /g,
REVIEW

as well as lattice defects. The RCT of 0.64  cm2 and

0.79  cm2 for FGS and Pt electrodes was measured,
respectively. For instance, the FGS solar cell showed a
RCT of 1.20 W cm2 at 0.5 V bias and a 10× greater RCT
than for Pt at no applied bias. The energy conversion effi-
ciencies of about 5.0% and 5.5% at 100 mW/cm2 AM
1.5 simulated light was measured for FGS with oxygen-
containing sites and Pt respectively. Roy-Mayhew et al.163
used FGS electrodes for DSSCs, using ethyl cellulose as
a binder and thereafter performing a partial thermolytic
process. Triiodide/iodide-, cobalt-, and sulfur-based com-
plexes were used as redox mediators in the DSSCs. FGS-
based electrodes showed lower effective RCT compared to
thermally decomposed chloroplatinic acid electrodes for
DSSCs containing these redox mediators. Figure 5 shows
the J –V curves of DSSCs using thermally decomposed
chloroplatinic acid (labeled in the figure as Pt) and FGS
counter electrodes: (a) N719 dye with iodine-based medi-
ator, (b) D35 dye with cobalt-based mediator, and (c) D35
Fig. 5. Photocurrent density–voltage (J –V  curves of DSSCs using
dye with sulfur-based mediator. The FGS electrode-based thermally decomposed chloroplatinic acid (here labeled as Pt) and func-
DSSCs showed PCEs of 6.8%, 4.5%, and 3.5% with the tionalized graphene sheet (FGS) as counter electrode. (a) N719 dye with
iodine, cobalt, and sulfur-based redox mediators, respec- iodine-based mediator electrolyte, (b) D35 dye with cobalt-based medi-
tively, which were equal to or greater than that of ther- ator electrolyte, and (c) D35 dye with sulfur-based mediator electrolyte.
Active area is 0.25 cm2 . Reprinted with permission from [163], J. D. Roy-
mally decomposed chloroplatinic acid electrodes for the Mayhew, et al., Functionalized graphene sheets as a versatile replacement
same three redox mediators, again, each one respectively. for platinum in dye-sensitized solar cells. ACS Appl. Mater. Interfaces
This study indicated that FGS/ethyl cellulose paste is a 4, 2794–2800 (2012). © 2012, American Chemical Society.
better replacement for Pt pastes in DSSCs.
To create optical transparency, Velten et al.164 applied change. The enhancement in electrolyte transparency low-
FLG nanoribbons either to counter electrodes or to an ered JSC from 17.6 mA/cm2 to 14.2 mA/cm2 , while the
electrolyte solution of iodide/triiodide redox couple with open VOC remained unchanged and FF increased from
N719 dye in the DSSC. The PCE of a DSSC device 45% to 55%. On the other hand, when FLG nanorib-
using FLG nanoribbons as the counter electrode did not bons were used in the electrolyte, the PCE increased from

1874 Sci. Adv. Mater., 7, 1863–1912, 2015

Singh and Nalwa
5.75% to 7.01% for DSSC devices due to the increase
of JSC from 9.9 mA/cm2 to 12.1 mA/cm2 , showing that
graphene ribbons can be used as an additive material
in the electrolyte. This electrolyte bleaching effect can
be used to improve performance of inverted and tandem
DSSCs. Chemical doping has been used to enhance the
PCE of graphene-based solar cells. Xue et al.165 used
nitrogen-doped graphene foam (N-GF), reduced graphene
oxide foam (rGOF), N-doped graphene (N-graphene),
and rGO films as counter electrodes for DSSCs. The
N-GF-based DSSC showed a PCE of 7.07%, similar to
the PCE of 7.44% for the Pt counter electrode. The
graphene foam-based counter electrodes exhibited higher
PCEs than spin-coated N-graphene and rGO films in the
I− /I− 166
3 redox couple with N719 dye. Luo et al. fabricated
DSSCs using nitrogen-doped and sulfur-doped reduced
GO (SRGO), as well as dual-doped reduced GO (NSRGO)
for a [Co(bpy)3]3+/2+ redox couple with N719 dye. PCEs
of 4.23% for SRGO and 4.73% for NSRGO counter elec-
trodes were measured and were higher compared with a Pt
electrode under similar conditions. Chang et al.167 used a
hybrid of graphene nanosheets (GNS) with graphene foam
(GF) as the counter electrode for DSSCs; it showed a PCE
of 7.70%, similar to that of a Pt electrode (PCE, 7.68%).
Porphyrin dyes have been explored for DSSCs. Mathew
et al.168 reported a PCE of 13%, a JSC of 18.1 mA cm−2 , a
VOC of 0.91 V, and a FF of 0.78 for a push–pull porphyrin-
based sensitizer coded SM315, and a PCE of 12% for
a SM371 sensitizer using a Co(II)/Co(III) redox media-
tor, a counter electrode made of graphene nanoplatelets,
and the working electrode was a 7 m–thick TiO2 film.
The push–pull porphyrin dyes, with a donor–-bridge
acceptor–type chemical structure, and the photovoltaic per-
formance of their DSSC devices are shown in Figure 6.
The current (J –V ) curves under AM 1.5G illumination as
well as incident photon-to-current efficiency (IPCE) spec-
trum evidence better performance for the SM315 sensi-
tizer than the SM371 dye. This study also indicated that
an iodide/triiodide redox mediator or Co(II)/Co(III) redox
mediator and push–pull porphyrin dye significantly influ-
ences the PCE of graphene-based DSSCs.
Both chemical functionaliztaion and physical forms
play an important role in DSSCs. Hua et al.169 used
stacked graphene platelet nanofibers (SGNF) for fabri-
cating DSSCs in the [Co(bpy)3]2+/3+ redox couple with
quinoxaline dye coded AQ308. The DSSC containing
0.2 mg mL−1 of SGNF showed a PCE of 9.81%. Cheng
et al.170 used graphene aerogels as a counter electrode for
DSSCs. The PCE of the DSSC was found to be depen-
dent on graphene aerogel film thickness. An 4.9 m-
thick graphene aerogel film showed a PCE 96% that of
a Pt electrode, while an 1.7 m-thick film loaded with
1 mol% Pt showed a PCE 98% that of a Pt electrode.
Ahn et al.171 prepared p-doped chemical vapor deposition
(CVD)–grown graphene nano-networks for DSSCs, which
Sci. Adv. Mater., 7, 1863–1912, 2015
Graphene-Based Dye-Sensitized Solar Cells: A Review
showed a PCE of 8.46%. This is a ∼6% improvement in
DSSCs using Pt as a reference electrode. Jeon et al.172
used edge-fluorinated graphene nanoplatelets (FGnPs) hav-
ing up to 3.4 wt% contents of fluorine as electrodes
for fabricating DSSCs and lithium-ion batteries. The
DSSCs containing FGnPs and Pt electrodes showed PCEs
of 10.1% and 9.61% in a [Co(bpy)3]2+/3+ redox cou-
ple with JK-306 dye (Fig. 7), respectively. A JSC of
14.05 mA cm−2 , VOC of 0.925 V, and FF of 0.458 yielded
a PCE of 5.96% observed for a hydrogenated graphene
nanoplatelets (HGnPs) counter electrode, much lower than
for the FGnPs electrode. A RCT of 852.4, 240  for
HGnPs, and 126.5, 42.23  for FGnPs were measured at
295.75 and 323.05 K, respectively, which was found to
decrease with increasing temperature. A cell resistance of
7.1  cm2 for FGnPs, 11.5  cm2 for Pt, and 183.5  cm2
for HGnPs counter electrodes show a faster kinetics for
[Co(bpy)3]2+/3+ reduction at the interface of FGnPs and
electrolytes compared with HGnPs and Pt. The DSSC fab-
ricated with the FGnPs electrode exhibited a higher PCE
than the Pt- and HGnPs-based electrodes. The FGnPs inher-
ited high charge polarization due to the high electronega-
tivity of fluorine, which contributes both to increased PCE
REVIEW
and to chemical stability. Das et al.173 also used fluorinated
graphene as a counter electrode in DSSCs, which showed
a PCE of 2.56% with 11 mA cm−2 current density. The flu-
orine groups contribute to higher PCE of graphene-based
DSSCs.
In another interesting study, Ju et al.174 used edge-
carboxylated graphene nanoplatelets (ECGnPs) as counter
electrodes in DSSCs for a [Co(bpy)3]2+/3+ redox couple
with JK-303 sensitizer (Fig. 7). The ECGnPs prepared
from graphite and dry ice using a ball milling method
were soluble in polar solvents because of the carboxylic
acids at the edges. The ECGnPs-based electrode exhibited
a lower RCT of 0.87  cm2 , compared with 2.19  cm2
for Pt, 2.63  cm2 for PEDOT:PSS, and 1.21  cm2 for
rGO counter electrodes. The DSSC showed PCE values of
9.31% for ECGnPs, 8.67% for Pt, 8.25% for PEDOT:PSS,
and 8.94% for rGO counter electrodes. It is evident that
the DSSC fabricated with an ECGnPs counter electrode
showed the highest PCE of the Pt, PEDOT:PSS, and rGo-
based electrodes.
The effect of thermal annealing on the PCE of DSSC
devices also has been studied. Jang et al.175 used graphene
nanosheets prepared by electrospray method for fabricat-
ing cathodes for DSSCs. The graphene nanosheets were
thermally annealed at 400  C for 4 h under argon; electri-
cal conductivity increased from 150 S/cm to 6000 S/cm,
a 40 times enhancement due to the removal of oxygen
functional groups from the surface. The PCE of thermally
annealed graphene nanosheets increased to 6.93% from
5.45% for the thermally untreated nanosheets; this is 95%
of the PCE of a Pt-based DSSC device. The FF of ther-
mally annealed graphene nanosheets was 69.7% compared
to 68.1% for a Pt counter electrode; the FF is correlated
1875
 Graphene-Based Dye-Sensitized Solar Cells: A Review Singh and Nalwa
REVIEW

Fig. 6. Chemical structures of push–pull porphyrin-based sensitizers coded as SM315, SM371. Both sensitizers have a porphyrin core and bis(2 ,4 -
bis(hexyloxy)-[1,1 -biphenyl]-4-yl)amine bulky donor, but the acceptor groups (R) are different. Redrawn and adapted from [168]. Photovoltaic perfor-
mance of DSSC devices fabricated with SM371 and SM315 dyes. J –V curves under AM 1.5G illumination and incident photon-to-current efficiency
(IPCE) spectrum of SM315 (black) and SM371 (red) dyes. Reprinted with permission from [168]. S. Mathew, et al., Dye-sensitized solar cells with
13% efficiency achieved through the molecular engineering of porphyrin sensitizers. Nature Chemistry 6, 242–247 (2014). © 2014, Nature Publishing
Group.

with internal series resistance. The RCT of 2.37  cm2 for
the thermally annealed graphene nanosheets was found to
be much lower than that of 4.07  cm2 for a Pt counter
electrode. In a similar experiment, the PCE of multi-walled
carbon nanotubes (MWCNTs) having 1 m film thickness
was found to be 85% of a Pt counter electrode. All these
studies demonstrate that DSSCs with graphene electrodes
perform better than or equally as well as conventional Pt
counter electrodes.
4.2. Graphene-Metal Composites for CEs
Graphene and graphene oxide composites with met-
als such as platinum (Pt), zinc oxide (ZnO), silver
nanowires, nickel oxide (NiO), NiS2 , CoS, MoS2 , TiN,
TaON, CdSe, tungsten (W), tungsten carbide (WC),
nickel phosphide, ruthenium oxide (RuO2 , tin sul-
fide (SnS2 , upconversion nanoparticles, ionic liquids,
carbon black, hemin, and polymers such as polypyrrole,
polythiophene, polyaniline, polystyrenesulfonate-doped

(JK-306 Dye) (JK-303 Dye)

Fig. 7. Chemical structures of JK-306 and JK-303 photosensitizers used in fabricating graphene-based DSSCs.

1876 Sci. Adv. Mater., 7, 1863–1912, 2015

Singh and Nalwa
poly(3,4-ethylenedioxythiophene) (PEDOT:PSS), poly(diallyl-
dimethylammonium chloride) (PDDA), polyethylene
oxide, and halide perovskites have been extensively stud-
ied. Table II lists JSC , VOC  FF, and PCE () of DSSCs
fabricated from graphene-based composites with a wide
variety of metals.176–210 Some important developments on
graphene materials-based DSSCs are discussed in detail
here. Li et al.176 used TaON nanoparticles and a reduced
graphene oxide (rGO) nanocomposite as a counter elec-
trode for [Co(bpy)3]3+/2+ (bpy = 2,2 -bipyridine)-mediated
DSSCs. The rGO–TaON nanocomposite demonstrated
higher electrocatalytic activity than that of TaON or rGO
alone. The rGO–TaON nanocomposite showed a PCE of
7.65% for the rGO–TaON counter electrode in a DSSC,
as well as electrochemical stability of the nanocomposite,
was much superior. In another study, the same research
team (Li et al.)177 used NiS2 nanoparticles in an rGO
nanocomposite (rGO/NiS2  counter electrode for reduction
of triiodide. Figure 8 shows (J –V ) curves of DSSCs with
NiS2 , NiS2 /RGO, RGO, and Pt counter electrodes under
simulated AM1.5 G light illumination (100 mW cm−2 .
DSSCs with the NiS2 /RGO composite counter electrode
yielded a highest PCE of 8.55%, whereas DSSCs with
NiS2 , rGO, and Pt counter electrodes under the same
conditions showed PCEs of 7.02%, 3.14%, and 8.15%,
respectively. The RCT for rGO, NiS2 , rGO/NiS2 , and Pt
were found to be 100.2  cm2 , 8.8  cm2 , 2.9  cm2 ,
and 0.5  cm2 , respectively. Here, the largest RCT for
rGO counter electrode pointed to its lowest catalytic
ability among all these counter electrodes. The NiS2 /rGO
nanocomposite with maximum PCE of 8.55% proves to be
an alternative to a conventional Pt counter electrode. Dao
et al.178 prepared nanohybrids of NiO nanoparticles and
rGO by dry plasma reduction The NiO/rGO nanohybrid
was used as an electrode for DSSCs, which showed the
PCE of 7.42%, comparable to the standard Pt counter
electrode (PCE, 8.18%). The electrochemical catalytic
activity of the NiO/rGO counter electrode was much
higher than the PCE of 1.53% for NiO nanoparticles,
4.48% for GO, and 5.18% for rGO. The charge transfer
resistance for the NiO/rGO nanocomposite was lower than
that of NiO nanoparticles and GO-based electrodes due to
a synergistic effect. Dao et al.179 prepared graphene-based
ruthenium oxide (RuO2  nanohybrid materials as a counter
electrode in DSSCs.
NiCu bimetallic nanoparticle-decorated graphene as
a counter electrode for DSSCs were used by Motlak
et al.180 The Ni-, Ni025 Cu075 -, Ni06 Cu04 - and Ni075 Cu025 -
decorated graphene were prepared by a hydrothermal
technique, which enhanced the catalytic activity toward
triiodide reduction and lower the resistance at the
electrolyte–counter electrode interface. Figure 9 shows
photocurrent density–voltage characteristics of DSSCs
with pristine graphene and NiCu bimetallic nanoparticle-
decorated graphene based counter electrodes. PCEs of
Sci. Adv. Mater., 7, 1863–1912, 2015
Graphene-Based Dye-Sensitized Solar Cells: A Review
1.72%, 2.39%, 1.24%, 2.87%, and 5.1% were measured
for pristine graphene, Ni-decorated graphene, Ni025 Cu075 -,
Ni06 Cu04 - and Ni075 Cu025 -decorated graphene, respec-
tively. The PCE of Ni075 Cu025 -decorated graphene was
found to be comparable with a Pt-based DSSC (PCE,
5.9%). The PCE of the Ni075 Cu025 -decorated graphene
counter electrode increased due to the lower RCT at the
interface of electrolyte and the NiCu bimetallic-graphene
film.
Metal nanoparticles and graphene composites have
attracted attention for DSSCs as well. Yang et al.181
used a nanocomposite of tin sulfide (SnS2  nanoparticles
with rGO in a DSSC by dispersing the SnS2 nanopar-
ticles onto graphene sheets, and made a comparison of
PCEs with different counter electrodes; PCEs of 7.12%,
5.58%, and 3.73% were measured for the SnS2 /rGO
nanocomposite, SnS2 nanoparticles, and graphene sheet
alone, respectively. The PCE of the SnS2 /rGO nanocom-
posite was slightly higher than that of a conventional Pt
counter electrode (6.79%). PCEs of 5.51%, 6.59%, 7.12%,
5.80%, 5.68%, and 5.27% were recorded for DSSCs
under AM1.5 illumination after annealing at 300  C,
350  C, 400  C, 450  C, 500  C, and 550  C, respec-
REVIEW
tively. PCE peaked at 400  C, and then started decreasing
at higher annealing temperatures. Dou et al.182 devel-
oped DSSCs with Ni12 P5 , Ni12 P5 /graphene, graphene, and
Pt counter electrodes. The DSSCs having Ni12 P5 and
graphene electrodes showed PCEs of 3.94% and 4.70%,
respectively, but PCE increased to 5.70% for a Ni12 P5
and graphene nanocomposite-based counter electrode. The
nanocomposite-based DSSC device is comparable to a
PCE of 6.08% for the Pt counter electrode. The RCT of
6.22  cm2 , 11.01  cm2 , and 17.41  cm2 for Ni12 P5 ,
Pt, and graphene electrodes, respectively, indicate bet-
ter electrocatalytic activity of the Ni12 P5 electrode than
that of the Pt counter electrode for the reduction of tri-
iodide ions. The graphene/Ni12P5 nanocomposite shows
a lower RCT of 4.93  cm2 . The impedance of the
graphene/Ni12P5 composite electrodes was found to be
much lower, yielding higher photovoltaic performance. Liu
et al.183 used a nanocomposite of molybdenum disulfide
(MoS2  and rGO as the counter electrode in DSSCs for
the reduction of triiodide (I− −
3  to iodide (I . The cur-
rent density of the MoS2 /rGO nanocomposite is higher
than those for MoS2 , rGO, and Pt-sputtered counter
electrodes as measured by cyclic voltammograms. The
MoS2 /rGO nanocomposite exhibited a RCT of 0.57  cm2
for the reduction of triiodide (I− 3 . The peak current den-
sities of MoS2 /rGO nanocomposites showed no degrada-
tion after 100 continuous cyclic voltammetry (CV) tests,
indicating a greater electrochemical stability, as well.
A PCE of 6.04% was measured for a DSSC with a
MoS2 /rGO nanocomposite counter electrode, which was
comparable to that of a conventional Pt counter electrode
(PCE, 6.38%).
1877
 Graphene-Based Dye-Sensitized Solar Cells: A Review Singh and Nalwa

Table II. Graphene-metal composites for DSSCs. Short-circuit photocurrent density (JSC ), open-circuit voltage (VOC ), fill factor (FF), and power
conversion efficiency (PCE, ), redox couples, and dyes used for fabricating DSSCs from composites of graphene or graphene oxide with metals and
their derivatives. The PCE of a DSSC with a standard Pt counter electrode is used as the reference electrode in a solar cell device.

Graphene-metal composites Redox couples Dye JSC (mA/cm2 ) VOC (V) FF (%) PCE (, %) Ref.
− −
Reduced graphene oxide (rGO) I /I 3 N719 1161 0747 262 227 [176]
Reduced graphene oxide (rGO)/TaON I− /I−
3 N719 1162 0775 381 343 [176]
TaON nanoparticles I− /I−
3 N719 783 0725 113 064 [176]
Pt reference I− /I−
3 N719 1308 0785 758 778 [176]
Reduced graphene oxide (rGO) I− /I−
3 N719 1098 0716 40 314 [177]
Reduced graphene oxide (rGO)/NiS2 I− /I−
3 N719 1655 0749 69 855 [177]
NiS2 only I− /I−
3 N719 1442 0738 66 702 [177]
Pt reference I− /I−
3 N719 1575 0739 70 815 [177]
Reduced graphene oxide (rGO) I− /I−
3 N719 1526 0767 4427 518 [178]
NiO nanoparticles/rGO nanohybrids I− /I−
3 N719 1557 0763 6240 742 [178]
Graphene oxide (GO) I− /I−
3 N719 1437 0775 4018 448 [178]
Pt-sputtered reference I− /I−
3 N719 1680 0763 6384 818 [178]
RuOa2 /reduced graphene oxide (rGO) I− /I−
3 N719 1613 0766 6733 832 [179]
RuO2 nanoparticles I− /I−
3 N719 1010 0760 3098 236 [179]
Pt reference I− /I−
3 N719 1701 078 6153 816 [179]
Ni-decorated graphene I− /I−
3 N719 1032 0547 420 239 [180]
Ni075 Cu025 -decorated graphene I− /I−
3 N719 1035 075 650 51 [180]
Pt reference I− /I−
3 N719 1612 0718 510 59 [180]
Pristine graphene I− /I−
3 N719 958 0431 420 172 [180]
SnS2 nanoparticlesb /reduced graphene oxide I− /I−
3 N719 1480 0718 6702 712 [181]
Reduced graphene oxide (rGO) I− /I−
N719 108 0661 5229 373 [181]
REVIEW

3
SnS2 only I− /I−
3 N719 136 0770 5328 558 [181]
Pt-sputtered reference I− /I−
3 N719 1400 0720 6736 679 [181]
Graphene/nickel phosphide (Ni12 P5 ) I− /I−
3 N719 1286 0727 61 570 [182]
Graphene I− /I−
3 N719 1288 0701 52 470 [182]
Nickel phosphide (Ni12 P5 ) I− /I−
3 N719 1224 0727 44 394 [182]
Pt reference I− /I−
3 N719 1312 0744 62 608 [182]
Graphene (1.2 wt.%)/ZnO hierarchically I− /I−
3 N719 1089 066 476 319 [184]
structured nanoparticle (HSN)
ZnO HSN only (3 m thickness) I− /I−3 N719 760 067 421 231 [184]
Hierarchically structured ZnO film I− /I−3 N3 109 067 481 351 [185]
Commercial ZnO film I− /I−3 N3 165 057 632 060 [185]
Graphene/ZnO nanoparticles bilayer I− /I−3 N719 175 05 456 398 [186]
ZnO nanoparticles I− /I−3 N719 113 045 473 240 [186]
Graphene nanosheets/ZnO nanorods – – 217 0765 67 812 [187]
CVD-Graphene oxide/ZnO nanorods I− /I−3 N719 656 0704 54 250 [188]
ZnO nanorods I− /I−3 N719 345 0591 58 118 [188]
Graphene nanoplatelets/Ag nanowire – – 645 055 52 161 [189]
Graphene nanosheets/Ag nanoparticles – – 1467 0732 72 772 [191]
CoS/graphene (60 wt%) composite I− /I−3 N719 1507 074 56 631 [192]
CoS only I− /I−3 N719 814 0743 58 351 [192]
Graphene only I− /I−3 N719 1366 0761 41 426 [192]
Pt reference I− /I−3 N719 1539 076 51 598 [192]
CoS-implanted graphene film I− /I−3 N719 128 072 364 342 [193]
Pristine graphene I− /I−3 N719 110 067 171 127 [193]
CoS/N-doped graphene I− /I−3 N749 2038 071 74 1071 [194]
Graphene/TiN composite I− /I−3 N719 1234 072 643 578 [195]
Nitrogen-doped graphene I− /I−3 N719 877 0641 5380 302 [195]
Graphene/Pt nanoparticles (27.43 wt%) I− /I−3 N3 667 074 59 291 [196]
Graphene I− /I−3 N3 394 062 42 101 [196]
Pt reference I− /I−3 N3 505 068 58 200 [196]
Graphene nanosheets/Pt monolayer I− /I−3 N719 1142 073 73 609 [197]
Graphene nanosheets (GNS) I− /I−3 N719 1064 071 25 185 [197]
Sputtered Pt I− /I−3 N719 1122 074 75 623 [197]
Microwave-exfoliated Graphene/Pt nanoparticles I− /I−3 N719 1275 074 71 669 [198]
Microwave-exfoliated Graphene (MEG) I− /I−3 N719 1316 069 50 449 [198]
Pt reference I− /I−3 N719 1209 073 70 629 [198]

1878 Sci. Adv. Mater., 7, 1863–1912, 2015

Singh and Nalwa Graphene-Based Dye-Sensitized Solar Cells: A Review

Table II. Continued.

Graphene-metal composites Redox couples Dye JSC (mA/cm2 ) VOC (V) FF (%) PCE (, %) Ref.
− −
Graphene nanosheets/Pt (20 wt%) I /I 3 N719 1588 0760 66 797 [199]
Graphene nanosheets/Pt (20 wt%, 400  C, 4 h) I− /I−
3 N719 1556 0830 69 891 [199]
Graphene nanosheets I− /I−
3 N719 1478 0770 39 444 [199]
Pt reference I− /I−
3 N719 1523 0830 70 885 [199]
Graphene nanosheets/Pt (20 wt%) I− /I−
3 – 1819 069 70 879 [200]
Graphene nanosheets/Pt (40 wt%) I− /I−
3 – 1720 070 70 831 [200]
Graphene nanosheets I− /I−
3 – 1708 070 64 765 [200]
Graphene nanosheets/Pt (1.6 wt%) I− /I−
3 N719 1125 0662 5231 389 [201]
Graphene nanosheets/Pt (2.4 wt%) I− /I−
3 N719 1116 0642 5198 372 [201]
Graphene nanosheets I− /I−
3 N719 802 0672 4852 261 [201]
Pt reference I− /I−
3 N719 1123 0672 5070 376 [201]
Graphene/Pt grids I− /I−
3 N719 287 043 32 040 [202]
Pt grids only I− /I−
3 N719 081 055 38 017 [202]
Graphene/Ni grids I− /I−
3 N719 133 033 57 025 [202]
Graphene/Ti grids I− /I−
3 N719 234 048 28 032 [202]
Graphene (25 wt%)/carbon black I− /I−
3 N719 1507 070 57 599 [203]
Graphene/carbon black (95 wt%) I− /I−
3 N719 1249 070 63 547 [203]
Pt reference I− /I−
3 N719 1335 070 65 609 [203]
Carbon/graphene nanocomposite [Co(bpy)3 ]3+/2+ – 760 084 77 969 [204]
Fe3 W3 C/WC/graphitic carbon (GC) hybrids I− /I−3 N719 130 074 73 710 [205]
WC/graphitic carbon (GC) hybrid I− /I−3 N719 1133 072 75 611 [205]
Graphitic carbon (GC) I− /I−3 N719 926 072 75 502 [205]
Pt reference I− /I−3 N719 140 073 73 749 [205]
Graphene/tungsten (50 wt%) composite I− /I−3 N719 1221 073 66 588 [206]

REVIEW
Graphene only I− /I−3 N719 1002 072 63 455 [206]
Tungsten only I− /I−3 N719 448 057 41 106 [206]
Pt reference I− /I−3 N719 1362 069 63 592 [206]
Hemin-functionalized reduced graphene oxidee I− /I−3 N719 575 065 31 245 [207]
Pt reference I− /I−3 N719 656 073 67 318 [207]
MoS2 /graphene flake (1.5 wt%) I− /I−3 N719 1241 071 68 598 [208]
Pt reference I− /I−3 N719 1243 075 67 623 [208]
Ni085 Se/reduced graphene oxide I− /I−3 N719 1520 078 66 782 [209]
Reduced graphene oxide (rGO) I− /I−3 N719 1281 077 41 404 [209]
Ni085 Se I− /I−3 N719 1320 076 68 682 [209]
Pt reference I− /I−3 N719 1480 076 67 754 [209]
Ta3 N5 /reduced graphene oxide I− /I−3 N719 1189 0762 318 288 [210]
Reduced graphene oxide (rGO) I− /I−3 N719 1162 0749 267 233 [210]
Ta3 N5 I− /I−3 N719 710 0714 126 064 [210]
Pt reference I− /I−3 N719 1318 0763 733 738 [210]

ZnO nanocrystalline materials with graphene also have
been used for DSSCs. Xu et al.184 used graphene scaf-
folds having ZnO hierarchically structured nanoparticle
(HSN) photoanodes for DSSCs. The 1.2 wt% graphene
incorporated into the ZnO photoanode exhibited a PCE
of 3.19%, which was increased by 38.09% compared
with a ZnO HSN photoanode (PCE, 2.31%). The high-
est PCE of 5.86% was measured for a 9 m–thick
graphene/ZnO photoanode-based DSSC device. The PCE
of a graphene/ZnO HSN photoanode was found to change
with different graphene loading and photoanode thickness.
Chou et al.185 also demonstrated a higher PCE of 3.51%
for the hierarchically structured ZnO film compared with
a PCE of 0.60% for a commercially obtained ZnO film.
Hsu et al.186 used graphene/ZnO nanoparticle composite
films for DSSCs, which showed a PCE of 3.98%. Chang
et al.187 fabricated DSSCs using graphene nanosheets/ZnO
nanorods as a counter electrode. The DSSC exhibited a
PCE of 8.12%, comparable to that of the conventional
Pt counter electrode (PCE, 8.82%). Ameen et al.188 used
vertically aligned ZnO nanorods on GO–coated FTO sub-
strates as photoanode for fabricating DSSC devices, where
a PCE of 2.5% was achieved due to the increase in surface
area of the photoanode assisted by higher loading of dye
molecules.
Silver nanomaterials and graphene hybrids also have
been used for DSSCs. Al-Mamun et al.189 prepared a
DSSC with a counter electrode made with silver nanowire
and graphene nanoplatelets (AgNW–GNPs). The DSSC
with AgNW–GNP electrode containing 0.88 g/cm2 GNP
loading showed a PCE of 1.61%, comparable to that of
a PCE of 1.87% for a standard Pt counter electrode. The
same research team190 used AgNW-GNP films for a cobalt
redox electrolyte in DSSCs. A lower RCT was observed
in the AgNW-GNP electrode compared to the Pt-based
counter electrode measured by electrochemical impedance

Sci. Adv. Mater., 7, 1863–1912, 2015 1879

 Graphene-Based Dye-Sensitized Solar Cells: A Review
Fig. 8. J –V curves of DSSCs with NiS2 , NiS2 /rGO, rGO, and
Pt counter electrodes under simulated AM 1.5G light illumination
(100 mW cm−2 . Reprinted with permission from [177], Z. Li, et al.,
NiS2 /reduced graphene oxide nanocomposites for efficient dye-sensitized
solar cells. J. Phys. Chem. C 117, 6561–6566 (2013). © 2013, American
Chemical Society.
spectroscopy (EIS). The DSSC showed a PCE of 2.44%
REVIEW
for the AgNW-GNP electrode compared to a PCE of
2.55% for the Pt-based electrode (PCE, 2.55%). Chang
et al.191 applied graphene sheets that incorporated a Ag
nanoparticles (Ag/GNs) composite as a counter electrode
for a DSSC, which exhibited a PCE of 7.72%.
Cobalt sulfide (CoS) and graphene composites have
been used as counter electrodes in the fabrication of
DSSCs. Wang et al.192 used a CoS/graphene hybrid-based
counter electrode in a DSSC. The composite counter elec-
trode was found to have high electrocatalytic activity
for iodine reduction, better than a Pt electrode. The CV
Fig. 9. J –V of DSSCs with pristine graphene (G) and NiCu bimetal-
lic nanoparticle-decorated graphene-based counter electrodes. Reprinted
with permission from [180], M. Motlak, et al., NiCu bimetallic
nanoparticle-decorated graphene as novel and cost-effective counter elec-
trode for dye-sensitized solar cells and electrocatalyst for methanol oxi-
dation. Appl. Catal. A 501, 41–47 (2015). © 2015, Elsevier.
1880
Singh and Nalwa
evidenced good stability after 100 continuous cycles for
the CoS/graphene electrode. The DSSC exhibited a PCE of
6.31% for the CoS/graphene composite counter electrode,
higher than that of a Pt electrode. Das et al.193 prepared
a DSSC from a CoS-implanted graphene (G-CoS) film
electrode. The G-CoS composite-based electrode showed
high electrocatalytic activity for iodine reduction with a
RCT of 5.05  cm2 and current density of 2.50 mA cm−2 .
The increased number of catalytic sites of G-CoS com-
posite and conducting path of graphene contributed to a
high PCE of 3.42% compared with 1.27% for a Pt counter
electrode. Bi et al.194 used a nitrogen-doped graphene/CoS
hybrid for a counter electrode of a DSSC device, which
showed a highest PCE of 10.71% on a PT-free counter
electrode. Graphene decorated with titanium nitride (TiN)
nanoparticles were used by Wen et al.195 for DSSCs for
an I−3 reduction, which had a PCE of 5.78% compared
with a PCE of 3.02% for a N-doped graphene film-based
electrode.
Using platinum (Pt) and graphene composites as counter
electrodes for DSSCs has attracted a great deal of atten-
tion. Bajpai et al.196 used FLG and Pt nanoparticles with
different Pt loadings as counter electrode in DSSCs. The
FLG/Pt composite with 27% Pt loading showed a PCE of
2.90%, which was 45% higher than a Pt thin film counter
electrode (2%). EIS evidenced a RCT of 2.36  cm2
for the FLG/Pt composite, in comparison to 7.73  cm2
for a standard Pt electrode, and 28.23  cm2 for a
graphene-based counter electrode. Gong et al.197 fabricated
DSSCs with a self-assembled graphene/Pt monolayer as
a counter electrode. The graphene nanosheets (GNS)/Pt
showed higher currents compared to a self-assembled Pt
monolayer, because graphene functions as a scaffold for
Pt nanoparticles; however, the GNS/Pt composite pro-
duced currents lower than sputtered Pt but comparable to
the drop-casted Pt. The DSSCs with drop-casted Pt and
sputtered Pt counter electrodes showed PCEs of 4.79%
and 6.23%, respectively. The PCE of an FTO electrode
was 0.13%, which increased to 1.85% after a graphene
monolayer was deposited on the FTO electrode. Further-
more, the PCE of the FTO/Pt electrode was 4.76%, which
was enhanced to 6.09% for the FTO/GNS/Pt compos-
ite film. Therefore, inclusion of graphene in a counter
electrode leads to higher PCE than drop-casted Pt, and
is comparable to sputtered Pt counter electrodes. When
TiO2 thick films were used in DSSCs, the monolayer
FTO/GNS/Pt composite electrode-based DSSC showed a
PCE of 7.66%, while the sputtered Pt electrode had a
PCE of 8.16%. The Pt loading was measured by an induc-
tively coupled plasma-atomic emission spectrometer (ICP-
AES), where Pt loading was found to be 308.9 g cm2
for sputtered Pt, 23.0 g cm2 for drop-casted Pt, and 0.3–
0.4 g cm2 for the FTO/Pt and FTO/GNS/Pt electrodes.
Both the self-assembled FTO/Pt and the FTO/GNS/Pt con-
sisting of smaller Pt amounts compared with sputtered
Sci. Adv. Mater., 7, 1863–1912, 2015
Singh and Nalwa Graphene-Based Dye-Sensitized Solar Cells: A Review

Pt and drop-casted Pt counter electrodes. Zhai et al.198
prepared composites of microwave-exfoliated graphene
(MEG) nanosheet with platinum nanoparticles (PtNPs)
using microwave exfoliation, ultra-sonication, and anneal-
ing processes. Figure 10 shows a schematic illustration for
preparing water-soluble, microwave-exfoliated graphene
nanosheet/platinum nanoparticles (MEG/PtNPs) compos-
ites, photographs of hydrophobic MEG flakes floating on
the deionized (DI) water, and water-soluble MEG/PtNPs
dispersed in the deionized water, a flexible MEG/PtNPs
composite film coated on ITO poly(ethylene naphthalate)
(PEN), FESEM, TEM, and HRTEM images of MEG flakes
and MEG/PtNPs composite nanosheet, electron diffrac-
tion pattern of MEG/PtNPs nanosheet, and an HRTEM
image of Pt nanoparticles. The flexible MEG/PtNPs com-
posite films are low-defect and show no cracks or defor-
mation under mechanical bending conditions. A RCT of
0.72  cm2 for PtNPs, 1.13  cm2 for MEG/PtNPs
composite film, and 14.29  cm2 for MEG counter elec-
trodes were measured. The MEG/PtNPs composite film
deposited on ITO/poly(ethylene naphthalate) (PEN) sub-
strates showed a PCE of 6.69%, higher than the PtNPs
counter electrode (PCE, 6.29%). MEG/PtNPs composite
film offers flexible and low-defect counter electrodes for
DSSCs. Kim et al.199 used graphene nanosheets (GNS) and
Pt nanoparticles as counter electrodes for DSSCs. Doping
of GNS with <10 wt% Pt nanoparticles enhanced elec-
trocatalytic activity of the DSSCs, which showed a PCE
of 8.91% for a GNS/Pt composite electrode after ther-
mal annealing at 400  C for 4 h under argon atmosphere,
compared with a PCE of 8.85% for a Pt counter elec-
trode. A RCT of 17,251  cm2 for GNS decreased to
2507  cm2 , 2,220  cm2 , 86  cm2 , and 27  cm2
after doping GNS with 1 wt%, 5 wt%, 10 wt%, and
20 wt% of Pt nanoparticles loading, respectively. The
sheet resistance of GNS was 7.36  cm2 . The 1 wt%

REVIEW

Fig. 10. (a) Schematic illustration for preparing water-soluble microwave-exfoliated graphene nanosheet/platinum nanoparticle (MEG/PtNPs) com-
posite; (b) photograph of MEG flakes floating on the deionized (DI) water (left) and water-soluble MEG/PtNPs dispersed in the DI water (right); (c)
flexible MEG/PtNPs composite film on ITO/poly(ethylene naphthalate) (PEN); (d) FESEM image of MEG flakes; (e) TEM image of MEG/PtNPs
composite nanosheet; (f) electron diffraction pattern of MEG/PtNPs nanosheet; (g) HRTEM image of Pt nanoparticles; (h) HRTEM image of graphene
(MEG/PtNPs nanosheet) where an inset is a fast Fourier transformation (FFT) pattern of square region; (i) inverse FFT of square region; (j) FESEM
image of MEG/PtNPs composite film; and (k) FESEM side-view of the MEG/PtNPs composite film. Reprinted with permission from [198], P. Zhai,
et al., Water-soluble microwave-exfoliated graphene nanosheet/platinum nanoparticle composite and its application in dye-sensitized solar cells. Elec-
trochim. Acta 132, 186–192 (2014). © 2014, Elsevier.

Sci. Adv. Mater., 7, 1863–1912, 2015 1881

 Graphene-Based Dye-Sensitized Solar Cells: A Review
loading of Pt nanoparticles yielded a sheet resistance of
6.17  cm2 , which increased to 6.37  cm2 , 6.82  cm2 ,
and 7.97  cm2 for 5 wt%, 10 wt%, and 20 wt% of
Pt nanoparticles loading, respectively. Yeh et al.200 used
different loading of Pt nanoparticles (10 wt%, 20 wt%,
40 wt%, 60 wt%) with pristine graphene (GN) for devel-
oping counter electrodes for DSSCs. The DSSCs with GN
showed a PCE of 7.65%, which was increased for a GN/Pt
nanocomposite to 8.79% with 20 wt% Pt nanoparticles
loading, which was even higher that sputtered Pt elec-
trode (PCE, 8.58%). PCEs of 8.17%, 8.31%, and 7.57%
for GN/Pt composite electrodes were observed for 10 wt%,
40 wt%, and 60 wt% loading of Pt nanoparticles, respec-
tively. The higher PCE of the GN/Pt composite electrode
having 20 wt% Pt nanoparticles is due to the higher elec-
trocatalytic activity for the triiodide ions (I−
3  reduction
and decreased charge transfer resistance at the interface
of the GN/Pt/electrolyte. Li et al.201 used graphene sheets
with 0.8 wt%, 1.6 wt%, and 2.4 wt% Pt nanoparticles
loading as counter electrodes for DSSCs. The graphene/Pt
composites electrodes showed PCEs of 3.71%, 3.89%, and
3.71% for 0.8 wt%, 1.6 wt%, and 2.4 wt% Pt loading,
REVIEW
respectively. The PCE started decreasing with the increase
of Pt loading to 2.4 wt% due to the aggregation of Pt
nanoparticles in the composite. At 1.6 wt% Pt loading, a
PCE of 3.89% for graphene/Pt composite is higher than
the PCE of 3.67% for the Pt film-based electrode. Dong
et al.202 used graphene on different metal grids as photo-
electrodes for DSSCs. The Pt grids were compared with
Ni grids and Ti grids with graphene. A PCE of 0.32%
for graphene/Ti grids, 0.25% for graphene/Ni grids, and
0.4% for graphene/Pt grids (without FTO or ITO supports)
was observed, compared to 0.17% for Pt grids alone. The
sheet resistance of graphene/Pt grids was found to be low:
∼3 /sq at 80% optical transparency.
Carbon-based materials, such as carbon black, acti-
vated carbon, and other forms of carbons have been
used for DSSCs. Miao et al.203 fabricated DSSCs with
crystalline graphene/carbon black composite counter elec-
trodes with a ratio of 1:3 wt% of graphene to car-
bon black. Six pastes of crystalline graphene and black
carbon with 5 wt% of polytetrafluoroethylene (PTFE)
having 0, 5%, 10%, 25%, 50%, and 95% graphene
weight ratio were prepared. PCEs of 5.04%, 5.54%,
5.99%, 5.28%, and 4.76% were recorded for 5 wt%,
10 wt%, 25 wt%, 50 wt%, and 95 wt% graphene
amounts with carbon black. The PCE optimized for the
25 wt% graphene/carbon black-based electrode and there-
after decreased with increasing graphene contents. Stefik
et al.204 reported a carbon-graphene composite prepared
from graphene nanoplatelets and poly(acrylonitrile). The
carbon/graphene nanocomposite had a RCT of ∼1  cm2
with 20 wt% graphene content, and DSSCs showed PCE
and fill factors comparable to Pt cathodes. Liao et al.205
used Fe3 W3 C/WC/graphitic carbon ternary hybrid-based
1882
Singh and Nalwa
DSSCs, which showed a PCE of 7.1% as counter elec-
trode. The PCE was found to be higher compared to
pure graphitic carbon (PCE, 5.02%) and WC/graphitic
carbon hybrids (PCE, 6.11%), indicating better catalytic
performance for Fe3 W3 C/WC/GC hybrid counter elec-
trodes. Munkhbayar et al.206 used graphene/tungsten (W)
nanocomposites as counter electrodes for DSSCs. Puri-
fied and ground graphene showed a PCE of 4.55%.
A graphene/W composite film had a PCE of 5.88%, sim-
ilar to that of a Pt counter electrode (PCE, 5.92%). Xu
et al.207 fabricated DSSCs with hemin-functionalized rGO
as a counter electrode. The carboxyl (COOH) groups of
hemin were covalently grafted to the graphene surface by
the amidation of the amino groups existing on the edges of
ethylene-diamine functionalized GO. A hemin/rGO com-
posite was used as a counter electrode in DSSCs; it exhib-
ited a PCE of 2.45%, which is 77% of a standard Pt
counter electrode under similar conditions.
Various types of metal derivatives with graphene have
been used for composite formation. Yue et al.208 used
molybdenum sulfide (MoS2 /graphene flake composite
film as counter electrode for DSSCs with N719 dye in a
I− /I−
3 redox couple. Electrocatalytic activity was found to
increase when graphene flakes were added to MoS2 film;
the current density of the MoS2 /graphene composite elec-
trode was higher than those of graphene, MoS2 , and Pt
counter electrodes owing to the lamellar structure. The RCT
of 3.98 W cm2 , 2.71  cm2 , 2.09  cm2 , and 2.01  cm2
were measured for graphene, MoS2 , MoS2 /graphene, and
Pt counter electrodes, respectively. Figure 11 shows
current density–voltage characteristics of DSSCs with
MoS2 /graphene counter electrodes in different thickness
and a comparison with a standard Pt counter electrode.
Fig. 11. J –V characteristics of DSSCs with MoS2 /graphene counter
electrodes in different thicknesses and a comparison with a standard Pt
counter electrode (PCE, 6.23%). Reprinted with permission from [208],
G. Yue, et al., A catalytic composite film of MoS2 /graphene flake as a
counter electrode for Pt-free dye-sensitized solar cells. Electrochim. Acta
85, 162–168 (2012). © 2012, Elsevier.
Sci. Adv. Mater., 7, 1863–1912, 2015
Singh and Nalwa
Both JSC and VOC increase with increasing plaster lay-
ers from 1 to 3, and thereafter decrease for 4 and 5 lay-
ers; therefore, the thickness of the MoS2 /graphene counter
electrode impacts the PCE of DSSCs. The MoS2 /graphene
counter electrode prepared by 3-layer plaster showed the
lowest RCT , indicating highest electrocatalytic activity. The
RCT of the MoS2 /graphene counter electrode decreased as
the graphene content increased from 0.5 wt% to 1.5 wt%.
When graphene content was increased to more than
2 wt%, the overall electrocatalytic activity decreased. The
MoS2 /graphene composite (1.5 wt% graphene) electrode
showed a RCT of 2.17  cm2 and a PCE of 5.98%, com-
parable to a PCE of 6.23% for a Pt electrode under AM1.5
illumination of 100 mW cm−2 . Liu et al.183 reported a
PCE of 6.04% for a MoS2 /rGO nanocomposite counter
electrode-based DSSC, comparable to a Pt counter elec-
trode (PCE, 6.38%). Zhang et al.209 used mesoporous
Ni085 Se nanospheres and rGO composite-based counter
electrodes for DSSCs. The low RCT of 0.39  cm2 for
the Ni085 Se/rGO composite electrode compared to those
of 1.76  cm2 for Ni085 Se, 0.90  cm2 for Pt, and
2.45  cm2 for rGO demonstrates higher electrocatalytic
activity for triiodide reduction. The PCE of 7.82% for
the Ni085 Se/rGO composite is higher compared to a PCE
of 7.54% for a Pt counter electrode. Both electrochem-
ical impedance spectra and CV supported positive syn-
ergetic effect between rGO and Ni085 Se, and the higher
charge transfer ability was comparable to the standard
Pt electrode. Li et al.210 used a rGO/Ta3 N5 composite
in organic dye 2-cyano-3-[5-(4-(diphenylamino)phenyl)-
3  3 ,4-tri-n-hexyl-[2 2 5  2 ]terthiophene] acrylic acid
(FNE29) for a [Co(bpy)3]3+/2+ mediated DSSC. The Ta3 N5
nanorods were incorporated on rGO nanosheets as a
counter electrode. The rGO/Ta3 N5 nanorods-based elec-
trode showed high electrical conductivity and a PCE of
7.85%, compared to a PCE of 7.59% for the Pt cath-
ode. The Ta3 N5 /rGO composite with I− /I− 3 redox couple in
N719 dye showed a PCE of 2.88%, lower than the PCE
of 7.38% for a Pt electrode under similar conditions. Bai
et al.211 used Cu2 ZnSnS4 /graphene composites as a counter
electrode in DSSCs, which showed a PCE of 7.81%, com-
pared to PCEs of 4.77% for Cu2 ZnSnS4 and 6.66% for
Pt counter electrodes. As evidenced here, a number of
factors have an impact on the photovoltaic performance
of DSSCs made of graphene composites with metals and
polymers, including the nature of materials used for pho-
toanode and counter electrodes, redox electrolytes, sensi-
tizing dyes, solar cell configuration; the ratio of contents;
thermal processing; the fabrication process, and molecular
interactions between electrodes and dyes.
4.3. Graphene-Carbon Nanotubes Composites for CEs
Carbon nanotubes (CNTs) are very interesting not only for
DSSCs but also other applications in the field of nanoelec-
tronics because of their high mechanical strength, optical
Sci. Adv. Mater., 7, 1863–1912, 2015
Graphene-Based Dye-Sensitized Solar Cells: A Review
transparency, electrical conductivity, high thermal stabil-
ity, and electrochemical activity. Platinum-free DSSCs are
of continued interest and therefore, CNTs-based materials
have been investigated as counter electrodes for DSSCs.
Hwang et al.212 reviewed the current status of CNTs as
counter electrodes in the fabrication of DSSC devices.
PCE values of CNT-based counter electrodes remain low
because the aggregation of CNTs restricts the charge-
transport process in the DSSCs. A synergetic approach of
coupling the unique properties of both graphene and CNTs
into a single composite system could induce better elec-
trocatalytic activity.
CNTs have been combined with graphene-based mate-
rials for constructing DSSCs. A large number of studies
have been conducted on DSSCs, where graphene/CNTs
composites were used as a photoanode. Table III summa-
rizes DSSCs based on graphene/CNTs composites using
photovoltaic performance. Photocurrent density (JSC ,
open-circuit voltage (VOC , fill factor (FF), and (PCE;
) are compared with a Pt electrode as the reference
cell.212–225 Some examples are worth mentioning here
to help evaluate how CNTs compare with graphene in
DSSCs. Li et al.213 used vertically aligned carbon nano-
REVIEW
tubes (VACNTs) grown by CVD on the flexible graphene
paper (GP) as a counter electrode for fabricating DSSCs.
The N719 dye in an electrolyte containing 0.6 M methyl-
hexylimidazolium iodide, 0.05 M iodine, 0.1 M LiI, and
0.5 M tert-butylpyridine in 3-methoxypropionitrile was
used. The bare GP electrode showed a rather low PCE of
1.50% but after coating a CNT layer on the GP paper,
PCE increased to 3.88% for the tangled carbon nano-
tubes (TCNTs)/GP film and 6.05% for the VACNT/GP
film. The PCE of the VACNT/GP film-based counter
electrode was 83% compared with the Pt film elec-
trode. The VACNT/GP films were mechanically strong
and flexible, as resistance increased by 3.3% after 10,000
bending cycles. Choi et al.214 prepared graphene on a
SiO2 /Si substrate and then multi-walled carbon nanotubes
(MWCNTs) were grown by CVD on top of graphene
to prepare electrodes for DSSCs. Choi et al.215 used
graphene-MWCNT composite as a counter electrode on a
DSSC by vertically aligning MWCNTs on graphene lay-
ers by the CVD process. The graphene-MWCNTs com-
posites showed a PCE of 3% in the iodide/triiodide
redox couple with N719 dye. Battumur et al.216 used a
composite of graphene nanosheet (40 wt%) and MWC-
NTs (60 wt%) as a counter electrode for a DSSC,
which exhibited a PCE of 4.0% in the iodide/triiodide
redox couple with N719 dye. The MWCNTs/graphene
nanosheets composites-based electrodes having 20 wt%,
40 wt%, 60 wt%, and 80 wt% graphene nanosheets con-
tent showed PCEs of 3.2%, 4.0%, 2.1%, and 1.6%, respec-
tively, compared to PCEs of 1% for graphene nanosheets,
3% for MWCNTs, and 5% for a Pt counter elec-
trode. Yeh et al.217 studied graphene nanopowder (GNP),
1883
 Graphene-Based Dye-Sensitized Solar Cells: A Review Singh and Nalwa

Table III. Graphene/carbon nanotubes (CNTs) composites-based counter electrodes used in DSSCs. Photocurrent density (JSC , open-circuit voltage
(VOC , fill factor (FF), and power conversion efficiency (PCE, ), redox couples, and dyes, used in fabricating DSSCs with graphene/CNTs composites
are summarized. The PCE of a DSSC with a standard Pt counter electrode is used as the reference electrode in a solar cell device.

Graphene/CNTs composites in DSSC Redox couples Dye JSC (mA/cm2 ) VOC (V) FF (%) PCE (, %) Ref.
− −
Graphene paper (GP) I /I 3 N719 1387 600 181 150 [213]
Vertically aligned carbon nanotubes/GP film I− /I−
3 N719 1424 680 624 605 [213]
Tangled carbon nanotubes/GP film I− /I−
3 N719 1368 616 461 388 [213]
Pt reference I− /I−
3 N719 1459 689 725 729 [213]
Graphene/MWCNT composite I− /I−
3 N719 895 072 70 446 [214]
Graphene based MWCNTs I− /I−
3 N719 560 076 70 30 [215]
Graphene nanoseet (40%)/MWCNT I− /I−
3 N719 88 077 58 40 [216]
MWCNTs I− /I−
3 N719 64 081 57 30 [216]
Graphene nanosheet I− /I−
3 N719 36 077 39 10 [216]
Pt reference I− /I−
3 N719 100 074 67 50 [216]
MWCNT/reduced graphene oxide nanoribbon I− /I−
3 YD2-o-C8 1687 070 59 691 [217]
Graphene nanopowder I− /I−
3 YD2-o-C8 1300 068 55 486 [217]
MWCNT I− /I−
3 YD2-o-C8 1571 066 57 593 [217]
Sputtered Pt reference I− /I−
3 YD2-o-C8 1769 069 60 726 [217]
MWCNT/graphene composite I− /I−
3 N719 1605 075 62 755 [219]
Graphene only I− /I−
3 N719 1309 075 47 464 [219]
MWCNT I− /I−
3 N719 1554 074 57 662 [219]
Pt reference I− /I−
3 N719 1627 079 69 880 [219]
Reduced graphene oxide nanoribbons (R-GONR) I− /I−
3 N719 1417 0729 32 331 [220]
R-GONR (16 wt%)/MWCNT hybrid I− /I−
3 N719 1673 0734 67 823 [220]
R-GONR (16 wt%)/MWCNT mixture I− /I−
3 N719 1428 0731 60 623 [220]
I− /I−
REVIEW

MWCNT 3 N719 1523 0727 55 609 [220]

Pt reference I− /I−
3 N719 1653 0731 63 761 [220]
RGO-functionalized MWCNT films (CF-rGO) I− /I−
3 N719 1525 068 51 529 [221]
GO-functionalized MWCNT films (CF-GO) I− /I−
3 N719 1554 068 29 315 [221]
Pt reference I− /I−
3 N719 1805 074 58 770 [221]
SWCNTs/reduced graphene oxide (80 wt%) I− /I−
3 N719 1281 086 76 837 [222]
SWCNTs I− /I−
3 N719 1456 075 71 775 [222]
Reduced graphene oxide I− /I−
3 N719 1282 078 72 719 [222]
Pt reference I− /I−
3 N719 1331 077 76 779 [222]
Graphene/SWCNTs composites I− /I−
3 N719 127 070 565 517 [223]
Graphene I− /I−
3 N719 131 070 636 587 [223]
SWCNTs I− /I−
3 N719 130 071 523 494 [223]
SWCNTs/graphene aerogels – – 2290 074 564 964 [224]
Pt reference – – 1775 077 548 756 [224]
Vertically aligned FWCNTs/graphene I− /I−3 N719 1783 071 65 82 [225]
Pt reference I− /I−3 N719 1386 072 64 64 [225]
VAFWCNTs/graphene on Ni foil I− /I−3 N719 923 072 59 34 [225]
Pt on ITO (flexible PEN substrate) I− /I−3 N719 794 071 60 39 [225]

MWCNTs, and MWCNT/reduced graphene oxide nanorib-
bon (MWCNT/rGONR) composites as counter electrode
materials for DSSCs using YD2-o-C8 porphyrin dye in
an iodide/triiodide (I− /I−
3  redox electrolyte. Figure 12
shows the chemical structure of YD2-o-C8 porphyrin dye
and photocurrent density versus voltage characteristics of
DSSCs having MWCNTs, GNP, and MWCNT/rGONR
composite-based counter electrodes. PCE was 6.91% for
the MWCNT/rGONR composite, 4.48% for bare graphene
nanopowder, and 5.93% for pristine MWCNT using
iodide/triiodide redox electrolyte with YD2-o-C8 por-
phyrin dye. A PCE of MWCNT/rGONR was found to be
comparable to a sputtered Pt counter electrode (7.26%).
The RCT of 2.13  cm2 , 1.63  cm2 , and 1.27  cm2
was observed for GNP, MWCNT, and MWCNT/rGONR
composites counter electrodes, respectively. The high JSC
value for MWCNT/rGONR composites may be due to
the higher number of electroactive sites and high sur-
face area for the triiodide reduction, leading to faster
dye regeneration. In another study, Zhu et al.218 studied
PCEs of graphene-MWCNT composites-based DSSCs by
varying the loading of MWCNT contents in the com-
posite between 20 to 80 wt%, where the maximum PCE
of 6.17% was recorded by a solar cell having a counter
electrode made of 60 wt% of MWCNTs and 40 wt%
of graphene loadings. Velten et al.219 used nanocompos-
ites of MWCNT sheets and graphene flakes as counter
electrodes in DSSCs and compared them with Pt counter
electrodes. The nanocomposite showed an improved PCE
of 7.55% over the 6.62% for MWCNTs alone or the
4.65% for graphene alone for the iodide/triiodide (I− /I−
3
redox reaction in a DSSC. The addition of graphene flakes

1884 Sci. Adv. Mater., 7, 1863–1912, 2015

Singh and Nalwa
Fig. 12. Redrawn chemical structure of YD2-o-C8 porphyrin photosensitizer (dye) and photocurrent density versus voltage characteristics of DSSCs
having multi-walled carbon nanotubes (MWCNTs), graphene nanopowder (GNP), and MWCNT/reduced graphene oxide nanoribbon (MWCNT/rGONR)
composites-based counter electrodes measured at AM 1.5G, 100 mW cm2 . Reprinted with permission from [217], M.-H. Yeh, et al., Multiwalled carbon
nanotube@reduced graphene oxide nanoribbon as the counter electrode for dye-sensitized solar cells. J. Phys. Chem. C 118, 16626–16634 (2014).
© 2014, American Chemical Society.
increased surface area and electrical conductivity of the
carbon MWCNTs and graphene flakes nanocomposite. The
fill factor of MWCNT/graphene composite was 62.7%,
higher than the 47.3% for graphene alone and the 57.6%
for dry spun carbon MWCNTs.
The hybrid materials of rGONR and MWCNTs as
counter electrodes were used by Yang et al.220 The partial-
unzipping method was used to form a bridged struc-
ture to rapidly transport electrons between rGONR and
MWCNTs. The DSSCs showed PCEs of 8.23%, 6.85%,
and 3.98% for hybrids having 16%, 55%, and 85%
wt% rGONR contents, respectively, indicating that PCEs
decreased with increasing rGONR wt%. The PCE of
DSSCs having a pure rGONR-based electrode was 3.31%,
and 6.09% for a pure CNTs electrode. As thickness of
the rGONR (16%)/CNT hybrid electrode increased from
50 nm to 1 m, the PCE values also increased from
2.55% to 8.22%. The optimal thickness for the highest
PCE of 8.23% was 500 nm for the rGONR (16%)/CNT
hybrid electrode. When rGONR and pure MWCNTs were
physically mixed in solution, the DSSC showed a PCE
of 6.23%, much lower than the rGONR (16 wt%)/CNT
hybrid counter electrode made by the unzipping method.
The rGONR (16% wt%)/CNT hybrid films were highly
flexible with excellent transparency (Fig. 13). The resis-
tance of flexible rGONR (16%)/CNT hybrid film on the
poly(ethylene naphthalate) (PEN) changed less than 2%
after bending for 1,000 cycles. The flexible hybrid films
showed a JSC of 5.20 mA cm−2 , VOC of 0.72 V, and fill
factor of 0.65, resulting in a PCE of 2.44% under AM
1.5 illumination when used as a counter electrode to fab-
ricate flexible DSSCs. Ma et al.221 used graphene oxide-
functionalized MWCNTs film as a counter electrode in
DSSCs where GO was used as a surfactant for the CNTs
colloidal dispersion. The CNTs have an outer diameter of
10 nm and about 5 walls. The rGO-functionalized CNT
films showed a PCE of 5.29%, which is 68.70% of a Pt
Sci. Adv. Mater., 7, 1863–1912, 2015
Graphene-Based Dye-Sensitized Solar Cells: A Review
counter electrode (PCE, 7.70%). The graphene films (GRs)
showed a JSC of 13.51 mA cm−2 , VOC of 0.48 V, and
fill factor of 0.2351, resulting in a PCE of 1.52%. The
PCE of a GO-functionalized, MWCNTs-based DSSC was
REVIEW
found to be 3.15%, much lower compared with a rGO-
functionalized MWCNT counter electrode-based DSSC,
which showed a PCE of 5.29%. The rGO enhanced electri-
cal conductivity, so the sheet resistance of rGO-MWCNTs
films was decreased, leading to a higher PCE value.
Like MWCNTs, the single-walled carbon nanotubes
(SWCNTs) and graphene nanocomposites have been
explored for DSSCs. Zheng et al.222 used nanocomposites
of gel-coated reduced graphene oxide (rGO) and SWC-
NTs as the counter electrode in a DSSC in iodide/triiodide
redox electrolyte with N719 dye. The rGO/SWCNT
nanocomposites were prepared through the gel forma-
tion in liquid polyethylene glycol (PEG) and thereafter
PEG removal by heating. The PEG gels of rGO/SWCNT
were coated on FTO substrate and composite films
Fig. 13. Photograph of a 50 nm–thick flexible R-GONR (16%)/
MWCNT composite film (labeled in the figure as R-GONR16% /CNT
hybrid film on the poly(ethylene naphthalate) (PEN) substrate (left). Pho-
tographs of a glass slide and a glass slide with 50-nm-thick R-GONR
(16%)/CNT hybrid film a paper marked with the logo of Fudan Univer-
sity (Shanghai, China) (right). Reprinted with permission from [220], Z.
Yang, et al., Carbon nanotubes bridged with graphene nanoribbons and
their use in high-efficiency dye-sensitized solar cells. Angew. Chem. Int.
Ed. 52, 3996–3999 (2013). © 2013, Wiley-VCH.
1885
 Graphene-Based Dye-Sensitized Solar Cells: A Review
were obtained after heating at 430  C for 5 min. The
rGO/SWCNT, SWCNTs, rGO, and Pt on FTO glass were
used as counter electrodes in DSSCs. The photovoltaic
properties of RGO/SWCNT composites with 5 wt%,
10 wt%, 20 wt%, 30 wt%, 40 wt%, 60 wt% and 80 wt%
SWCNT loadings were compared. Figure 14 shows cur-
rent density–voltage characteristics of DSSCs with a rGO
(80 wt%)/SWCNT (20 wt%) composite, its SEM image,
and comparison with Pt counter electrodes after 7 days of
storing. The DSSC having a 80 wt% rGO/20 wt% SWC-
NTs composite showed the highest PCE of 8.37%, higher
than PCE of 7.79% for the control Pt counter electrode.
The VOC value showed an increase from 0.86 V to 0.90 V
after seven days. The rGO, having a large surface area,
contributed to high electrocatalytic activity, and SWCNTs
yielded high electrical conductivity for the nanocompos-
ites. The DSSC with iodide/triiodide electrolyte had both
higher VOC and PCE.
Graphene and SWCNTs composites for DSSCs were
studied by Kim et al.223 The optical transmittance of
62% for graphene, 70% for SWCNTs, and 67% for
graphene/SWCNTs composite electrodes were observed at
550 nm. The graphene, SWCNTs, and graphene/SWCNTs
REVIEW
composite-based counter electrodes showed charge trans-
fer resistances of 16.2  cm2 , 35.3  cm2 , and 17.6  cm2
with electrolytes, and PCEs of 5.87%, 4.94%, and 5.17%,
respectively. Ma et al.224 used SWCNT/graphene aero-
gels as a Pt-free transparent counter electrode for DSSCs,
which showed a PCE of 8.31%, compared to 7.56% for the
platinum electrode. A PCE of 9.64% was recorded when
assisted by a mirror. The high PCE could be due to high
electrocatalytic activity and electrical conductivity induced
by the SWCNTs and the catalytic activity of graphene.
Dong et al.225 used covalently bonded, vertically aligned
few-walled carbon nanotubes (VAFWCNTs)/graphene on
Ni foil as an electrode for a DSSC with N719 dye.
The series resistance of VAFWCNTs/graphene/Ni cathode
was 23 , compared to 24.5  for a Pt cathode. The
charge transfer resistance of 0.91  cm2 for VAFWC-
NTs/graphene/Ni was 20 times lower than that of the Pt
(a) rGO+SWCNTS (b)
Fig. 14. J –V characteristics of DSSCs with a rGO (80 wt%)/SWCNT (20 wt%) composite and its SEM image, and comparison with Pt counter
electrodes after 7 days of storing. The variations of JSC , JOC , FF, and PCE of DSSCs with different SWCNT loadings in the composites. Reprinted with
permission from [222], H. Zheng, et al., Highly efficient iodide/triiodide dye-sensitized solar cells with gel-coated reduced graphene oxide/single-walled
carbon nanotube composites as the counter electrode exhibiting an open-circuit voltage of 0.90 V. ACS Appl. Mater. Interfaces 5, 6657–6664 (2013).
© 2013, American Chemical Society.
1886
Singh and Nalwa
cathode (19.6  cm2 , indicating a faster electron transfer
at the interface of cathode and electrolyte. The VAFWC-
NTs/graphene/Ni cathode-based DSSC is mechanically
flexible, which showed a PCE of 3.9%, and which was
higher than a flexible DSSC based on a Pt/ITO/PEN cath-
ode (3.4%); this is inconsistent with lower charge-transfer
resistance. The VAFWCNTs/graphene/Ni cathode having
100–150 m length exhibited a PCE of 8.2%, much higher
than that of a sputtered Pt cathode in a rigid DSSC.
4.4. Graphene-Polymer Composites for CEs
The nanocomposites of graphene with -conjugated
polymers such as polypyrrole, polyaniline, and poly(3-
alkylthiophene) also have been explored as counter elec-
trodes in DSSCs. Chen et al.226 used graphene quantum
dots (GQDs) to dope polypyrrole film on FTO glass to
develop counter electrodes for DSSCs. The GQD-doped
polypyrrole films had a more porous structure than did
simple polypyrrole film. Figure 15 shows current density–
voltage characteristics of DSSCs based on standard Pt,
polypyrrole (PPy), and different concentrations GQDs
ratios (3%, 10%, 15%, 20%, 25%, and 30%) as counter
electrodes under AM 1.5G light illumination of 100 mW
cm−2 and under dark conditions, PCEs as a function of
GQDs ratio for GQDs-doped PPy, and IPCE spectrum
of DSSCs with polypyrrole and GQDs (10%)-doped PPy
counter electrodes. PCE values increased with increasing
GQDs concentration up to 10% and thereafter decreased
with higher GQDs content. The GQD-doped polypyrrole
film-based counter electrode exhibited a PCE of 5.27% for
DSSCs with 10% doping, which is 20% higher than that
of pure polypyrrole film (PCE, 4.46%) but slightly lower
than that of Pt counter electrode-based DSSCs. The cat-
alytic activity of the GQD/polypyrrole counter electrode
was comparable to that of standard Pt counter electrodes.
The nanocomposites of polypyrrole/reduced graphene
oxide (PPy/rGO) were synthesized by Liu et al.227 for CV
measurements, where composites showed better catalytic
performance for triiodide reduction. A PCE of 6.45% was
measured for the PPy/rGO-based DSSC. A plastic counter
Sci. Adv. Mater., 7, 1863–1912, 2015
Singh and Nalwa Graphene-Based Dye-Sensitized Solar Cells: A Review

REVIEW
Fig. 15. Current density (I ) and voltage (V ) characteristics of DSSCs based on standard Pt, polypyrrole (PPy), and different concentrations of graphene
quantum dots (GQDs) ratio (3%, 10%, 15%, 20%, 25%, and 30%) as counter electrodes (a) under AM1.5G light illumination of 100 mW cm−2 ,
(c) under dark conditions, (b) PCEs as a function of GQDs ratio for GQDs-doped PPy, and (d) IPCE spectrum of DSSCs with polypyrrole and
GQDs (10%)-doped PPy counter electrodes. Reprinted with permission from [226], L. Chen, et al., Graphene quantum-dot-doped polypyrrole counter
electrode for high-performance dye-sensitized solar cells. ACS Appl. Mater. Interfaces 5, 2047–2052 (2013). © 2013, American Chemical Society.

electrode with PPy/rGO composites exhibited a PCE of
4.25%, which was comparable to that of a Pt counter
electrode (4.83%). Lim et al.228 incorporated polypyrrole
nanoparticles into rGO sheets by electrochemical polymer-
ization on an ITO surface. The DSSC fabricated from a
rGO/polypyrrole nanocomposite-based electrode showed a
PCE of 2.21%, comparable to a PCE of 2.19% for a sput-
tered Pt counter electrode. The PCE of rGO/polypyrrole
nanocomposites changed as a function of deposition time;
PCEs of 0.85%, 1.06%, 2.21%, 1.15%, and 0.39% were
observed for deposition times of 10, 50, 100, 250, and
500 seconds, respectively. A RCT of 14.8  cm2 for
rGO/polypyrrole electrode and a RCT of 14.3  cm2 for
a sputtered Pt electrode was measured, showing identi-
cal electrocatalytic activities for the triiodide reduction.
Ramasamy et al.229 prepared rGO/polypyrrole composites
by in situ polymerization and then poly(3,4 ethylene-
dioxythiophene) (PEDOT) was electrodeposited on this
composite. The rGO/polypyrrole/PEDOT was used as
counter electrode in DSSCs, which demonstrated a
PCE of 7.1%, comparable to a Pt counter electrode
under similar conditions. Bora et al.230 prepared a poly-
thiophene/graphene composite by liquid/liquid interfacial
polymerization as a counter electrode for DSSCs, which
showed a PCE of 4.8%, comparable to that of a Pt counter
electrode.
In another study, He et al.231 used a polyaniline (PANi)
and graphene complex as the counter electrode in DSSCs,
where a PCE of 7.70% was recorded from DSSCs con-
taining counter electrodes of polyaniline with 8 wt%
graphene compared to 6.40% for a pure polyaniline
counter electrode. The RCT of 18.97  cm2 for the
PANi/graphene (8 wt%) complex electrode was found to
be five times smaller compared with the RCT of 92.91 
cm2 for the pure PANi electrode from EIS measure-
ments. PCEs of 6.93%, 7.25%, and 7.70%, and RCT val-
ues of 36.56  cm2 , 18.56  cm2 , and 11.49  cm2
for PANi-graphene (1 wt%), PANi-graphene (4 wt%),

Sci. Adv. Mater., 7, 1863–1912, 2015 1887

 Graphene-Based Dye-Sensitized Solar Cells: A Review Singh and Nalwa

and PANi-graphene (8 wt%) counter electrodes, respec-
tively, were recorded, showing an increasing order with
increased graphene concentration. In another study, He
et al.232 fabricated DSSCs using a PANi and graphene
complex as counter electrodes. Figure 16 shows SEM pho-
tographs of pure PANi and PANi-8 wt% graphene com-
plex counter electrodes, Nyquist plots, corresponding EIS
data, and EIS plots and J –V curves of DSSCs from pure
PANi and PANi-graphene complex counter electrodes.
The SEM shows compact aggregations for PANi due to
strong hydrogen bonding but a porous structure for PANi-8
wt% graphene complex, which allows increased electrolyte
loading and the easy migration of iodide/triiodide redox
couples. The PANi chains are attached on the graphene
surface by the covalent bonding. The easy electron trans-
fer from graphene to polyaniline by covalent bonds facili-
tates the enhancement of electrocatalytic and photovoltaic
activities. The Nyquist plots indicate impedance character-
istics for standard Pt, pure PANi, and PANi-graphene com-
plex counter electrodes. The RCT values of 4.96  cm2 ,
188.80  cm2 , and 13.0  cm2 for PANi-8 wt% graphene
REVIEW
complex, PANi, and Pt counter electrodes, respectively,
were measured from EIS method. The lowest RCT value
of PANi-8 wt% graphene complex indicates the highest
triiodide reduction due to increased electrocatalytic activ-
ity. The optimum PCE of 7.78% was recorded for the
PANi-8 wt% graphene complex, which is much higher
compared to PCE values of 6.24% for a pure polyani-
line and 6.52% for Pt counter electrode. The PANi-
graphene complex formation is an effective strategy for
enhancing both charge transfer and the efficiency of
DSSCs.
DSSCs were fabricated using polyaniline–single-walled
nanotube (PANi–SWCNT) complexes by He et al.233 A
DSSC with PANi-4 wt% SWCNT complex electrodes
showed a PCE of 7.81%, compared to a PCE of 6.24%
for a pure PANi electrode. PCE values were 6.70%,
7.07%, and 7.81% for 1 wt%, 2 wt%, and 4 wt%
SWCNT amounts, respectively; therefore, PCE increased
with increasing SWCNT contents in the complex. The RCT
values were 171  cm2 , 61.93  cm2 , 51.71  cm2 ,
and 38.68  cm2 for PANi, PANi-1 wt% SWCNT,

Fig. 16. SEM photographs of (a) pure PANi, and (b) PANi-8 wt% graphene complex counter electrodes. (c) Nyquist plots indicate impedance
characteristics for standard Pt, pure PANi, and PANi-graphene complex counter electrodes. The corresponding EIS data and EIS plots are shown.
(d) J –V curves of DSSCs from pure PANi and PANi-graphene complex counter electrodes. Reprinted with permission from [232], B. He, et al., Robust
polyaniline-graphene complex counter electrodes for efficient dye-sensitized solar cells. ACS Appl. Mater. Interfaces 6, 8230–8236 (2014). © 2014,
American Chemical Society.

1888 Sci. Adv. Mater., 7, 1863–1912, 2015

Singh and Nalwa
PANi-2 wt% SWCNT, and PANi-4 wt% SWCNT com-
plexes, respectively. From the same research group,
Wang et al.234 used polyaniline-SWCNT/GO multilay-
ers as counter electrodes in DSSCs. The (PANi-4 wt%
SWCNTs/GO)5 multilayer-based electrodes showed a PCE
of 6.88%. The PCE values were dependent on the SWCNT
contents as well as on the bilayer number. The PCEs of
DSSCs with a (PANi-SWCNT/GO)n multilayer, where n
is 1, 3, and 5 bilayers, were 1.58%, 3.91%, and 6.88%,
respectively. PCEs of 4.28%, 5.38%, and 6.88% were
measured for 1 wt%, 2 wt%, and 4 wt% SWCNT con-
tents, respectively, compared to a PCE of 2.55% for
the (PANi/GO)5 electrode. The covalent bonding between
SWCNTs (–C ) and PANi (–NH–) contributes to rapid
charge transfer.
Wang et al.235 also used polyaniline-graphene com-
plex/graphene oxide (PANi-G/GO)n (where n is the num-
ber of bilayers) multilayers as counter electrodes. The
catalytic activity of DSSCs with multilayer electrodes
was found to increase with the number of bilayers and
graphene content. The (PANi-10 wt% G/GO)10 , (PANi-
8 wt% G/GO)10 , and (PANi-4 wt% G/GO)10 multilayer-
based DSSCs showed optimized PCE values of 7.88%,
7.83%, and 6.38%, respectively, and 6.13% for a stan-
dard Pt counter electrode. The (PANi-10 wt% G/GO)5 ,
(PANi-8 wt% G/GO)5 , and (PANi-4 wt% G/GO)5 mul-
tilayer electrodes showed RCT values of 116.6  cm2 ,
118.5  cm2 , and 358.2  cm2 , and PCEs of 6.61%,
6.03%, and 4.21%, respectively. The PCE values of DSSCs
increased with the increasing number of bilayers and
graphene content in counter electrodes. The layer-by-layer
self-assembly is a very attractive strategy for preparing
(PANi-G/GO)n counter electrodes with high PCEs for
increasing triiodide reduction. Yang et al.236 assembled
a multi-interfacial polyaniline-graphene/Pt (PANi-G/Pt)n
counter electrode using a layer-by-layer method for DSSCs
with various deposition cycles (n = 1, 3, 5, 7, and 9) to
examine the effect on electrocatalytic activity. The DSSC
device with a (PANi-10 wt% G/Pt)9 electrode showed a
PCE of 7.45% for triiodide (I− 3  reduction. In compari-
son, PCEs were 6.48% for (PANi-4wt%G/Pt)9 and 6.65%
for (PANi-8 wt%G/Pt)9 multilayer counter electrodes. The
PCE values of 2.58%, 4.99%, 5.63%, 6.29%, and 7.45%,
and RCT values of 4938  cm2 , 985.9  cm2 , 290  cm2 ,
205.5  cm2 , and 136.3  cm2 were measured for 1, 3,
5, 7, and 9 deposition cycles, respectively; therefore, PCE
increased and RCT decreased with the increasing number of
deposition cycles. The complex formation between PANi
and graphene helps in accelerating the electron migration
from graphene to polyaniline, and the inclusion of Pt in
a PANi-G complex provides more interfaces for triiodide
reduction. Chen et al.237 used a composite film of PEDOT
and nitrogen-doped graphene as a counter electrode for a
DSSC. The DSSC made of a composite counter electrode
showed a PCE of 8.30%, whereas a DSSC with a standard
Sci. Adv. Mater., 7, 1863–1912, 2015
Graphene-Based Dye-Sensitized Solar Cells: A Review
Pt counter electrode had a PCE of 8.17% for front-side
illumination.
Porous PANi/rGO hybrids using MnO2 for polymer-
ization of aniline (M-PANi/rGO) were developed by Sun
et al.238 and then compared with PANi/rGO hybrids
synthesized via conventional polymerization method (C-
PANi/rGO). The DSSCs with C-PANi/rGO hybrids
showed a current density (JSC  of 11.64 mA cm−2 and
a PCE of 5.62%, compared to a JSC of 12.88 mA cm−2
and a PCE of 6.15% for M-PANI/rGO hybrids, and a
PCE of 6.73% for a Pt counter electrode. This indicates
that a hierarchically porous M-PANI/rGO hybrid-based
electrode has comparable efficiency to Pt as a counter
electrode for DSSCs. Lee et al.239 fabricated poly(3,4-
ethylenedioxythiophene) (PEDOT)/graphene counter elec-
trodes on a flexible PET substrate. The PEDOT, graphene,
and graphene/PEDOT films showed a sheet resistance
of 141 /sq, 60 /sq, and 62 /sq, respectively.
The PCE values were 6.68% for Pt, 5.62% for pure
PEDOT, and 6.26% for graphene/PEDOT counter elec-
trodes. The optical transparency of a graphene/PEDOT-
based DSSC was over 70% at 550 nm, similar to a
Pt-based DSSC. Hong et al.240 prepared counter electrodes
REVIEW
from graphene and poly(styreneslufonate)–doped poly(3,4-
ethylenedioxythiophene) (PEDOT:PSS) composite films.
The graphene/PEDOT–PSS films were deposited on ITO
substrates as counter electrodes of DSSCs. A 60 nm–
thick graphene/PEDOT:PSS composite film containing
1 wt% graphene showed >80% transmittance at visible
wavelengths and a PCE of 4.5% for 1 wt% graphene
under irradiation of 100 mW AM1.5 white light, in
comparison to a PCE of 6.3% for a Pt counter elec-
trode for triiodide reduction with N719 dye. The PCE
of a graphene/PEDOT:PSS-based electrode increased from
2.3% to 4.5% as the graphene content in the compos-
ite increased from 0 wt% to 1 wt%. The cyclic voltam-
mograms for graphene/PEDOT:PSS, PEDOT:PSS, and Pt
counter electrodes were recorded, where the cyclic voltam-
mograms were similar for graphene/PEDOT:PSS and for
Pt electrodes. The redox current density of I2 = I−
3 at the
graphene/PEDOT:PSS electrode was noted to be much
higher compared to the PEDOT:PSS electrode, which
demonstrated that the graphene-containing electrode had
stronger electrocatalytic activity.
DSSCs using electrolyte Z946 and ionic liquid
electrolyte Z952 in a C106TBA sensitizer from
poly(diallyldimethylammonium chloride) (PDDA) and
electrochemically reduced graphene oxide (ERGO)
[PDDA/ERGO]11 deposited multilayer (number of layers
is 11) onto ITO glass as counter electrode were devel-
oped by Xu et al.241 and thereafter compared with elec-
trolyte Z946 with Pt/FTO counter electrode in a C106TBA
sensitizer. The [PDDA/ERGO]11 /ITO electrode with elec-
trolyte Z946 showed a PCE of 9.54% while the control
DSSC device using platinized FTO glass counter elec-
trode had a PCE of 9.14% under similar experimental
1889
 Graphene-Based Dye-Sensitized Solar Cells: A Review Singh and Nalwa

conditions. The [PDDA/ERGO]11 /ITO electrode with elec-
trolyte Z952 showed a PCE of 7.66%. The DSSCs with
graphene in solvent-free ionic liquid electrolytes exhibited
high photovoltaic performance. The electron-withdrawing
character of PDDA enhanced the electrocatalytic activi-
ties. Table IV summarizes the short-circuit photocurrent
density (JSC , open-circuit voltage (VOC , fill factor (FF),
and power conversion efficiency (PCE, ), redox cou-
ples, and molecular dyes used for fabricating DSSCs
from graphene-polymer composites-based counter elec-
trodes. The PCE of a DSSC with a standard Pt counter
electrode is used as the reference electrode in a solar cell
device. The graphene/polymer composite shows excellent
potential to replace conventional Pt counter electrodes in
DSSCs.
4.5. Effect of Heteroatom Doping on
Graphene-Based CEs
The effect of chemical doping on the PCE of graphene-
based DSSCs has been reported by several research
groups. Heteroatom chemical doping increases the elec-
trical conductivity, charge transfer, and PCE of DSSCs.
Ju et al.154 reported enhancement of PCE for N-doped
graphene nanoplatelets (N-GNPs) as counter electrode in

Table IV. Short-circuit photocurrent density (JSC , open-circuit voltage (VOC , fill factor (FF), and power conversion efficiency (PCE, ), redox
couples, and dyes used for fabricating DSSCs from graphene-polymer composites-based counter electrodes. The PCE of a DSSC with a standard Pt
counter electrode is used as the reference electrode in a solar cell device.

Graphene-polymer composites Redox couples Dye JSC (mA/cm2  VOC (V) FF (%) PCE (, %) Ref.
− −
Polypyrrole/graphene quantum dots (10%) I /I 3 N719 1436 0732 508 527 [226]
Polypyrrole I− /I−
3 N719 1283 0715 486 446 [226]
Pt reference I− /I−
3 N719 1281 0696 675 602 [226]
Polypyrrole/reduced graphene oxide (rGO) I− /I−
3 N719 1548 0695 60 645 [227]
Polypyrrole only I− /I−
N719 1354 0685 50 464 [227]
REVIEW

3
Pt reference I− /I−
3 N719 1545 0700 66 714 [227]
Polypyrrole/reduced graphene oxide (rGO) I− /I−
3 N719 749 070 42 221 [228]
Sputtered Pt reference I− /I−
3 N719 512 071 60 219 [228]
Polyaniline/graphene (8 wt%) I− /I−
3 N719 1655 0699 067 770 [231]
Polyaniline/graphene (4 wt%) I− /I−
3 N719 1573 0708 065 725 [231]
Polyaniline (PANi) I− /I−
3 N719 1521 0678 062 640 [231]
Polyaniline/graphene (1 wt%) complex I− /I−
3 N719 1384 0726 067 671 [232]
Polyaniline/graphene (8 wt%) complex I− /I−
3 N719 1485 0737 071 778 [232]
Polyaniline/graphene (15 wt%) complex I− /I−
3 N719 1497 0712 065 689 [232]
Polyaniline (PANi) I− /I−
3 N719 1196 0712 073 624 [232]
Pt reference I− /I−
3 N719 1393 0714 066 652 [232]
Polyaniline (PANi) I− /I−
3 N719 1196 0712 073 624 [233]
Polyaniline-4 wt% SWCNT complex I− /I−
3 N719 1488 0734 071 781 [233]
(Polyaniline-SWCNT/GO)1 multilayer I− /I−
3 N719 1068 0764 0194 158 [234]
(Polyaniline-SWCNT/GO)3 multilayer I− /I−
3 N719 1481 0745 0354 391 [234]
(Polyaniline-SWCNT/GO)5 multilayer I− /I−
3 N719 1305 0755 0698 688 [234]
(Polyaniline-graphene (10 wt%)/GO)n (n = 10) I− /I−
3 N719 1679 0727 0646 788 [235]
(Polyaniline-graphene (10 wt%)/GO)n (n = 5) I− /I−
3 N719 1346 0735 0668 661 [235]
(Polyaniline-graphene (8 wt%)/GO)n (n = 10) I− /I−
3 N719 1702 0717 0642 783 [235]
(Polyaniline-graphene (8 wt%)/GO)n (n = 5) I− /I−
3 N719 1214 0740 0671 603 [235]
Polyaniline-graphene (4 wt%)/GO)n (n = 10) I− /I−
3 N719 1448 0684 0644 638 [235]
(Polyaniline-graphene (4 wt%)/GO)n (n = 5) I− /I−
3 N719 1526 0679 0406 421 [235]
(Polyaniline-10 wt% graphene)/Pt)9 I− /I−
3 N719 1522 0725 0675 745 [236]
(Polyaniline-10 wt% graphene)/Pt)3 I− /I−
3 N719 1209 0665 0621 499 [236]
Polyaniline/reduced graphene oxide (rGO) – – 1288 074 65 615 [238]
Graphene/PEDOT I− /I−3 N719 1260 077 63 626 [239]
PEDOT only I− /I−3 N719 1260 077 58 562 [239]
Pt reference I− /I−3 N719 124 077 70 668 [239]
Graphene/PEDOT-PSSa composite I− /I−3 N719 1296 072 48 45 [240]
PEDOT (0.8 wt%)-PSS (0.5 wt%) I− /I−3 N719 1099 072 28 23 [240]
Pt reference I− /I−3 N719 1305 072 68 63 [240]
E-Reduce graphene oxide/PDDAa I− /I−3 (Z952) C106TBAb 1519 0654 76 766 [241]
E-Reduce graphene oxide/PDDA I− /I−3 (Z946) C106TBA 1877 0692 74 954 [241]
Pt/FTO reference I− /I−3 (Z946) C106TBA 1811 0686 74 914 [241]

Notes: a PDDA = poly(diallyldimethylammonium chloride); b C106TBA = TBARu(4,4-bis(5-(hexylthio)thiophen-2-yl)-2,2-bipyridine) (4-carboxylicacid-4-carboxylate-2,2-bi-

pyridine).

1890 Sci. Adv. Mater., 7, 1863–1912, 2015

Singh and Nalwa
a [Co(bpy)3]3+/2+ redox electrolyte, outperforming the Pt
counter electrode (PCE of 9.05% vs. 8.43%) in DSSCs.
Xue et al.165 studied nitrogen-doped graphene foams
(N-GFs) as counter electrodes for DSSCs. The N-doped
graphene foams had a 7.6% nitrogen content and was
deposited on an FTO substrate as a counter electrode,
which showed a PCE of 7.07%, while the DSSC with
a Pt counter electrode had a PCE of 7.44%. The photo-
voltaic performance was compared with DSSCs fabricated
using graphene oxide foam (rGOF), spin-coated N-doped
graphene, and rGO films, as well as with Pt. The N-
doped graphene foams performed better than spin-coated
graphene films, whereas both nitrogen doping and foam-
like structure contributed to a higher efficiency of DSSCs.
Luo et al.166 demonstrated that DSSCs containing sulfur-
doped reduced GO (SrGO), as well as nitrogen and sulfur
dual-doped reduced GO (NSrGO) have higher PCEs of
4.23% and 4.73%, respectively, which is higher than that
of a Pt counter electrode. Fang et al.242 prepared boron
(B)-doped graphene films by mixing GO and B2 O3 in a 1:2
ratio and then grinding and thermally annealing the mix-
ture at 1200  C for 4 h as illustrated in Figure 17. Finally,
the B-doped graphene was obtained after refluxing the
mixture in 3-M NaOH solution, which removes residual
B2 O3 from the graphene mixture. Both scanning electron
microscopy (SEM) and transmission electron microscopy
(TEM) images confirmed the removal of B2 O3 from the
graphene mixture, as no particle-like structures were vis-
ible. Pristine graphene also was prepared by annealing
GO under identical conditions. The graphene, B-doped
graphene, and Pt electrodes showed charge transfer resis-
tance of 18.55, 1.37, and 8.40 /sq, respectively. The B-
doped graphene containing 0.09, 1.13 and 2.36 mass ratios
of B2 O3 to GO exhibited PCEs of 4.16, 6.73 and 6.16%,
respectively. The B-doped graphene showed a maximum
PCE of 6.73% as a counter electrode in a DSSC with N719
dye for the triiodide reduction, which was better than the
PCE of 3.29% for pristine graphene and 6.34% for a Pt
counter electrode. This clearly demonstrates the contribu-
tion of boron doping in graphene-based DSSCs.
Nitrogen-doped microwave radiation–exfoliated
graphene (N-MEG) nanosheets as Pt-free counter elec-
trodes for DSSCs were used by Zhai et al.243 The N-MEG
was prepared by using cyanamide (NH2 CN) at room
temperature. A DSSC efficiency of 7.18% was measured
for the N-MEG counter electrode, which was comparable
Fig. 17. Synthesis scheme for boron-doped graphene. Reprinted with
permission from [242], H. Fang, et al., Boron-doped graphene as a high-
efficiency counter electrode for dye-sensitized solar cells. Chem. Com-
mun. 50, 3328–3330 (2014). © 2014, Royal Society of Chemistry.
Sci. Adv. Mater., 7, 1863–1912, 2015
Graphene-Based Dye-Sensitized Solar Cells: A Review
to a Pt counter electrode (7.58%) and 1.6 times that of
MEG nanosheets. The series resistance for the N-MEG
counter electrode was 1.29 /cm2 and less than that of
the MEG counter electrode (1.71 /cm2  due to improved
conductivity by the N-doping. Song et al.244 reported on
N-doped porous graphene foams as the counter electrode
material for DSSCs in conjunction with an iodide-based
electrolyte and a sulfide-based electrolyte. A PCE of
4.5% was recorded for the iodide-based electrolyte and
2.1% for the sulfide-based electrolyte. These reports seem
to be good steps toward fabricating metal-free counter
electrodes for DSSCs. Meng et al.245 used nitrogen-doped
graphene nanoribbons (N-GNRs) as counter electrodes
for DSSCs with an iodide/triiodide based electrolyte,
which showed a PCE of 8.57%, compared to a PCE of
8.01% for GNRs and 7.84% for Pt counter electrodes.
This indicates the role of N species on GNRs for the
triiodide reduction. Wang et al.246 prepared nitrogen-
doped graphene/TiO2 nanohybrids from self-assembly
of pyrene-modified H2 Ti3 O7 nanosheets with graphene
sheets and used as counter electrodes for DSSC. The
PCE values were 5.04% for the N-doped TiO2 /graphene
REVIEW
nanohybrid, 4.44% for the TiO2 /graphene nanohybrid,
and 6.40% for the Pt reference. The nitrogen-doped
graphene/TiO2 hybrid at 700  C exhibited a higher JSC of
13.73 mA cm−2 and a PCE of 5.04% compared to the
nitrogen-doped graphene/TiO2 at 570  C (PCE, 5.03%;
JSC = 1242 mA cm−2  but the PCE was lower than a
standard Pt counter electrode. The nanohybrids prepared
at higher temperature have higher electrocatalytic activity
toward triiodide reduction. Hou et al.247 demonstrated that
the N-doping of graphene lowers the charge transfer resis-
tance, improves the electrocatalytic activity of graphene
toward triiodide reduction, and therefore enhances the
photovoltaic performance of DSSCs. The nitrogen states,
rather than N content, significantly influence the catalytic
activity, where pyridinic and quaternary nitrogen states
offer more active sites for triiodide reduction. Kannan
et al.248 reported a PCE of 7.42% for DSSCs with nitrogen
and sulfur co-doped graphene nanosheets with the I− 3 /I
−
redox reaction, which was comparable to 7.56% for a
Pt counter electrode and higher than that of nitrogen- or
sulfur-doped graphene electrodes.
A very interesting chemical doping study was con-
ducted by Jung et al.249 by comparing standard Pt, pristine
graphene (PG), and B-doped graphene (BG) as counter
electrodes in a [Co(bpy)3]3+/2+ redox couple with JK-
303 photosensitizer for DSSCs, and then for an iodine-
based electrolyte (I− /I−
3 ). Figures 18(a)–(d) show current–
voltage curves of the DSSCs with standard Pt, PG, and
BG counter electrodes under AM 1.5G illumination, CV
at a scan rate of 10 mV/s for the [Co(bpy)3]3+/2+ redox
couple with Pt, PG, and BG working electrodes, Pt as the
counter electrode, Ag/Ag+ as the reference electrode, and
0.1 M LiClO4 as the supporting electrolyte, Nyquist plots
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 Graphene-Based Dye-Sensitized Solar Cells: A Review Singh and Nalwa

Fig. 18. (a–d) Current–voltage curves of DSSCs with standard Pt, pristine graphene (PG), and boron-doped graphene (BG) counter electrodes under
AM 1.5G illumination. (b) Cyclic voltammograms at a scan rate of 10 mV/s for the [Co(bpy)3 ]2+/3+ redox couple with Pt, PG, and BG working
REVIEW

electrodes; Pt as the counter electrode; Ag/Ag+ as the reference electrode; and 0.1 M LiClO4 as the supporting electrolyte. (c) Nyquist plots on
symmetrical dummy cells measured at 0 V from 106 to 0.1 Hz with Pt, PG, and BG electrodes. (d) Electrochemical stability of identical dummy
cells after 100 cycling potentials. For comparision purposes, Figure 18 (e, f) shows J –V curves of DSSCs with Pt, PG, and BG counter electrodes for
iodine-based electrolyte (I− /I−3 ) under AM 1.5G illumination, and Nyquist plots obtained at 0 V from 106 to 0.1 Hz with Pt, PG, and BG electrodes
on symmetrical dummy cells. Reprinted with permission from [249], S. M. Jung, et al., B-doped graphene as an electrochemically superior metal-
free cathode material as compared to Pt over a Co(II)/Co(III) electrolyte for dye-sensitized solar cell. Chem. Mater. 26, 3586–3591 (2014). © 2014,
American Chemical Society.

on symmetrical dummy cells measured at 0 V from 106
to 0.1 Hz with Pt, PG, and BG electrodes. Figures 18(e),
(f) represent J –V curves of DSSCs with Pt, PG, and
BG counter electrodes for iodine-based electrolyte (I− /I−3)
under AM 1.5G illumination and Nyquist plots obtained
at 0 V from 106 to 0.1 Hz with Pt, PG, and BG electrodes
on symmetrical dummy cells. The cathodic peak currents
for the reduction of [Co(bpy)3]3+/2+ were 0.14 mA cm−2
for Pt, 0.16 mA cm−2 for PG, and 0.23 mA cm−2 for the
BG electrode. The BG electrode shows larger peak cur-
rent density and narrower peak-to-peak separation com-
pared with the Pt electrode, indicating a faster reduction
rate on the surface of the BG electrode than on the Pt
electrode. The RCT values at the electrode/electrolyte inter-
face calculated from the equivalent circuit (EC) model
were 2.39  cm2 , 0.75  cm2 , and 0.57  cm2 for stan-
dard Pt, pristine graphene, and B-doped graphene elec-
trodes, respectively. From the Tafel polarization curves,
the slope of the tangent to the B-doped graphene was
higher than that of standard Pt and pristine graphene, indi-
cating a larger exchange current density (J0  for the B-
doped graphene electrode. The B-doped graphene-based
DSSC with smaller RCT or larger J0 could generate higher
JSC than DSSCs with Pt and pristine graphene counter
electrodes. The Nyquist plots were recorded from the
dummy DSSCs after 100 cycling potential. The RCT values
of the BG and PG electrodes were increased to 1.44
 cm2 and 1.66  cm2 , respectively, while it significantly
increased to 7.21  cm2 for the Pt electrode. The PG
and BG electrodes also showed higher stability than in
the [Co(bpy)3]3+/2+ medium. The DSSC fabricated with
Pt showed a JSC of 13.44 mA cm−2 , VOC of 885 mV, and
FF of 71.0%, resulting in a PCE of 8.45%. The DSSC
with pristine graphene exhibited a higher JSC of 13.51
mA cm−2 , FF of 74.9%, and PCE of 8.80%. The photo-
voltaic performance was further increased for the B-doped
graphene, showing a JSC of 13.73 mA cm−2 , VOC of 887
mV, FF of 75.6%, and PCE of 9.21%. The JSC , FF, and
PCE values of the B-doped graphene-based DSSCs were
higher compared with standard Pt and pristine graphene-
based DSSCs, which clearly shows the effect of chemical
doping on the photovoltaic performance of graphene-based
DSSCs. The series resistance and charge-transfer resis-
tance of the Pt counter electrode were 1.89 /cm2 and
2.84 /cm2 , higher in comparison to 1.86 /cm2 and 1.41
/cm2 for the B-doped graphene electrode, respectively;
therefore, the B-doped graphene has high electrocatalytic
activity for the [Co(bpy)3]3+/2+ reduction, which increases
the photovoltaic performance of DSSCs. For the iodine-
based electrolyte, the DSSCs exhibited PCEs of 2.46% for

1892 Sci. Adv. Mater., 7, 1863–1912, 2015

Singh and Nalwa
the pristine graphene, 6.11% for the B-doped graphene
counter electrode, and 7.33% for the standard Pt counter
electrode. Although this is poor performance in compari-
son with the [Co(bpy)3]3+/2+ -based redox electrolyte, still
there is a significant enhancement in PCE value in the
iodine-based electrolyte (I− /I− 3 ) after B-doping.
The N-doped graphene from pristine GO with
urea in a hypothermal reaction was synthesized by
Zhang et al.250 to use as a cathode in the DSSCs
for [Co(bpy)3]3+/2+ complex redox with a new
sensitizer, 3-[6-[4-[4-dihexyloxybiphenyl-4-yl-amino-]phenyl
[-4,4 -dihexylcyclopenta-[2,1-b:3,4-b]dithiphene-2-yl]-2-cyano-
acrylic acid (XS-57). The maximum nitrogen content
was 7.6 wt% and thermal annealing increased exchange
current density. The N-doped graphene cathode showed a
PCE of 8.2%. Lin et al.251 used N-doped graphene/Pt/FTO
counter electrodes for DSSCs. The DSSC fabricated with
graphene/FTO electrode showed a JSC of 13.24 mA cm−2 ,
VOC of 710 mV, and FF of 31.0%, resulting in a PCE of
2.94%, while for N-doped graphene/FTO electrodes, all
parameters increased, to a JSC of 13.26 mA cm−2 , VOC of
718 mV, and FF of 61.0%, resulting in a PCE of 5.84%.
The DSSCs fabricated with N-doped graphene/Pt/FTO
(NGR/Pt/FTO) counter electrodes showed a PCE of
9.38%, which is much higher than those of the DSSCs
with Pt/FTO (PCE, 7.53%) and N-doped GR/FTO counter
electrode (5.84%) in a I− /I− 3 redox couple with N719
photosensitizer.
Chemical doping with heteroatoms increases the PCE
of DSSCs because it contributes to higher surface
hydrophilicity and electrical conductivity, which corre-
spondingly leads to increased electrode/electrolyte interac-
tions and charge transfer.252 253 The heteroatom doping of
graphene increases charge transfer efficiency and higher
electrocatalytic activity of DSSCs. Battacharjee254 con-
ducted first principles studies on the understanding of
chemical activation of graphene carbon atoms due to
nitrogen doping and pointed out that activated carbon
atoms facilitate absorption of radicals. Wang et al.255 have
suggested various strategies for designing nitrogen-doped
graphene, including co-doping with boron, sulfur, and
phosphorus, controlling doping levels, conjugated poly-
mer/graphene hybrid formation, etc., to tailor electrical and
optical properties.
5. GRAPHENE-BASED PHOTOANODES
Indiun tin oxide (ITO) is the most common transparent
conducting electrode (TCE) used in a wide variety of
functional devices in electronic and photonic industries.
ITO is interesting due to its high optical transparency and
electrical conductivity, as well as for its ease of fabrica-
tion into thin films. ITO being expensive, brittle, and not
cost-effective to use in manufacturing, alternative mate-
rials have been explored, such as transparent conducting
oxides, conducting polymers, carbon nanotubes, graphene,
Sci. Adv. Mater., 7, 1863–1912, 2015
Graphene-Based Dye-Sensitized Solar Cells: A Review
etc. Besides many other requirements, high optical trans-
parency and low sheet resistance are two main criteria to
select a desirable TCE material for DSSCs. Bae et al.256
reported a sheet resistance of 30 /sq at 90% trans-
parency for a four-layer film prepared from a layer-by-
layer method, and a sheet resistance of 125 /sq at 97.4%
transparency for the CVD-grown graphene monolayer. Zhu
et al.257 developed TCE films using a graphene/metallic
grid hybrid on a glass or PET film. The sheet resis-
tance of hybrid transparent electrodes was found to be
3 /sq at 80% transmittance and 20 /sq at over 90%
transmittance. The graphene/metal grid hybrid graphene
transparent electrode showed transmittance range of 70–
91%. These studies indicate that graphene-based mate-
rials qualify as TCEs and have a great potential as a
replacement of ITO and FTO electrodes. Wang et al.258
used graphene films as window electrodes for DSSCs.
A 10-nm graphene film showing electrical conductivity
of 550 S/cm and optical transparency of ~70% at 1000–
3000 nm has been used as a transparent conducting elec-
trode for DSSCs. The sheet resistance of ca.10 nm–thick
graphene film thermally treated at 1100  C was found
to be 1.8 k/sq. A graphene/TiO2/dye/spiro-OMeTAD/Au
REVIEW
DSSC device showed a PCE of 0.26% compared to a PCE
of 0.84% for a FTO-based DSSC. Kim et al.259 applied
GO/TiO2 nanocomposites as an interfacial layer between
an FTO layer and TiO2 film, which resulted in an increase
in VOC of 54 mV and an increase in PCE from 4.89%
to 5.26%. Yen et al.260 prepared a hybrid of graphene
and acid-treated multi-walled carbon nanotubes (MWC-
NTs) and incorporated it into a TiO2 matrix to work as an
electrode in DSSCs. The hybrid offers higher dye adsorp-
tion and reduces charge recombination. DSSCs based on
the graphene/MWCNT hybrid showed a PCE of 6.11%,
which is 31% higher than for TiO2 -based DSSCs.
A large number of studies have been conducted on
DSSCs in which graphene–TiO2 composites were used
as a photoanode. Graphene–TiO2 composites showing the
impact of graphene contents on DSSC efficiency are
discussed here. Zhao et al.261 used graphene and tita-
nia film electrodes because of high porosity and large
specific surface area to promote adsorption of the sensi-
tizing dye. A DSSC based on a graphene/titania photoan-
ode showed a PCE of 7.52% under a simulated irradiation
of 100 mW/cm2 . Lee et al.262 used monolayer graphene
networks with TiO2 as a photoanode in DSSCs, which
yielded a 31% increase in PCE over that of a TiO2 anode,
and then a further 10% increase after integrating a 3D
tubular-structure graphene path. The highest PCE of 9.2%
was recorded for the 3D graphene-TiO2 hybrid network
foam. In this study, 4-nitrobenzenediazonium tetrafluo-
roborate (4-NBD) was used to control electron leakage
and N719 dye was replaced by the ruthenium complex
C106TBA dye, which resulted in enhanced PCE val-
ues that were higher than that of the rGO-TiO2 multi-
composite photoanode. Tang and Hu263 used two types of
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graphene-modified TiO2 composites to fabricate DSSCs:
graphene/TiO2 multilayer films prepared by supercritical
treatment (Gr-SCT) and graphene/titanate nanotubes (Gr-
TNTs) films. PCEs of 6.46% for Gr-SCT and 7.54%
for Gr-TNTs photoanodes were measured, showing an
increase of 33.8% and 20.6% compared with a TiO2 pho-
toanode under similar conditions. The PCE reached as
high as 8.67% for the Gr-SCT-TiO2 /Gr-TNTs photoanode,
which is higher than for a pure TiO2 photoanode (PCE,
6.25%).
TiO2 nanoparticles and reduced graphene oxide
(TiO2 /rGO) hybrids with varying rGO contents
(0–16 wt%) for the DSSCs were used Cheng et al.264
Figure 19 shows the photocurrent density versus voltage
characteristics and incident photon-to-current efficiency
(IPCE) spectra of the 5 DSSCs having different amounts
of rGO in TiO2 /RGO-based electrodes. DSSCs containing
1.6 wt% of graphene content showed the highest conver-
sion efficiency, at 7.68%, which was 1.6× greater than
(a) 20
1.6 wt.%
REVIEW
Current density (mA/cm2)
that for pure anatase–TiO2 nanoparticles (4.78%). The
PCE of TiO2 /rGO photoanodes increased from 0.8 wt%
(PCE of 5.34%) to 1.6 wt% graphene content but there-
after the PCE showed a decrease as graphene contents
were increased to 4 wt% (PCE of 4.24%) and 16 wt%
(PCE of 3.54%). This study shows that a small content of
rGO is sufficient to enhance the electrochemical catalytic
activity in the DSSC. In these DSSCs, the graphene plays
a role in accelerating the electron transfer process and
reducing the charge recombination.
Composites of rGO/TiO2 nanocrystals were prepared by
solvothermal method by Shu et al.265 to use as a pho-
toanode in DSSCs. The rGO/TiO2 composite films con-
taining 0.75 wt% rGO showed the highest PCE of 5.5%
as photoanode, compared to 4.2% for pure TiO2 photoan-
ode films; efficiency increased by 31% due to graphene
content. The rGO in TiO2 composites decreased the resis-
tance. The charge transfer resistance decreased from 26.1
/sq for pure TiO2 to 24.5 /sq for 0.75 wt% rGO/TiO2
composites. This indicates an increased charge transfer
at the TiO2 /electrolyte interface with rGO. The rGO not
only reduces RCT but also gives rise to a longer lifetime
of the electron transfer in DSSCs. Song et al.266 reported

TiO2
15
enhancement of electron transport by the rGO–TiO2 Schot-
0.8 wt.% tky junction from dye to TiO2 . Ding et al.267 prepared
10
rGO/TiO2 nanocomposites at room temperature and used
vitamin C for reduction purpose. The rGO/TiO2 nanopar-
ticles films were used as a photoanode for DSSCs, which
4 wt.% showed a PCE of 7.89%, a 30% increase compared to a
5
16 wt.% pure TiO2 photoanode. Sacco et al.268 used graphene/TiO2
1
nanocomposites as photoanodes. The GO/TiO2 nanocom-
0 posites with 0.25 wt% GO content showed an optimized
0.0 0.2 0.4 0.6 0.8 PCE of 5.62%, twice that of a bare TiO2 photoanode. The
Voltage (V) incorporation of graphene increased the lifetime of elec-
(b) 60 trons because of the reduction of recombination of charge
carriers.
1.6 wt.% rGO sheets were deposited onto a TiO2 nanotube array
0.8 wt.%
as a photoanode in DSSCs by Luan et al.269 The JSC
40 was found to increase with longer electrophoretic depo-
TiO2 sition (EPD) time used for rGO deposition, but showed
IPCE (%)

a decrease with increased EPD time thereafter; a maxi-

mum JSC of 8.87 mA cm−2 was obtained at 30 seconds.
20 The DSSC based on 6.8 m-long TiO2 nanotubes with
30 seconds EPD time showed the highest PCE of 4.10%,
while a DSSC having bare TiO2 nanotubes (without rGO)
4 wt.%
16 wt.% had a PCE of 2.97% and JSC of 6.24 mA cm−2 . There
0
was a 38% improvement in PCE value of a DSSC fab-
400 500 600 700 800
ricated with TiO2 nanotubes/rGO electrode compared to
Wavelength (nm)
bare TiO2 nanotubes. The deposition of rGO on 16.8 m-
Fig. 19. (a) J –V characteristics and (b) incident photon-to-current effi- long bamboo-type TiO2 nanotube arrays further increased
ciency (IPCE) spectra of the 5 DSSCs having different amounts of PCE to 6.01% due to the higher surface area of bamboo-
reduced graphene oxide (rGO) in TiO2 /rGO-based electrodes. Reprinted type TiO2 nanotubes, facilitating more dye loading. Tang
with permission from [264], G. Cheng, et al., Novel preparation of
anatase TiO2 /reduced graphene oxide hybrids for high-performance dye-
et al.270 reported in situ incorporation of graphene sheets
sensitized solar cells. ACS Appl. Mater. Interfaces 5, 6635–6642 (2013). (GSs) in nanostructured TiO2 films via a molecular graft-
© 2013, American Chemical Society. ing method for DSSCs. The electrical conductivity of TiO2

1894 Sci. Adv. Mater., 7, 1863–1912, 2015

Singh and Nalwa
film increased more than 2 orders of magnitude by molec-
ular grafting of GSs, and the PCE of the DSSC was found
to be more than 5 times higher for GS/TiO2 compos-
ite films than for the TiO2 electrode, which is associated
with efficient dye loading of GS/TiO2 composite film com-
pared to bare TiO2 film. The PCE was found to be GS
content-dependent and reached a maximum of 1.68% at
0.03 mg/mL GS content and then showed a decrease with
the increasing of GS content because the transmittance
decreased at high GS content. The control DSSC device
without GS showed a PCE of 0.32%. Such an improve-
ment in PCE of GS/TiO2 composite films is due to the
decreased charge-transfer resistance after adding GS to the
TiO2 film because the resistivity of the GS/TiO2 compos-
ite films decreased gradually with increasing GS content,
reaching to 285  cm at 0.05 mg/mL GS concentration.
Madhavan et al.271 prepared TiO2 /graphene nanocompos-
ites via molten salt technique and studied the effect of
graphene content (0.2–10 wt%) on photovoltaic properties.
The conductivity measurements showed that the mean spe-
cific conductance of TiO2 /graphene nanocomposites was
15–55% higher compared to the TiO2 nanoparticles. The
optimized PCE of 5.41% was measured for TiO2 /graphene
nanocomposites having 0.5% graphene content as a pho-
toanode in DSSCs compared to a PCE of 4.11% for a
control TiO2 photoanode-based DSSC. The charge-transfer
resistance was found to be 30  cm2 for the TiO2 /graphene
nanocomposite compared to 45  cm2 for the TiO2 pho-
toanode, showing the superior photovoltaic performance of
nanocomposite film.
DSSCs applying TiO2 nanotube arrays as a photoan-
ode were fabricated by Song et al.,272 and were attached
to a transparent substrate using a graphene/TiO2 compos-
ite paste. The effect of the graphene concentration on
the graphene-TiO2/TiO2 nanotubes composites film-based
DSSCs was studied as a function of graphene content
of TiO2 in the paste. With 0.1 wt% loading of graphene
in TiO2 pastes, the optimized PCE of 6.29% was mea-
sured for graphene-TiO2/TiO2 nanotubes composites-based
DSSC, a 44% increase compared to a PCE of 4.35% for
bare TiO2 . As the graphene content was raised to 0.15 wt%
in TiO2 pastes, the PCE decreased to 4.87%. The enhance-
ment in PCE was because graphene facilitated electron
transfer. Solar light can be absorbed by graphene, which
could decrease the PCE of DSSCs. Durantini et al.273
developed DSSCs using graphene film and TiO2 /graphene
paste, which showed a higher PCE than a DSSC fab-
ricated with a commercial TiO2 paste. Yang et al.274
formed 2D bridges of graphene onto TiO2 photoanodes of
DSSCs. With the incorporation of graphene bridges, the
short-circuit current density increased by 45% and PCE
increased by 39% in comparison to a nanocrystalline TiO2
photoanode. PCEs of 6.97%, 1.52%, and 0.46% were mea-
sured for 0.6 wt%, 2.5 wt%, and 8.5 wt% graphene load-
ing, respectively. The 2D graphene bridge plays a role in
Sci. Adv. Mater., 7, 1863–1912, 2015
Graphene-Based Dye-Sensitized Solar Cells: A Review
enhancing both the charge transport rate as well as light-
collection efficiency. The 2D graphene proved to be better
than the 1D nanomaterial composite electrode of car-
bon nanotube (CNT). The CNT cannot disperse and con-
nect well to nanostructured TiO2 particles, which probably
results in lower efficiency than for graphene. Tsai et al.275
reported enhancement of PCE using graphene/TiO2 com-
posites as a working electrode in DSSCs. Field emission
scanning electron microscope (FE-SEM) as well as atomic
force microscopy (AFM) showed a uniform distribution
of graphene around the TiO2 particles. The dye absorp-
tion was found to increase with increasing graphene con-
tent up to 1 wt%. PCEs of 6.32%, 6.57%, 6.86%, and
6.29% were measured for 0.01 wt%, 0.1 wt%, 1 wt%,
and 10 wt% graphene content, respectively. At 1 wt%
graphene content in TiO2 film, the PCE increased from
5.98% to 6.86%, which is inconsistent with a decrease
in charge transfer resistance with increasing graphene
content.
TiO2 –graphene composite-based DSSCs were fabricated
by Peining et al.276 using screen-printing and doctor blad-
ing techniques. The PCE was found to be electrode
REVIEW
thickness–dependent. TiO2 -graphene nanocomposite-based
electrodes yielded PCEs of 6.03%, 6.49%, and 5.90% for
9-, 11-, and 13-m-thick films, respectively. Figure 20(a)
shows the photocurrent–voltage characteristics of com-
posite electrodes with different graphene content, varying
from 0.25 wt% to 0.75 wt%, and for a 0.5 wt% phys-
ical mixture of TiO2 and graphene. The PCE of TiO2 –
graphene composite electrode was optimal at 0.5 wt% of
graphene content. A graphene content–dependent study
also was performed by Kim et al.277 by fabricating DSSCs
with graphene-linked TiO2 electrode films. The PCE was
enhanced to 6.05% for 0.1 wt% graphene–TiO2 compos-
ite with N719 dye in comparison to 4.42% for pure TiO2
anatase. Figure 20(b) shows the IPCE curves for DSSCs
fabricated with pure TiO2 anatase and graphene–TiO2
composites. The highest quantum efficiency of 44% also
was observed for 1.0 wt% of graphene content. A quantum
efficiency of 33% was recorded for TiO2 -based devices,
which increased to 44% for DSSCs fabricated with com-
posites having 1.0 wt% graphene content. Overall, the
quantum efficiency was increased by 11% due to the
graphene–TiO2 electrode because it induced more photons.
Madhavan et al.278 developed electrospun TiO2 –graphene
composite nanofibers using poly(vinylpyrrolidone). The
fiber’s morphology decreased when graphene contents of
up to 1 wt% were used; therefore, graphene content of 0.0–
0.7 wt% was employed for DSSCs. The specific conduc-
tance for TiO2 –graphene composites was found to be 2×
greater than electrospun TiO2 fibers. The TiO2 –graphene
fiber composites used as photoanodes in DSSCs yielded a
PCE of 7.6%, resulting in a 21% enhancement over bare
TiO2 fibers. Zhu et al.279 fabricated DSSCs using TiO2 film
photoanodes having 0.4 wt%, 1.6 wt%, 2.4 wt%, and 3.2
1895
 Graphene-Based Dye-Sensitized Solar Cells: A Review Singh and Nalwa

Fig. 20. (a) Photocurrent versus voltage characteristics at different graphene concentrations for graphene/TiO2 -based electrodes in DSSCs. Reprinted
with permission from [276], Z. Peining, et al., Facile fabrication of TiO2 –graphene composite with enhanced photovoltaic and photocatalytic properties
by electrospinning. ACS Appl. Mater. Interfaces 4, 581–585 (2012). © 2012, American Chemical Society. (b) Incident photon-to-current efficiency
(IPCE) curves of DSSCs fabricated with pure TiO2 anatase and graphene–TiO2 composite-based electrodes having 1.0, 5.0, and 10.0 wt% graphene
contents. Reprinted with permission from [277], A. Y. Kim, et al., Photovoltaic efficiencies on dye-sensitized solar cells assembled with graphene-linked
TiO2 anode films. Bull. Korean Chem. Soc. 33, 3355–3360 (2012). © 2012, The Korean Chemical Society.

wt% graphene content. Figure 21 shows the photocurrent to the greater dye absorption on the TiO2 surface due to
versus voltage characteristics of TiO2 –graphene composite graphene doping, which causes the reduction of electron
REVIEW

electrodes with graphene contents varying from 0.0 wt%
to 3.2 wt%. DSSCs containing 1.6 wt% graphene in the
TiO2 photoanode showed the highest PCE of 3.69%; as
the graphene contents were increased to 2.4 wt% in the
composite, the PCE decreased by 60%. The PCE of the
graphene–TiO2 composite was 48% greater than that of
the bare TiO2 film electrode. The higher amount of dye
is adsorbed onto the TiO2 surface with 1.6 wt% graphene
doping. The efficiency improvement in DSSCs is attributed
6 attached to functionalized graphene sheet (FGS) mats. The
5
1.6 wt.%
Current density (mA/cm2)
recombination and the enhancement of electron transport
in TiO2 film. These studies showed that the graphene–
TiO2 composite exhibited better photovoltaic and photo-
catalytic properties than that of a pure TiO2 electrode.
Hsu et al.280 demonstrated a PCE increase from 1.45%
for bare TiO2 film to 3.98% for a graphene/TiO2 compos-
ite, showing a 170% enhancement after adding a graphene
layer. Moula et al.281 also reported an enhancement of
photocurrent in DSSCs using bismuth (Bi)-doped TiO2 -
graphene as a carrier transport. The Bi-doped TiO2 nano-
crystals, prepared by sol–gel hydrothermal method, were
DSSCs were fabricated from commercial TiO2 nanopow-
der, and FGS-based mats. The photocurrent density of

the DSSCs with Bi-doped TiO2 was higher than undoped

4 TiO2 and commercial P25. The increased PCE of Bi-
0.4 wt.% doped TiO2 resulted from a wider absorption in the UV-vis
3 2.4 wt.% region. Jang et al.282 used different amounts of 3D crum-
TiO2
pled graphene (3D CGR) in TiO2 film as a photoanode
2 for DSSCs. The DSSCs having 0.003 wt%, 0.01 wt%,
and 0.03 wt% of 3D CGR in a 3D CGR composite-based
1
3.2 wt.% photoanode showed conversion efficiencies of 5.1%, 6.3%,
and 4.6%, respectively, which were higher than for pure
0 TiO2 photoanode-based DSSCs. Chen et al.283 reported
0.0 0.2 0.4 0.6 0.8
fabricated DSSCs with a TiO2 /graphene/TiO2 sandwich
Voltage (V) structure. The DSSC based on a TiO2 /graphene/TiO2 sand-
Fig. 21. J –V characteristics at different graphene concentrations for wich structure showed a PCE of 3.93%, which is 60%
graphene/TiO2 -based electrodes in DSSCs. Bare TiO2 film and TiO2 higher compared with a traditional DSSC structure (PEC,
films containing 0.4, 1.6, 2.4, and 3.2 wt% graphene contents are named 2.46%). The TiO2 /graphene/TiO2 sandwich-based DSSC
as electrodes 1, 2, 3, 4, and 5, respectively. Reprinted with permis- showed an increase in short-circuit current density (JSC ,
sion from [279], G. Zhu, et al., Enhanced performance of dye-sensitized
solar cells by graphene-incorporated nanocrystalline TiO2 films. Nanosci.
open-circuit voltage (VOC , and PCE compared to a con-
Nanotechnol. Lett. 5, 154–158 (2013). © 2013, American Scientific ventional DSSC structure due to efficient light absorption
Publishers. in the visible range.

1896 Sci. Adv. Mater., 7, 1863–1912, 2015

Singh and Nalwa
The insertion of a graphene quantum dots (GQDs)
layer between perovskite and TiO2 increased the PCE of
perovskite solar cells from 8.81% to 10.15% as reported
by Zhu et al.284 The insertion of GQDs yielded quench-
ing of perovskite photoluminescence at ∼760 nm, which
consequently increased the IPCE and the absorbed photon-
to-current conversion efficiency (APCE) of solar cells.
The GQDs caused faster electron extraction at times of
90–106 ps in the CH3 NH3 PbI3 /GQDs/TiO2 film compared
to 260–307 ps in the CH3 NH3 PbI3 /TiO2 film. Several other
studies on graphene–TiO2 composite-based DSSCs have
been reported243–245 that also supported the notion that
the PCEs of graphene–TiO2 composites are greater than
those of pure TiO2 -based DSSCs, and that in interactions
between TiO2 photoanode and dye molecules, the nature of
the redox electrolyte can influence the overall photovoltaic
performance of a DSSC device.
In quantum dot-sensitized solar cells (QDSSCs), the
quantum dots act as light absorber instead of a dye.
The potential for using graphene in QDSSCs has been
explored. Zhu et al.285 also reported QDSSCs based on
a TiO2 film photoanode having different amounts of
graphene. The solar cells having 0.8 wt% graphene in
the TiO2 photoanode showed a maximum PCE of 1.44%,
which was 56% greater than that of a TiO2 film pho-
toanode with no graphene. Zhu et al.286 used graphene
frameworks as an electron transport medium for TiO2
photoanode-based QDSSCs. The 1.5 wt% GFs incorpora-
tion into the TiO2 photoanode yielded a maximum PCE of
4.2% for QDSSCs, which was higher compared to a TiO2
photoanode and conventional graphene electrodes. SEM
images showed the coarse morphology of graphene/TiO2
electrode films, where GFs/TiO2 electrode films have
large pores, which facilitates the higher absorption of
photo-sensitizer leading to higher efficiency. Sun et al.287
fabricated QDSSCs using graphene-CdSe composite as a
photoanode. The CdSe to GO ratio was 4.5:1 for an opti-
mized PCE of 0.72%. There has been significant progress
in graphene-based photoanodes for DSSCs.288–290 Table V
lists graphene-based photoanodes for DSSCs.258–287 The
photovoltaic parameters, short-circuit photocurrent den-
sity (JSC , open-circuit voltage (VOC , fill factor (FF), and
power conversion efficiency (PCE; , redox couples, and
dyes used in DSSCs of graphene photoanodes, includ-
ing graphene/TiO2 nanocomposites, are compared with a
TiO2 electrode as the reference cell. One of the interest-
ing outcomes clearly noticeable here is that graphene–TiO2
nanocomposites exhibit superior photovoltaic performance
than that of pure TiO2 used as a photoanode in DSSCs.
The PCE of DSSCs is significantly impacted by graphene
content but it does have a plateau: PCE increases only up
to a certain amount of graphene content in the composite;
thereafter, PCE starts to decrease as graphene content is
further increased in the composite.
Sci. Adv. Mater., 7, 1863–1912, 2015
Graphene-Based Dye-Sensitized Solar Cells: A Review
6. GRAPHENE-BASED ELECTROLYTES
Liquid electrolytes with different redox couples are
used for fabricating DSSCs, and they can facilitate
charge carrier transport and regeneration of photosen-
sitizing dye molecules. Wu et al.137 summarized dif-
ferent types of electrolytes for DSSCs, including ionic
liquid electrolytes, in reference with an iodide/triiodide
redox couple, as well as iodide/triiodide-free media-
tors, quasi solid-state electrolytes based on thermoplastic
polymers, thermosetting polymers, polymer composites,
quasi-solid ionic liquid electrolytes, and solid-state hole-
transport materials, including solid-state ionic conductors,
inorganic and organic hole-transport materials, and per-
ovskite solar cells. Liquid electrolytes used in DSSCs
are volatile, toxic, and they inherit other disadvantages.
Graphene is a solid material, easily processed into dif-
ferent physical forms with high thermal stability; there-
fore, graphene-based materials have been integrated into
electrolytes for fabricating DSSCs. Ahmad et al.291 incor-
porated graphene, SWCNTs, and SWCNTs/graphene into
1-methyl-3-propylimidazolium iodide (PMII) ionic liquid
as electrolytes for DSSCs. The quasi solid-state elec-
REVIEW
trolytes were sandwiched between TiO2 and Pt electrodes
to fabricate DSSCs. The pure PMII ionic liquid electrolyte-
based DSSC showed a PCE of 0.16%. When 5 wt%,
10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%,
and 40 wt% graphene contents were added in PMII, the
PCE values increased to 0.18%, 0.21%, 0.79%, 0.90%,
1.20%, 2.10%, 0.59%, and 0.48%, respectively; therefore,
the PCE of graphene based quasi solid-state electrolytes
increased from 0.16% to 2.10% with increasing graphene
content up to 30 wt% and thereafter decreased. Above
30 wt% graphene, the ionic electrolyte become a very
high-viscosity liquid, unable to penetrate into the TiO2
layer; it therefore leads to a decrease in PCE. PCE val-
ues of 0.25%, 1.43%, 0.56%, 0.46%, and 0.40% were
observed for 1 wt%, 7 wt%, 10 wt%, 13 wt%, and 16 wt%
SWCNT content; therefore, the PCE of a SWCNTs-based
DSSC increased from 0.16% to 1.43%, up to 7 wt%
SWCNT content, and then started decreasing with increas-
ing SWCNT content, which may be due to aggregation
of SWCNTs. The interesting quasi-solid electrolyte is the
hybrid of graphene and SWCNTs. The 3 wt% graphene
and 12 wt% SWCNTs mixture showed a PCE increase
from 0.16% to 2.50%, while the 12 wt% graphene and
3 wt% SWCNTs mixture showed a PCE of 1.39%. The
graphene and SWCNTs contribute to an increase in PCE
as an effective charge transporter in the ionic liquids and
as a catalyst for triiodide reduction. The ionic liquid could
also facilitate self-organization of graphene and SWCNTs,
which provides an efficient electron transfer. The time-
dependent stability of the quasi-solid DSSCs was also
studied. Figure 22 shows the stability of PCEs of DSSCs
based on pure graphene, SWCNTs, graphene/SWCNT
electrolytes, and PMII reference only. The DSSCs were
1897
 Graphene-Based Dye-Sensitized Solar Cells: A Review Singh and Nalwa

Table V. Graphene-based photoanodes in DSSCs. The photovoltaic parameters short-circuit photocurrent density (JSC ), open-circuit voltage (VOC ), fill
factor (FF), and power conversion efficiency (PCE; ), redox couples, and dyes used in DSSCs of graphene/TiO2 nanocomposites are compared with
a TiO2 electrode as the reference cell.

Graphene photoanodes Redox couples Dye JSC (mA/cm2  VOC (V) FF (%) PCE (, %) Ref.
a − −
Graphene/TiO2 /spiro-OMeTAD I /I 3 N3 110 070 36 026 [258]
F-doped SnO2 I− /I −
3 N3 302 076 36 084 [258]
Graphene/TiO2 hybrid network foam I− /I −
3 C106TBA 167 075 74 92 [262]
TiO2 network foams I− /I −
3 C106TBA 152 075 74 84 [262]
Graphene/TiO2 hybrid network foam (+4NBD) I− /I −
3 N719 146 072 64 67 [262]
TiO2 network foams (+4NBD)a I− /I −
3 N719 123 072 65 58 [262]
TiO2 film I− /I −
3 N719 83 070 75 44 [262]
TiO2 /reduced graphene oxide (1.6 wt%) I− /I −
3 N719 1839 0682 612 768 [264]
Pure TiO2 anatase I− /I −
3 N719 132 0691 524 478 [264]
Reduced graphene oxide (0.75 wt%)/TiO2 I− /I −
3 N719 1216 0668 677 55 [265]
TiO2 only I− /I −
3 N719 1075 0686 566 42 [265]
Reduced graphene oxide/TiO2 – D9 182 0576 579 606 [266]
TiO2 only – D9 164 0597 520 509 [266]
Reduced graphene oxide (0.75 wt%)/TiO2 I− /I−3 N719 152 0708 733 789 [267]
Reduced graphene oxide (1.25 wt%)/TiO2 I− /I−3 N719 118 0687 673 546 [267]
TiO2 only I− /I−3 N719 122 0715 695 606 [267]
Reduced graphene oxide (0.25 wt%)/TiO2 I− /I−3 N719 1304 0645 67 562 [268]
TiO2 only I− /I−3 N719 618 0606 71 267 [268]
Reduced graphene oxide nanosheets/TiO2 nanotubes I− /I−3 N719 887 077 60 410 [269]
RGO nanosheets/TiO2 nanotubes (bamboo-type) I− /I−3 N719 1251 077 624 601 [269]
REVIEW

TiO2 only I− /I−3 N719 624 073 652 297 [269]

Graphene sheet/TiO2 nanoparticles I− /I−3 N719 667 056 45 168 [270]
TiO2 only I− /I−3 N719 195 052 31 032 [270]
TiO2 /graphene nanocomposite (0.5 wt%) I− /I−3 N749 568 072 6645 541 [271]
TiO2 only I− /I−3 N749 472 067 6493 411 [271]
Graphene (0.1 wt%)–TiO2 NPs/TiO2 nanotubes I− /I−3 N719 1659 069 56 629 [272]
TiO2 only I− /I−3 N719 1226 069 51 435 [272]
Graphene/TiO2 (13 wt%) paste I− /I−3 N719 132 072 73 71 [273]
TiO2 only I− /I−3 N719 101 071 70 51 [273]
Graphene film I− /I−3 N719 140 073 72 73 [273]
Graphene (0.6 wt%)/TiO2 I− /I−3 N3 1629 069 62 697 [274]
TiO2 only I− /I−3 N3 1126 069 645 501 [274]
Carbon nanotube (0.4 wt%)/TiO2 I− /I−3 N3 335 042 411 058 [274]
Graphene (1 wt%)/TiO2 composite I− /I−3 N719 1992 070 488 686 [275]
TiO2 only I− /I−3 N719 1883 0684 4648 598 [275]
Graphene (0.5 wt%)/TiO2 composite I− /I−3 N3 1278 082 62 649 [276]
TiO2 only I− /I−3 N3 958 082 62 489 [276]
Graphene (1.0 wt%)/TiO2 composite I− /I−3 N719 1289 068 69 605 [277]
Graphene (5.0 wt%)/TiO2 composite I− /I−3 N719 1115 071 66 522 [277]
TiO2 only I− /I−3 N719 869 077 66 442 [277]
TiO2 /Graphene (0.7 wt%) composite I− /I−3 N719 162 071 66 76 [278]
TiO2 nanofiber only I− /I−3 N719 139 071 63 63 [278]
TiO2 /graphene (1.6 wt%) composite I− /I−3 N719 520 070 61 369 [279]
TiO2 /graphene (0.4 wt%) composite I− /I−3 N719 402 069 61 282 [279]
TiO2 only I− /I−3 N719 394 065 59 249 [279]
TiO2 /graphene composite I− /I−3 N719 175 050 456 398 [280]
TiO2 only I− /I−3 N719 690 050 419 145 [280]
5% Bismuth-doped TiO2 –graphene oxide I− /I−3 N3 1185 0505 68 407 [281]
5% Bismuth-doped TiO2 nanocrystals I− /I−3 N3 740 0510 62 234 [281]
TiO2 nanocrystals I− /I−3 N3 265 0500 62 082 [281]
3D crumpled graphene (0.01 wt%)/TiO2 film – – 1508 065 6437 63 [282]
Pure TiO2 – – 1092 065 5982 43 [282]
TiO2 /graphene/TiO2 sandwich structure I− /I−3 N719 1122 06 58 393 [283]
TiO2 /graphene I− /I−3 N719 8044 055 56 246 [283]
CH3 NH3 PbI3 /graphene quantum dots/TiO2 – – 1706 0937 635 1015 [284]
CH3 NH3 PbI3 /TiO2 – – 1543 0939 612 881 [284]

1898 Sci. Adv. Mater., 7, 1863–1912, 2015

Singh and Nalwa Graphene-Based Dye-Sensitized Solar Cells: A Review

Table V. Continued.

Graphene photoanodes Redox couples Dye JSC (mA/cm2  VOC (V) FF (%) PCE (, %) Ref.

Reduced graphene oxide (1.5 wt%)/TiO2 – – 1370 058 4519 358 [286]
Graphene (1.5 wt%)/TiO2 – – 1589 058 4559 420 [286]
TiO2 only – – 1241 057 4492 317 [286]
Graphene-CdSe (4.5:1 ratio) – – 580 0354 3691 076 [287]
Graphene – – 015 0192 3213 0009 [287]
CdSe – – 006 0423 6434 0016 [287]

Note: a 4-nitrobenzenediazonium tetrafluoroborate (4-NBD).

stored in desiccators and their I –V characteristics were
measured up to 1000 h at intervals of 120 hours. The PCEs
for all DSSCs decreased after five days, then started to
stabilize and thereafter followed a gradual decrease. PCE
values after 1000 h of SWCNT, graphene, and graphene
(12 wt%)/SWCNTs (3 wt%) were found to decrease from
1.43% to 1.02%, 2.10% to 1.61%, and 2.50% to 1.55%,
respectively. The PCE of a PMII-based DSSC was found
to increase after 120 h, then gradually decrease, reach-
ing 0.50% after 1000 h. The graphene-based DSSC was
found to be most stable, which could be because the high
graphene loading electrolyte provides a protective layer to
spectroscopy (EIS). The RCT was found to further decrease
from 67  cm2 (only PMII) to 0.88  cm2 for SWCNTs-
based quasi solid-state electrolytes. A RCT of 66.9  cm2 ,
0.77  cm2 , 1.49  cm2 , and 1.84  cm2 for PMII,
SWCNT, graphene/SWCNT, and graphene, respectively,
were obtained from fitting the EIS data. The PCE of
the graphene/SWCNT-based quasi solid-state electrolyte-
based DSSC was found to increase from 1.78% for a
10 m–thick transparent working electrode to 2.50% for
the same thickness of opaque electrode, and to 2.96%
for a 15-m bilayer electrode. However, the PCE of the
graphene/PMII was found to decrease from 2.10% for

the TiO2 layer.
The effect of thickness of the TiO2 layer on PCEs of
graphene and SWCNTs quasi solid-state electrolytes-based
DSSCs was demonstrated by Byrne et al.292 The PCE
of a SWCNT-based quasi solid-state electrolyte increased
from 1.43% to 3.49%. The PCE of graphene and SWC-
NTs increased from 2.50% to 2.93%. The graphene-
containing quasi solid-state electrolytes showed a small
decrease in PCE, from 2.10% to 1.96%, due to the
high viscosity of the electrolyte. RCT decreased from
67  cm2 for only PMII to 1.35  cm2 after adding
graphene-SWCNT into PMII, 50 times lower compared
to pure PMII as measured by electrochemical impedance
REVIEW
a 10 m–thick opaque electrode to 1.96% for a 15-m
bilayer electrode.
Graphene, GO, and nanographite were incorporated
by Yuan et al.293 into microporous poly(acrylic acid)-
cetyltrimethylammonium bromide (PAA-CTAB) conduct-
ing gel electrolytes for DSSCs, which exhibited PCEs
of 7.06%, 6.35%, and 6.17%, respectively, in compari-
son to a PCE of 6.07% from a pure PAA-CTAB-based
DSSC. In another study, Yuan et al.294 used microporous
a polyacrylate–poly(ethylene glycol) (PAA–PEG) matrix
to incorporate graphene, GO, and graphite. Figure 23
shows the photocurrent density–voltage characteristics of

Fig. 22. Stability of PCEs of DSSCs based on pure graphene, SWC-
NTs, graphene/SWCNT electrolytes, and PMII reference only. Reprinted
with permission from [291], I. Ahmad, et al., Graphene, carbon nano-
tube and ionic liquid mixtures: Towards new quasi solid-state electrolytes
for dye sensitised solar cells. J. Mater. Chem. 21, 16990–16996 (2011).
© 2011, Royal Society of Chemistry.
Fig. 23. J –V characteristics of DSSCs based on gel electrolytes
of PAA–PEG/graphene, PAA–PEG/graphene oxide, PAA–PEG/graphite,
and PAA–PEG. Reprinted with permission from [294], S. Yuan, et al.,
Efficient quasi-solid-state dye-sensitized solar cells from graphene incor-
porated conducting gel electrolytes. J. Mater. Chem. A 2, 2814–2821
(2014). © 2014, Royal Society of Chemistry.

Sci. Adv. Mater., 7, 1863–1912, 2015 1899

 Graphene-Based Dye-Sensitized Solar Cells: A Review
DSSCs based on gel electrolytes of PAA–PEG/graphene,
PAA–PEG/GO, PAA–PEG/graphite, and PAA–PEG. The
conducting materials can form interconnected channels
within a microporous PAA–PEG matrix, which can facil-
itate the triiodide reduction in DSSCs from the inter-
face of Pt/gel electrolyte to microporous conducting gel
electrolyte. DSSCs fabricated using PAA–PEG/graphene,
PAA–PEG/GO, and PAA–PEG/graphite showed PCEs of
7.74%, 6.49%, and 5.63%, respectively, much higher com-
pared to a PCE of 5.02% for a pure PAA–PEG-based
DSSC. The PCE of a PAA–PEG/graphene-based DSSC
is 1.5 times higher than that of pure PAA–PEG, showing
significant enhancement due to graphene inclusion. This
indicates applications of microporous-conducting gel elec-
trolytes in quasi solid-state DSSCs.
Microporous polyacrylamide (PAAm) and graphene
conducting gel electrolytes for quasi solid-state QDSSCs
were used by Duan et al.,295 which showed a PCE of
2.34%, compared to 1.64% for a microporous PAAm-
based device. The PCE increased from 2.24% to 2.34%
for the microporous PAAm-7 wt% graphene gel elec-
trolyte and from 1.36% to 1.64% for microporous PAAm
REVIEW
gel electrolyte. The PCE values of DSSCs for PAAm-
3 wt% graphene, PAAm-5 wt% graphene, PAAm-7 wt%
graphene, PAAm-9 wt% graphene, and pure PAAm-based
gel electrolytes were 1.67%, 1.84%, 2.24%, 1.88%, and
1.36%, respectively. RCT of 8.718  cm2 3.381  cm2 ,
2.075  cm2 , 3.094  cm2 , and 12.57  cm2 for
PAAm-3 wt% graphene, PAAm-5 wt% graphene, PAAm-
7 wt% graphene, PAAm-9 wt% graphene, and pure PAAm,
respectively, supported the similar trend, showing highest
charge transfer and electrocatalytic activity for the PAAm-
7 wt% graphene gel electrolyte. Lin et al.296 prepared
ionic liquid-tethered graphene oxide (IL-GO) by tether-
ing 1-(3-aminopropyl)-3-methylimi-dazolium bromide to a
GO structure and thereafter using anion exchange with
bis(trifluoromethanesulfonyl)imide ions. The ionic liquid-
based composite electrolytes were prepared for DSSCs
from IL-GO and 1-propyl-3-methylimidazolium iodide
(PMII). The IL-GO was found to increase the conductiv-
ity of the electrolyte, and the short-circuit current density,
open-circuit voltage, and PCE of DSSCs. The DSSCs con-
taining 4 wt% of IL-GO composite electrolytes exhibited
a PCE of 7.04%. The IL-GO/IL composite electrolytes
offer an alternate to volatile liquid electrolytes for DSSCs.
Chan et al.297 synthesized a hybrid polymer gel elec-
trolyte using polyacrylonitrile (PAN) and graphene for a
quasi-solid DSSC. The exfoliated 2D graphenes were used
within a polymer gel electrolyte to facilitate the diffusion
of iodide/triiodide (I− /I−
3  redox couples in the electrolyte.
The ratio of graphene was varied in the PAN polymer gel
electrolyte to optimize the ionic conductivity and photo-
voltaic properties of the DSSC. The PCE of the DSSC
with 0.2 wt% graphene was 5.41%, 1.5 times higher than
that of the liquid-state cell (PCE, 3.72%).
1900
Singh and Nalwa
The graphene flakes in ionic liquid (IL) 1-propyl-3-
methyl imidazolium iodide (PMII) were used by Brennan
et al.298 to prepare a new electrolyte for DSSCs. The 3 wt%
of graphene nanoflakes was mixed into the ionic liquid
PMII for the new electrolytes, which showed more than 25
times enhancement in PCE of the DSSC. Such an improve-
ment in PCE can be result from graphene being both an
efficient charge transfer agent and a catalyst for I−3 reduc-
tion in the electrolyte. The interactions between the ionic
liquid and graphene may form self-organized assemblies
that facilitate easy electron transfer through the electrolyte
and also form quasi-solid electrolytes at higher concentra-
tions of graphene. The quasi solid-based DSSC could solve
problems of electrolyte leakage and stop degradation of
materials. Akhtar et al.299 developed a new composite elec-
trolyte from graphene and polyethylene oxide (PEO) for
DSSCs. The graphene–PEO composite electrolyte showed
rapid generation of iodide ions in the redox couple. A com-
posite electrolyte containing 0.5 wt% graphene showed
ionic conductivity of 3.32 mS/cm, more than PEO and
other composite electrolytes. A DSSC device containing
0.5 wt% graphene exhibited a short-circuit current of 18.32
mA cm−2 , an open-circuit voltage of 0.592 V, fill factor
of 0.48, and yielded a PCE of 5.23%. The high photo-
voltaic performance may be due to efficient generation of
iodide ions in the redox couple and high ionic conductiv-
ity. Velten et al.164 used FLG nanoribbons in the electrolyte
of an iodide/triiodide redox couple in a DSSC device to
generate optical transparency and examine the reversible
bleaching effect of the electrolyte on the DSSC device.
The PCE of DSSC with FLG nanoribbons showed no
degradation after the electrolyte turned optically transpar-
ent. The incorporation of FLG nanoribbons into the elec-
trolyte by ultrasonication increased PCE for an inverted
DSSC device from 5.75% to 7.01% due to an increase in
photocurrent density from 9.9 mA/cm2 to 12.1 mA/cm2 .
This study indicated that the electrolyte bleaching effect
can be applied to enhance the PCE of inverted and
tandem DSSCs. Chen et al.300 reported an all-graphene
quasi solid-state DSSC having a graphene/polyacrylate-
poly(ethylene glycol) (PAA–PEG) gel electrolyte with
iodide/triiodide redox couple, a graphene/TiO2 photoan-
ode, and a graphene counter electrode where a PCE of
3.62% was measured. Gun et al.301 demonstrated the use
of graphene oxide–acetonitrile organogel as quasi-solid
electrolyte for an iodide/triiodide redox couple in DSSCs.
The PCE of DSSCs with 1% graphene oxide gel elec-
trolytes was found to be 7.5%, which is higher than a PCE
of 6.9% for pure liquid electrolyte without any graphene
oxide content. Jung et al.302 functionalized graphene using
1-octyl-2,3-dimethylimidazolium iodide (ODI) as an elec-
tron acceptor for an iodide/triiodide redox couple in a
DSSC, which showed higher electrocatalytic activity. The
ODI-graphene electrolyte-based DSSC devices showed a
higher PCE than an electrolyte without graphene. Table VI
Sci. Adv. Mater., 7, 1863–1912, 2015
Singh and Nalwa Graphene-Based Dye-Sensitized Solar Cells: A Review

Table VI. Graphene-based materials used as quasi solid-state electrolytes in DSSCs. Photocurrent density (JSC , open-circuit voltage (VOC , fill factor
(FF), and power conversion efficiency (PCE, , redox couples, and dyes used in fabricating DSSCs with graphene electrolytes are summarized.

Graphene based electrolytes Redox couples Dye JSC (mA/cm2  VOC (V) FF (%) PCE (, %) Ref.

Graphene (30 wt%)/PMIIa ionic liquid I− /I−3 N719 530 062 49 210 [291]
SWCNTs (7 wt%)/PMII ionic liquid I− /I−3 N719 519 054 41 143 [291]
SWCNTs (3 wt%)/graphene (12 wt%) I− /I−3 N719 732 059 44 250 [291]
SWCNTs (12 wt%)/graphene (3 wt%) I− /I−3 N719 466 0561 43 139 [291]
PMII ionic liquidd I− /I−3 N719 037 057 64 016 [291]
Graphene (12 wt%)/SWCNTs (3 wt%)/PMII I− /I−3 N719 789 064 58 293 [292]
Graphene (30 wt%)/PMII ionic liquid I− /I−3 N719 689 060 47 196 [292]
SWCNTs (7 wt%)/PMII ionic liquid I− /I−3 N719 735 071 67 349 [292]
PAA-CTABb /graphene gel I− /I−3 N719 1383 0731 698 706 [293]
PAA-CTAB/graphene oxide gel I− /I−3 N719 1374 0687 627 635 [293]
PAA-CTAB/nanographite gel I− /I−3 N719 1230 0669 750 617 [293]
PAA-CTAB gel I− /I−3 N719 1215 0696 718 607 [293]
PAA-PEGc /graphene I− /I−3 N719 150 0731 68 774 [294]
PAA-PEG/graphene oxide I− /I−3 N719 150 0696 69 649 [294]
PAA-PEG/graphite I− /I−3 N719 122 0675 60 563 [294]
PAA-PEG I− /I−3 N719 113 0663 66 502 [294]
Polyacrylamide (PAAm) I− /I−3 N719 821 0533 311 136 [295]
Microporous polyacrylamide (PAAm) I− /I−3 N719 878 0554 337 164 [295]
PAAm-7 wt% Graphene I− /I−3 N719 963 0590 394 224 [295]
Microporous PAAm-7 wt% Graphene I− /I−3 N719 1147 0590 346 234 [295]
Graphene nanoflakes (1 wt%)/PMII I− /I−3 Z907d 858 061 49 260 [298]
PMII ionic liquid I− /I−3 Z907 059 057 31 010 [298]

REVIEW
Graphene/polyethylene oxide I− /I−3 N719 1832 059 48 523 [299]
Graphene nanoribbons (inverted DSSC) I− /I−3 N719 9984 0760 758 575 [164]
Graphene nanoribbons/electrolyte I− /I−3 N719 12185 0760 757 701 [164]

Notes: a PMII = 1-methyl-3-propylimidazolium iodide (PMII) ionic liquid; b poly(acrylic acid)-cetyltrimethylammonium bromide (PAA-CTAB); c polyacrylate–poly(ethylene
glycol) (PAA–PEG); d (Z907) cis-Bis(isothiocyanato)(2,2 -bipyridyl-4,4 -dicarboxylato)(4,4 -di-nonyl-2 -bipyridyl)ruthenium(II).

summarizes graphene-based materials used as quasi solid-
state electrolytes in DSSCs. Photocurrent density (JSC ,
open-circuit voltage (VOC , fill factor (FF), and power
conversion efficiency (PCE, , redox couples, and dyes,
used in fabricating DSSCs with graphene electrolytes, are
summarized. The above studies show that graphene-based
materials can be incorporated into electrolytes as an addi-
tive for enhancing the PCE of DSSCs.
7. GRAPHENE-BASED PHOTOSENSITIZERS
Photosensitizing dyes play an important role in harvest-
ing sunlight in a DSSC device. A photosensitizer with
a longer range of spectral absorption can absorb more
sunlight. Although ruthenium-based dyes have been com-
monly used as photosensitizers in fabricating DSSCs,
hundreds of different types organic dyes have been syn-
thesized. Ye et al.145 reviewed photosensitizers based on
ruthenium polypyridyl dyes, porphyrin dyes, and quantum
dot sensitizers, halide perovskites, upconversion nanopar-
ticles, etc. Hagfeldt et al.123 also reviewed all types of
synthetic organic dyes explored to enhance the PCE of
DSSCs. A single layer of graphene shows 97.7% optical
transparency as reported by Nair et al.,23 and so it has gen-
erated some interest in the study of graphene-based materi-
als as photosensitizers for DSSCs. Yan et al.303 synthesized
black graphene quantum dots (GQDs) with uniform size to
be used as photosensitizers for solar cells. GQDs consist
of 168 conjugated carbon atoms and are highly soluble in
organic solvents such as toluene, chloroform, and tetrahy-
drofuran. The absorption spectrum in dichloromethane
showed an absorbance maximum at 591 nm with molar
extinction coefficients of 10 × 105 M−1 cm−1 , which was
an order of magnitude larger compared to metal complexes
used in DSSCs. Energy levels calculated from the tight
binding model showed the highest occupied and the lowest
unoccupied molecular orbitals (HOMO and LUMO) at 5.3
and 3.8 eV, respectively, which is below the vacuum level,
which supports using GQDs as a sensitizer in DSSCs.
Hamilton et al.304 prepared assemblies of colloidal GQDs
with peripheral 2 ,4 ,6 -trialkyl phenyl groups, which were
soluble in common organic solvents. DSSCs sensitized by
GQDs exhibit higher PCEs.
In an interesting study, Ji et al.305 reported in situ
preparation of graphene molecules (GMs) on a TiO2 sur-
face using a functionalized polyphenylene precursor pre-
adsorbed on a TiO2 surface via Scholl reaction. Figure 24
shows the in situ synthesis of graphene molecules on
TiO2 surface from polyphenylene precursor (P1) function-
alized with COOH groups. The nanocrystalline TiO2 film
is exposed to a dichloromethane (CH2 Cl2  solution of P1
at room temperature, which facilitates adsorption of P1
onto the TiO2 film. The TiO2 /P1 film is washed with

Sci. Adv. Mater., 7, 1863–1912, 2015 1901

 Graphene-Based Dye-Sensitized Solar Cells: A Review Singh and Nalwa
REVIEW

Fig. 24. In situ synthesis of graphene molecules (GMs) on TiO2 surface. The color change of TiO2 /P1 after Scholl reaction, energy diagram of the
FTO/TiO2 /GM/electrolyte/Pt/FTO electrode based device, and J –V characteristics of a GM-based device in dark (black) and under one sun, AM 1.5
illumination (red). Reprinted with permission from [305], Z. Ji, et al., In situ synthesis of graphene molecules on TiO2 : Application in sensitized solar
cells. ACS Appl. Mater. Interfaces 6, 20473–20478 (2014). © 2014, American Chemical Society.

dichloromethane and exposed to an argon-saturated solu-
tion of FeCl3 in CH3 NO2 /CH2 Cl2 at room temperature.
Within a few seconds, the film became colored, which
indicates conjugation of aromatic phenyl rings of the
surface-adsorbed P1 molecules. The chemical composition
of GMs was found to be C132 H36 (COOH)2 . The surface-
adsorbed GMs structurally are equivalent to a solution-
processed method and eliminate aggregations of GMs.
The surface-adsorbed GMs can be reduced or oxidized
by interfacial charge transfer, in addition to functioning
as a sensitizer for metal oxides in solar cells. The sen-
sitized solar cells fabricated from mesoscopic GM/TiO2
films and iodide-based liquid electrolyte exhibited a JSC of
2.5 mA cm−2 , a VOC of 0.55 V, and a FF of 0.65, resulting
in a PCE of 0.87%, which is the highest efficiency for the
GM-based sensitized solar cell. The performance of GM-
based sensitized solar cell devices was reproducible and
showed stability up to 3 weeks.
In another study, Zhang et al.306 prepared assembly of
ZnS nanoparticles on a GO sheet by a wet chemistry pro-
cess where the rGO and interfacial contact between ZnS
nanoparticles and the rGO sheet were established. The
ZnS–RrGO nanocomposites function as a photosensitizer
for ZnS instead of acting as an electron reservoir. Williams
et al.307 suggested graphene-based materials as hot carrier
chromophores for solar cells. The graphene quantum dots
(GQDs) were anchored to the surface of TiO2 via car-
boxyl group linkers. Mihalache et al.308 developed a hybrid
DSSC using GQDs as co-sensitizer. The TiO2 /GQD/dye
hybrid solar cell used standard N3 dye, however, when
GQDs were used with N3 dye as co-sensitizers, an
enhancement in PCE was observed. The recombination
processes at the interface of TiO2 /electrolyte was hin-
dered by the GQDs. San Esteban and Enriquez309 used
anthocyanin dye co-adsorbed with graphene for enhanc-
ing the PCE of DSSCs. Graphene was mixed with antho-
cyanin dye and then co-adsorbed on the mesoporous titania
surface. PCE values were compared with DSSCs hav-
ing anthocyanin only and graphene/titania composite. The
incorporation of graphene led to increased PCEs for TiO2
as a photoanode composite and for anthocyanin:graphene
dispersion. The PCE increased by 2.4 times for antho-
cyanin:graphene because graphene offered additional
conducting pathways for electrons. Supur et al.310 syn-
thesized ordered assemblies of GO layers functionalized
with cationic tetrakis(1-methylpyridinium-4yl)porphyrin
p-toluene sulfonate (Por), N ,N  -di(2-(trimethylammonium
iodide) ethylene) perylenediimide (PDI), and anionic
Zn(II) phthalocyanine tetrasulfonic acid (ZnPc) dyes. In
(GO-Por-PDI-ZnPc)n hybrid assemblies, the ZnPc acts as
electron donor and PDI acts as an electron acceptor. The
GO-based 3D assemblies harvest the sunlight from UV to
near infrared (NIR) regions. There has been some progress

1902 Sci. Adv. Mater., 7, 1863–1912, 2015

Singh and Nalwa
in using graphene-based materials as photosensitizers, but
overall it is a nascent area of research with more signifi-
cant work to be done for achieving high PCEs for DSSCs
with graphene sensitizers if ever matching with conven-
tional organic photosensitizing dyes.
The progress made in different types of thin film solar
cells over the period of 1990–2015 for perovskite-based
materials, organic photovoltaics (OPV), amorphous sili-
con (a-Si), DSSCs, and quantum dots (QDs) have been
reviewed and compared.311–316 The perovskite materials
show steady progress in solar cell devices. The PCEs of
perovskite-based hybrid halide solar cells have been con-
tinuously increasing, which stood at 15.9% as of 2014,
and which has reached up to 20.1% in 2015.17 The
authors present here research articles from easily acces-
sible sources, discussed here in detail. A large number
of research articles have been published in the literature
on DSSCs so interested readers are advised to look for
more information accordingly. The demand for energy is
steadily growing in our daily life where solar energy has
been identified as one of the cleanest sources. The chal-
lenge is to find alternatives to the traditional semiconductor
solar cells. From the commercial point of view, TiO2 is
easily available at low cost of production and has no tox-
icity; therefore, TiO2 -based DSSCs offer advantages over
silicon-based photovoltaic solar cells. Current research is
aimed at finding a new generation of commercially viable
inorganic and organic materials for dye-sensitized and
bulk heterojunction solar cells. Some of the inorganic and
organic materials used in today’s photovoltaic solar cell
technologies are toxic, carcinogenic, and environmentally
hazardous; therefore, ecofriendly nontoxic materials mim-
icking the natural process of photosynthesis are in great
demand. Another challenge is the degradation of solar
cell devices under ambient conditions. Besides achieving
higher photovoltaic performance of DSSCs, major prob-
lems such as environmental stability, toxicity to humans
and the environment, cost-effective production, and ease
of fabrication are important challenges for using graphene
and graphene-based materials for fabricating DSSCs for
commercial purposes and large-scale industrial production.
8. CONCLUSION AND PERSPECTIVE
In this article we have summarized the photovoltaic data
of various types of graphene-based DSSCs. A high PCE
of 13% for a DSSC based on graphene nanoplatelets
counter electrodes with a push–pull porphyrin sensi-
tizer using a Co(II)/Co(III) redox mediator has been
achieved.168 DSSCs based on edge-fluorinated and edge-
carboxylated graphene nanoplatelets in [Co(bpy)3]2+/3+
with JK-306 photosensitizer exhibited PCEs of 10.1%172
and 9.31%,174 respectively, which is higher than that of
a standard Pt counter electrode. DSSCs consisting of
graphene nanocomposites with titanium dioxide TiO2 , car-
bon nanotubes, polymers, semiconductors, ionic liquids,
Sci. Adv. Mater., 7, 1863–1912, 2015
Graphene-Based Dye-Sensitized Solar Cells: A Review
metals, upconversion nanoparticles, and halide perovskites
were discussed in detail and compared with standard ref-
erence solar cells. Graphene and graphene oxide-based
solar cells have emerged as an important class of pho-
tovoltaic material in the past few years. Graphene–TiO2
nanocomposites-based photoanodes have been extensively
studied, exhibiting much better photovoltaic performance
than pure TiO2 -based DSSCs. The photovoltaic perfor-
mance of DSSCs is significantly influenced by a number of
factors, including types of electrode materials, electrolytes,
and photosensitizers, as well as by the solar cell’s struc-
ture. The novel porphyrin dyes, halide perovskites, and
upconversion nanoparticles seem to play a role in enhanc-
ing the PCE of graphene-based DSSCs. Additionally,
nanofabrication and processing of graphene-based mate-
rials into quantum dots, nanofoams, nanoplatelets, aero-
gels, fibers, multilayers, paper, sheets, nanoparticles, and
nanoflakes, as well as chemical functionalization and het-
eroatomic doping, also influence the PCE of DSSCs.
Therefore, a number of factors can affect the PCE of
graphene-based DSSCs. Graphene-based materials show a
great potential to replace critically important metal such
as Pt as the counter electrodes for fabricating DSSCs.
REVIEW
The low loading contents of graphene not only offer
excellent optical transparency and mechanical flexibility
to DSSC devices, but also higher PCE, and in some
cases outperform the conventional Pt counter electrode.
Heteroatom doping was found to significantly improve
the photovoltaic performance of graphene-based DSSCs.
Graphene-based materials used as quasi solid-state elec-
trolytes for DSSCs also are promising. The develop-
ment of solution-processable GQDs as photosensitizers
for solar cells is quite interesting, but much work is
needed to achieve higher PCE. Organic dye molecules
such as pull-push porphyrins show excellent potential
for further improving PCE of graphene-based DSSCs
where chemists could significantly contribute to designing
novel photosensitive chromophores. Graphene materials
offer tremendous opportunities for chemical functional-
ization and compatible integration with other inorganic
and organic materials; therefore, a significant improve-
ment in graphene-based DSSCs is anticipated in the near
future. Graphene-based materials may cause cytotoxicity
to human like other nanostructured materials317–325 and
render susceptibility to environmental degradation. In gen-
eral, one of the main disadvantages of DSSCs is their
liquid redox electrolytes which are unstable at high or
low temperatures and the organic solvents used therein are
not only toxic and volatile but also hazardous to human
health and environment, and dissolve sealants and metal
connectors, therefore, replacing the liquid redox elec-
trolytes with solid systems is highly desirable. Although
significant developments have been made in the applica-
tions of graphene-based materials for DSSCs, there are
a few research and development directions to optimize
1903
 Graphene-Based Dye-Sensitized Solar Cells: A Review
both graphene materials and their photovoltaic proper-
ties. The development of new graphene functionalized
robust materials and composites, as well as new sensitizing
dyes and electrolytes, could pave a way for highly effi-
cient DSSCs. Besides higher photovoltaic performance of
graphene-based DSSCs, achieving environmental stability,
nontoxicity of liquid electrolytes, cost-effectiveness, and
ease of fabrication are still important challenges for indus-
trial applications. Graphene-based DSSCs are improving
steadily but slowly and have great potential for large-scale
commercial production.
Disclaimer
The scientific data contained in this review article are for
information purposes only. The authors, editors, and pub-
lisher cannot accept the liability of any kind whatsoever
for the accuracy of contents and data or any omissions or
errors or a claim of completeness.
Acknowledgments: Eric Singh expresses his sincere
thanks to Martin Kirby at the Hart High School for his
excellent teaching in Advanced Placement (AP) Physics B
REVIEW
and C, and his continuous encouragement. The authors are
thankful to Dr. Ahmad Umar of Najran University in Saudi
Arabia for providing valuable comments. The authors are
grateful to Professor Qunwei Tang of Ocean University of
China for providing reprints of his research activities.
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