Critical Reviews in Solid State and Materials Sciences

ISSN: 1040-8436 (Print) 1547-6561 (Online) Journal homepage: http://www.tandfonline.com/loi/bsms20

Synthesis of Graphene and Its Applications: A

Review

Wonbong Choi , Indranil Lahiri , Raghunandan Seelaboyina & Yong Soo Kang

To cite this article: Wonbong Choi , Indranil Lahiri , Raghunandan Seelaboyina & Yong Soo Kang
(2010) Synthesis of Graphene and Its Applications: A Review, Critical Reviews in Solid State and
Materials Sciences, 35:1, 52-71, DOI: 10.1080/10408430903505036

To link to this article: https://doi.org/10.1080/10408430903505036

Published online: 05 Feb 2010.

Submit your article to this journal

Article views: 21475

View related articles

Citing articles: 537 View citing articles

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=bsms20
Critical Reviews in Solid State and Materials Sciences, 35:52–71, 2010
Copyright
c Taylor and Francis Group, LLC
ISSN: 1040-8436 print / 1547-6561 online
DOI: 10.1080/10408430903505036

Synthesis of Graphene and Its Applications: A Review

Wonbong Choi,1,∗ Indranil Lahiri,1 Raghunandan Seelaboyina,1

and Yong Soo Kang2
1
Nanomaterials and Devices Laboratory, Florida International University, Miami, Florida, USA
2
Department of Energy Engineering, Hanyang University, Seoul, Korea

Graphene, one-atom-thick planar sheet of carbon atoms densely packed in a honeycomb

crystal lattice, has grabbed appreciable attention due to its exceptional electronic and op-
toelectronic properties. The reported properties and applications of this two-dimensional
form of carbon structure have opened up new opportunities for the future devices and
systems. Although graphene is known as one of the best electronic materials, synthesiz-
ing single sheet of graphene has been less explored. This review article aims to present an
overview of the advancement of research in graphene, in the area of synthesis, properties
and applications, such as field emission, sensors, electronics, and energy. Wherever applica-
ble, the limitations of present knowledgebase and future research directions have also been
highlighted.

Keywords electronic properties, growth techniques, sensors, transistors, electrodes, rechargeable

battery

Table of Contents

1. INTRODUCTION ...................................................................................................................................................53

2. PROPERTIES OF GRAPHENE ..............................................................................................................................53

2.1. Properties of Single- and Bi-layer Graphene ........................................................................................................53
2.2. Properties of Few-Layer Graphene ......................................................................................................................55

3. GRAPHENE SYNTHESIS METHODS ...................................................................................................................56

3.1. Exfoliation and Cleavage ...................................................................................................................................56
3.2. Thermal Chemical Vapor Deposition Techniques ..................................................................................................57
3.3. Plasma Enhanced Chemical Vapor Deposition Techniques ....................................................................................58
3.4. Other Processing Routes ....................................................................................................................................58
3.4.1. Chemical Methods ..................................................................................................................................58
3.4.2. Thermal Decomposition of SiC ................................................................................................................59
3.4.3. Thermal Decomposition on Other Substrates .............................................................................................60
3.4.4. Un-zipping CNTs and Other Methods .......................................................................................................60

4. APPLICATIONS OF GRAPHENE ..........................................................................................................................61

4.1. Graphene Field Emission (FE) ............................................................................................................................61
4.2. Graphene Based Gas and Bio Sensors .................................................................................................................61
4.3. Field Effect Transistors (FET) ............................................................................................................................64
4.4. Transparent Electrodes .......................................................................................................................................65
4.5. Battery .............................................................................................................................................................66

5. SUMMARY .............................................................................................................................................................67

REFERENCES ............................................................................................................................................................67
∗
E-mail: choiw@fiu.edu
52
 SYNTHESIS OF GRAPHENE AND ITS APPLICATIONS
1. INTRODUCTION
In recent years graphene, a one-atom-thick planar sheet of
sp2 -bonded carbon atoms densely packed in a honeycomb crys-
tal lattice, has grabbed appreciable attention to be used as a next
generation electronic material, due to its exceptional proper-
ties including high current density, ballistic transport, chemical
inertness, high thermal conductivity, optical transmittance and
super hydrophobicity at nanometer scale.1,2 The first graphene
was extracted from graphite using a technique called microme-
chanical cleavage.3 This approach allowed easy production of
high-quality graphene crystallites and further led to enormous
experimental activities.4
Intrinsic graphene is characterized as a semi-metal or zero-
gap semiconductor and its unique electronic properties produce
an unexpectedly high opacity for an atomic monolayer, with a
startlingly low absorption ratio of 2.3% of white light.5 Electri-
cal characterization has shown a remarkably high electron mo-
bility at room temperature, with experimentally reported values
in excess of 15,000 cm2 V−1 s−1 .3 The corresponding resistivity
of the graphene sheet would be 10−6 ohm–cm, less than the re-
sistivity of silver, the lowest resistivity substance known at room
temperature.6 Graphene nano ribbons (GNRs), with zigzag or
armchair configuration, show different electrical property; the
zigzag GNRs are metallic, while armchairs can be either metal-
lic or semiconductor. The energy band gap of armchair GNRs
are inversely proportional to the width.6
Exceptional electrical properties of graphene have attracted
applications for future electronics such as ballistic transistors,
field emitter, components of integrated circuits, transparent con-
ducting electrodes and sensors. Graphene has a high electron (or
hole) mobility as well as low Johnson noise (electronic noise
generated by the thermal agitation of the charge carriers inside an
electrical conductor at equilibrium, which happens regardless of
any applied voltage), allowing it to be utilized as the channel in a
field effect transistor (FET). Combination of excellent electrical
property and low noise make graphene an excellent sensor. Its
entire volume is exposed to the surrounding due to its 2D struc-
ture, making it very efficient to detect adsorbed molecules. The
high electrical conductivity and high optical transparency pro-
mote graphene as a candidate for transparent conducting elec-
trodes, required for applications in touch-screens, liquid crystal
displays, organic photovoltaic cells and organic light-emitting
diodes (OLEDs).6
Most of these interesting applications require growth of
single-layer graphene on a suitable substrate, which is very
difficult to control and yet to be achieved. Many reports are
available on graphene synthesis and most of those are based
on mechanical exfoliation from graphite or thermal graphiti-
zation of a SiC surface6,8−11 and recently, by chemical vapor
deposition.12 This article begins with a brief overview of prop-
erties of graphene and then reviews synthesis technologies, to-
gether with a brief discussion of their feasibility and potential
applications including field emission, electronics, sensors and
energy.
53
2. PROPERTIES OF GRAPHENE
Keeping in view of the scientific interest generated by
graphene and its possible future involvement in electronics and
sensing applications, lot of research effort are devoted in un-
derstanding the structure and properties of graphene. Detailed
discussion of properties of graphene is out of the scope of this
article, which may be found in some recent review articles.13,14
This section aims to introduce the basic properties of graphene,
so that the applications are well understood. The following sub-
sections will discuss, in short, attractive properties of single-,
bi- and few-layer graphene.
2.1. Properties of Single- and Bi-layer Graphene
Before introducing the properties of graphene, it is imperative
to understand the structure of graphene. A single-layer graphene
is defined as a single two-dimensional hexagonal sheet of car-
bon atoms (Figure 1a).15 Bi-layer and few-layer graphene has
2 and 3 to 10 layers of such two-dimensional sheets, respec-
tively. Graphene structures consisting more than 10 such layers
are considered as thick graphene sheet and are of less scien-
tific interest. In bi- and few-layer graphene, C atoms can be
stacked in different ways, generating hexagonal or AA stack-
ing, Bernal or AB stacking and rhombohedral or ABC stack-
ing (Figure 1b). Graphene has a hybridized sp2 bonding. It
shows three in-plane σ bonds/atom and π orbitals perpendic-
ular to the plane (Figure 1c). While the strong σ bonds work
as the rigid backbone of the hexagonal structure, the out-of-
plane π bonds control interaction between different graphene
layers.
The simplest way to differentiate between different thick-
nesses of graphene is through optical microscopy on Si substrate
with a 285 nm SiO2 capping layer, by using contrast spectra.16
The best way to understand the structure of graphene is by TEM.
However, TEM, being a destructive analytical tool, may not be
suitable always. Careful investigation of local Raman spectra,
obtained from different portions of graphene can give an idea
about the thickness of the graphene (Figure 2). Number of layers
in a graphene film can be estimated from the intensity, shape
and position of the G and 2D bands. While 2D-band changes
its shape, width and position with increasing number of layers,
G-band peak position shows a down-shift with number of layers
(Figure 2b).
Single-layer graphene (SLG) is unique in electronic struc-
ture, as it shows band-overlap in two conical points (K and
K ) in the Brillouin zone (Figure 3). The charge carriers in
this structure, known as mass-less Dirac fermions, are electrons
losing their rest mass, m0 and can best be described by (2 +
1)-dimensional Dirac equations.13,14,18 Thus, SLG is expected
to show some unusual properties, as compared with metals and
semiconductors and typical of a semi-metal.
SLG shows room-temperature ambipolar characteristics,
i.e., the charge carriers can be alternated between holes and
electrons depending upon the nature of the gate voltage.3
54 W. CHOI ET AL.

FIG. 1. (a) Graphene structure of single two-dimensional hexagonal sheet of carbon atoms, (b) three most common structures and
stacking sequences of graphene and (c) Schematic of the in-plane σ bonds and the π orbitals perpendicular to the plane of the
graphene sheets (b and c reprinted with permission from Hass et al.15 Copyright 2008: IOP).

Anomalous (half-integer) quantum Hall effect (QHE), at low
temperature and room temperature has also been reported for
this structure.19,20 These unusual properties of SLG has made
it suitable for applications in electronics, as well as one of the
most suitable materials for studying basic quantum physics phe-
nomena. Among other properties that have received consider-
able interest, the most important is the gas sensing ability. It
was found that adsorbed gas molecules modify the local carrier
concentration and a subsequent change in the resistance. Us-
ing this property of SLG, Schedin and collegoues21 prepared
micron-level gas sensors, which can detect adsorption and des-
orption of single molecules of gases like CO, H2 O, NH3 and
NO2 . Molecular sensing capability could be achieved in this
material, as graphene is electronically a very good low-noise
material. Low-noise electronic structure also helped in prepara-
tion of truly two-dimensional nano electromechanical systems
(NEMS) from SLG.22
Single-layer graphene is also being credited as one of
the strongest materials. Strength of a defect-free, mono-layer
graphene was measured by using nano-indentation technique
and also modeled using atomistic simulation method.23,24

FIG. 2. (a) TEM images of graphene films with different thick-

nesses, (b) typical Raman spectra obtained from different thick-
ness regions of graphene film (with increasing number of lay- FIG. 3. Electronic band structure of single-layer graphene.
ers from bottom to top). (Reprinted with permission from the (Reprinted with permission from Rao et al.13 Copyright 2009:
Macmillan Publisher Ltd: Nature,17 Copyright 2009.) Royal Society of Chemistry.)
 SYNTHESIS OF GRAPHENE AND ITS APPLICATIONS
Young’s modulus of this structure was predicted to be ∼1.0 TPa,
in both the methods. Using such mechanically strong graphene
sheets, Chen et al. have prepared graphene papers, which were
found to be bio-compatible also.25 Such exciting new properties
of graphene are expected to open up new frontiers in graphene
application.
Bi-layer graphene shows a gapless state with parabolic bands
touching at K and K , in contrast to conical bands of single-layer
graphene. Thus, bi-layer graphene is considered as a gapless
semiconductor. In contrast to single-layer graphene, charge car-
riers in bi-layer graphene have finite mass and called massive
Dirac fermions. The structure also shows an anomalous QHE,
but different from that of single-layer graphene and as a result, it
remains metallic at the neutrality points.26 However, application
of a gate voltage can change the carrier concentration and intro-
duces asymmetry between the two layers. This results in forma-
tion of a semiconducting gap and restoration of normal QHE.27
However, Zhou et al. has shown that an energy band gap
of ∼0.26 eV is produced in graphene, when it is epitaxially
grown on SiC substrate.28 Such a structure, with a finite band-
gap, makes graphene more suitable for application in electronics
industries. It was found that the band gap decreases with increas-
ing number of layers and approaches zero, as the structure has
more than four layers. This substrate-induced band gap opening
was proposed to be caused by graphene-substrate interaction
and breaking of sublattice symmetry. In a related study, it was
claimed that graphene, epitaxially grown on C-terminated sur-
face of 4H-SiC, has a different stacking sequence.29 As a result,
the structure, irrespective of its number of layers (up to ∼10
layers thick), shows an electronic structure similar to that of
single-layer graphene and behaves like SLG. Thus, synthesis
methods play an important role in determining the structure and
properties of graphene.
In an interesting application of gaseous molecule adsorption
on epitaxially grown graphene surface, it was shown that a
controlled molecular treatment (by gases like H2 and NO2 ) can
trigger a reversible metal-to-insulator transition in single- and
bi-layer graphene.30,31 Treatment of graphene sheets by atomic
hydrogen is known to produce insulating or semiconducting
graphane, a two-dimensional hydrocarbon structure. Moreover,
single- and bi-layer graphene shows very high transparency for
light waves in the range of ultra-violet to infra-red, making it
suitable for applications as transparent electrode in solar cells.32
2.2. Properties of Few-Layer Graphene
Analysis of the band structure of few-layer graphene (FLG)
shows no gap. The structure becomes increasingly metallic with
more number of layers in it.33 FLG shows very high surface area,
almost comparable to that of single-layer graphene. As a result,
it shows good gas adsorption property, which is verified for H2
and CO2 .34 At 300K and 100 bar, FLG samples were found to
uptake up to 3 wt% H2 , which is very high.
FLG has also shown good capability to be functionalized
by different covalent and non-covalent modifications, in order
55
to solubilize them in various solvents. Amide-functionalized
FLG was found to be soluble in organic solvents like carbon
tetrachloride (CCl4 ), dichloromethane (DCM) etc.35 FLG was
found to become water-soluble, after reacting with concentrated
H2 SO4 and HNO3 .36 However, all such kind of functionalization
through covalent modification was found to affect the electronic
structure and thus, properties of FLG. Hence, functionaliza-
tion through non-covalent modification was necessary, which
can be performed effectively by wrapping with polyethylene
glycol (PLG), to make it water-soluble, without modifying its
electronic structure.36 Apart from functionalization, decoration
with metallic nano-particles also become necessary to make
the structure more suitable for usage in electronics, optics and
biotechnology related applications. FLG was found to be easily
decorated with Pt, Ag, and Au nano-particles, in a single-step
chemical process.13,37 Such decoration enhances its application
in opto-electronics.
Chemical modification of graphene also leads to change
in magnetic properties of graphene, by changing the edge
characteristics.38 Edge-state of graphene has attracted consid-
erable attention in recent years, as it can lead to new mag-
netic properties of graphene, including ferromagnetism. It was
found that the edge-state of FLG can be modified in a num-
ber of ways, by varying the type of molecules adsorbed on
graphene. Such structural modifications are expected to gener-
ate new magnetism based applications of graphene; the most
important field being memory devices. The ease with which the
structure of graphene could be modified, by functionalization or
other chemical treatments, has prompted application in biotech-
nology related fields. Recently, Varghese et al. have conducted
a detailed study to understand the interaction of graphene with
DNA nucleobases and nucleosides.39 The interaction energies
were found to be almost similar to that of single wall carbon
nanotubes. However, more detailed research efforts need to be
concentrated in this area, before commenting on suitability of
graphene in bio applications.
FLG has also been used effectively as part of composite elec-
trodes in new generation Li-ion batteries due to its ability to take
part in electrochemical reactions.40,41 Graphene showed similar
or better kinetics in many electrochemical systems than that of
graphite or activated carbon (widely used in this type of appli-
cations). Such composite electrodes were found to enhance the
performance of the batteries. Application of graphene in energy
storage devices, such as batteries and supercapacitors, are very
recent; but the success of the reported studies are expected to
attract more research efforts in this field.
All varieties of graphene, single-, bi-, and few-layer, have
found potential applications in fields of electronics, memory,
biotechnology, sensor, energy storage devices etc. As synthe-
sis methods control the structure and properties of graphene, a
variety of processing techniques are used by researchers, espe-
cially for large scale production. The subsequent sections will
discuss different synthesis techniques of graphene and its main
applications, reported so far.
56 W. CHOI ET AL.
3. GRAPHENE SYNTHESIS METHODS
Synthesis of monolayer graphite was tried as early as in
1975, when B. Lang et al.42 showed formation of mono- and
multi-layered graphite by thermal decomposition of carbon on
single crystal Pt substrates. However, due to lack of consis-
tency between properties of such sheets, formed on different
crystal planes of Pt and failure to identify the beneficial appli-
cations of the product, the process was not studied extensively,
at that period of time. After a long gap, scattered attempts to
produce graphene were reported again from 1999.43,44 How-
ever, Novoselov et al. has been credited for the discovery of
graphene in 2004.3,45 They have first shown repeatable synthe-
sis of graphene through exfoliation. The technique has been and
is being followed since then, along with efforts to develop new
processing routes for efficient synthesis of large-scale graphene.
The synthesis routes of graphene can be broadly categorized into
different sections, as delineated below.
3.1. Exfoliation and Cleavage
Graphite is stacked layers of many graphene sheets, bonded
together by week van der Waals force. Thus, in principle, it
is possible to produce graphene from a high purity graphite
sheet, if these bonds can be broken. Exfoliation and cleavage
use mechanical or chemical energy to break these week bonds
and separate out individual graphene sheets. The first attempt
in this direction was by Viculis et al., who have used potassium
metal to intercalate a pure graphite sheet and then exfoliate
it with ethanol to form dispersion of C sheets.8 During soni-
cation, the exfoliated nano-carbon sheets formed nanoscrolls.
TEM analysis showed presence of 40 ± 15 layers in each sheet.
Though these carbon nanoscrolls were much thicker than few-
layer graphene, the process showed that, in practice too, it is
possible to separate layers of graphene from graphite. The pro-
cess needed modification to finally produce FLG. It took almost
20 more months to find a solution, when Novoselov et al. re-
ported FLG and even SLG formation by exfoliation.3
Exfoliation is basically a repeated peeling process. In the
study of Novoselov et al., a commercially available highly ori-
ented pyrolytic graphite (HOPG) sheet of 1 mm thickness was
subjected to dry etching in oxygen plasma to make many 5 µm
deep mesas (of area 0.4 to 4 mm2 ). This was then put on a pho-
toresist and baked, to stick the mesas to the photoresist. Then, a
scotch tape was used to peel off layers from the graphite sheet.
Thin flakes, attached to the photoresist, released in acetone and
transferred to a Si substrate, were found to have single- to few-
layer graphene sheets. The technique was later used to produce
two-dimensional atomic crystals of many other materials, in-
cluding BN, MoS2 also.45 This process of producing graphene
sheets was found to be very reliable and easy and thus, attracted
the immediate attention of the scientific community.46−48 In
slight variations of the original process, it was shown that large
(∼10 µm) and flat graphene flakes can be produced by ma-
nipulating the substrate bonding of HOPG on Si substrate and
controlled exfoliation.49 In another approach, mm-sized single-
to few-layer graphene was produced by bonding bulk graphite
to borosilicate glass followed by exfoliation, to leave single or
few layer of graphene on the substrate.50 Both of these advance-
ments stressed on modifying the bonding with the substrate to
generate large-area graphene sheets. These methods show good
promise to be scaled up to industrial level production for large-
size graphene based electronic devices.
In a little different approach of exfoliation in liquid phase,
Stankovich et al. proposed to use hydrophobicity of graphite
oxide (GO) and exfoliated GO nanosheets by ultrasonication
in aqueous suspension and attempted reduction of the films in
hydrazine hydrate at 100◦ C for 24 h.51,52 The product, how-
ever, was not fully reduced and found to have some amount
of oxygen left in the structure. Hence, it can be called as par-
tially reduced exfoliated nano graphite oxide sheets. Acting on
the pros and cons of this liquid phase exfoliation process, Her-
nandez et al. came up with a new way of producing single- to
few-layer graphene sheets, through dispersion and exfoliation of
pure graphite in N-methyl-pyrrolidone.53 The monolayer yield
was 1 wt%, which could be improved up to 12 wt%, with fur-
ther processing. The success of the process is dictated by the
fact that the energy required to exfoliate graphite into single-
layer graphene was countered by the solvent-graphene interac-
tion, with the solvent having similar surface energy as that of
graphene. This process of liquid based exfoliation of graphite
in organic solvent has the promise of large-scale production of
graphene. A similar kind of process was used by Lotya et al.
to produce single- to few-layer graphene, by making disper-
sion of graphite powder in sodium dodecylbenzene sulfonate
(SDBS), followed by sonication, to exfoliate the graphite into
graphene.54 Figure 4 presents images of graphene, produced
by these methods. There were many such attempts to produce
graphene either from graphite or graphite oxide powder and
using different solvents.55−58
The process of exfoliation shows good promise to synthe-
size large scale graphene and some of the recent modifica-
FIG. 4. High resolution transmission electron microscopy
(HRTEM) images (bright field) of (A) single-layer53 and (B) bi-
layer graphene.54 (Reproduced with permission from Macmil-
lan Publishers Ltd: Nature Nanotechnol,53 Copyright 2008, and
Lotya et al.54 Copyright 2009: American Chemical Society.)
 SYNTHESIS OF GRAPHENE AND ITS APPLICATIONS
tions, through liquid phase exfoliation, have made it possible
to produce large-size also. However, the liquid phase exfoli-
ated products suffer from the limitation that the structure has
lot of defects, due to oxidation and reduction processes, leading
to much poor electrical properties of graphene. The future im-
provisations need to concentrate on controlling the number of
layers and minimizing impurity levels to lead this process into
an industrial scale production level.
3.2. Thermal Chemical Vapor Deposition Techniques
Synthesis of graphene through thermal chemical vapor de-
position (CVD) has been quite new. The first report on planar
few layer graphene (PFLG), synthesized by CVD, was found
in 2006.59 In this work, a natural, eco-friendly, low cost pre-
cursor, camphor, was used to synthesize graphene on Ni foils.
Camphor was first evaporated at 180◦ C and then pyrolyzed, in
another chamber of the CVD furnace, at 700 to 850◦ C, using
argon as the carrier gas. Upon natural cooling to room temper-
ature, few-layer graphene sheets were observed on the Ni foils.
Graphene, thus produced, was found to have multiple folds (in
HRTEM images) and estimated to have approximately 35 lay-
ers of graphene sheets. This study opened up a new processing
route for graphene synthesis, though several issues like control-
ling the number of layers, minimizing the folds etc, were yet to
be solved.
In another approach, 1 to 2 nm thick graphene sheet was
reported to be grown on Ni substrate by thermal CVD, while the
same treatment failed to synthesize graphene on Si.60 The pro-
cess used a precursor gas mixture of H2 and CH4 (92:8 ratio), a
total gas pressure of 80 Torr and was activated by DC discharge.
Nanometer thick (confirmed by Auger Electron Spectroscopy)
graphitic films were found to have atomically smooth microme-
ter size regions, separated by ridges. While the ridge formation
was proposed to be due to difference in thermal expansion coeffi-
cients of Ni and graphite, the nucleation process was attributed
to heteroepitaxial growth of graphene on Ni(111). Later, Yu
et al. have reported three to four layer graphene formation on
polycrystalline Ni foils (of 500 µm thickness), through ther-
mal CVD process.61 A precursor gas mixture of CH4 , H2 and
Ar (0.15:1:2 ratio), at a total flow rate of 315 sccm, was used
for the synthesis process, allowing 20 min at 1000◦ C for the
synthesis process. HRTEM and Raman spectroscopic analyses
confirmed formation of graphene on Ni under moderate cooling
rates only, while high and low cooling rates were found to be
detrimental to graphene synthesis process. This difference in
graphene formation was attributed to solubility of C in Ni and
the kinetics of C segregation. Ni has a good solubility for carbon
atoms. At slow cooling rate, C atoms get sufficient time to dif-
fuse into bulk Ni and no segregation is found on the surface. At
a moderate cooling rate, C atoms segregate and forms graphene,
while at a higher rate also C atoms segregate out of Ni, but form
a less crystalline, defective graphitic structure. This study gave
the necessary input about the growth mechanism of graphene in
CVD process.
57
Having understood the mechanism of graphene growth, the
next thrust was on growing graphene on a large scale and sev-
eral research groups concentrated their efforts on this issue.62
Wang et al. proposed a new method of growing substrate-free
few-layered graphene.63 They used MgO-supported Co cata-
lysts to grow graphene in a ceramic boat, at 1000◦ C for 30 min,
under a gas envelope of CH4 and Ar (1:4 volume ratio, total
375 mL/min flow rate). Product of reaction was further washed
by concentrated HCl to remove MgO and Co, followed by sev-
eral distilled water wash and drying at 70◦ C. It was claimed
that 500 mg of catalyst powder mixture can produce 50 mg
of graphene. SEM, HRTEM and Raman spectroscopic analysis
of the structure confirmed presence of rippled graphene sheets,
having at least five layers. Though the mechanism of graphene
formation by this route is still under investigation, the process
showed a new window for large scale production of graphene.
Another recent report has shown growth of single to few
layer graphene on polycrystalline Ni film of 1-2 cm2 , by
thermal CVD.12 The Ni film (500 nm thick) was evaporated on
a SiO2 /Si substrate and was annealed in Ar+H2 atmosphere,
at 900 to 1000◦ C, for 10 to 20 minutes. This annealing step
created Ni grains of 5 to 20 µm in size. After CVD at 900
to 1000◦ C for 5 to 10 minutes, using 5 to 25 sccm CH4 and
1500 sccm H2 , graphene was found to form on the Ni — the
size of each graphene being restricted by the Ni grain size.
The graphene was later transferred to any substrate, keeping
its electrical properties unchanged, thus making them suitable
for various electronic applications. Graphene, thus synthesized
and transferred onto a glass substrate, has shown ∼90% optical
transmittance. High transmittance and electrical properties,
along with the capability to be synthesized on a large size
and even on a pre-patterned substrate, may find interesting
applications in next generation solar cells. An independent
study by de Arco et al. has also reported similar properties
from graphene, following identical synthesis approach.64 In
an almost similar approach, Kim et al. have shown growth
of graphene on Ni film (300 nm thick), deposited on SiO2 /Si
substrate.17 It was claimed that the thickness of the Ni film was
optimized for best quality of graphene. Graphene synthesis was
performed in a CVD chamber, using a gas mixture of CH4 , H2
and Ar (50:65:200 sccm), at a temperature of 1000◦ C, followed
by a rapid cooling (10◦ C s−1 ) in Ar envelope. It was found that
the high cooling rate was important to minimize the number
of layers and for efficient transfer of these layers onto other
substrates. This graphene was later successfully transferred
onto flexible, transparent substrate, made up of polydimethyl-
siloxane (PDMS) without affecting its properties and showing
80% transparency in visible spectrum. It was observed by the
authors that application of an aqueous FeCl3 solution etches
the nickel layers in a mild pH value, without causing formation
of gaseous products or precipitates. Gaseous products, as is
produced by HNO3 etching, damage the graphene structure.17
In a very recent development, highly crystalline few-layer
graphene was grown directly on 1 cm2 area of polycrystalline
58 W. CHOI ET AL.
FIG. 5. (a) SEM images of as-grown graphene films on thin
(300-nm) Ni layers and thick (1-mm) Ni foils (inset)17 ; (b)
HRTEM image of few layered graphene, showing individual
graphene sheets with the edges of the graphitized layers.63
(Reprinted with permission from Macmillan Publishers Ltd:
Nature,17 Copyright 2009, and Wang et al.63 Copyright 2009:
Wiley-VCH Verlag GmbH & Co.)
Ni substrates, by carefully controlling the gas ratio, growth
time and temperature.65 Figure 5 shows some SEM images of
the graphene synthesized through this route.
In further development of the process, graphene was found
to be synthesized on a 1 cm2 area of Cu foil by thermal CVD
process.66 Graphene, thus produced, was of high quality and
uniformity. Graphene was also transferred by two different and
simple techniques to different substrates, enabling their appli-
cation in various fields. However, it was found that graphene
growth on Cu substrate was self-limiting, probably due to lim-
ited solubility of C in Cu. The process was claimed to be a
surface-catalyzed process rather than a precipitation process, as
has been reported for Ni.61
The recent achievements in graphene growth by thermal
CVD has confirmed reproducibility of good quality graphene
on a centimeter scale substrate and successful transfer to many
other substrates including Si, glass and PDMS. These devel-
opments create new pathways for application of graphene in
photovoltaic and flexible electronics. However, in near future,
issues like growth of graphene on wafer size substrates, con-
trolling efficiently the number of layers should be solved, for
creating more interest in actual applications.
3.3. Plasma Enhanced Chemical Vapor Deposition
Techniques
Interest in synthesizing graphene through plasma enhanced
chemical vapor deposition (PECVD) is contemporary to that of
exfoliation. The earliest report, by Obraztsov et al., has proposed
a dc discharge PECVD method to produce so called nanostruc-
tured graphite-like carbon (NG).67 The process used Si wafer
and Ni, W, Mo and some other metal sheets as substrates and
a gas mixture of CH4 and H2 (0% to 25% CH4 ), with a to-
tal gas pressure of 10 to 150 Torr. The NG film produced by
this process looks thicker at most of the places, except at some
twisted portions. The first report on single-to few-layer graphene
by PECVD was found in 2004.68,69 A radio frequency PECVD
system was used to synthesize graphene on a variety of sub-
strates (Si, W, Mo, Zr, Ti, Hf, Nb, Ta, Cr, 304 stainless steel,
SiO2 , Al2 O3 ), without any special surface preparation operation
or catalyst deposition. The graphene sheets, produced in a gas
mixture of 5–100% CH4 in H2 (total pressure 12 Pa), at 900W
power and 680◦ C substrate temperature, was found to have sub-
nanometer thickness and erected from the substrate surface.
Simplicity of the process immediately attracted attention of the
scientific community and the same kind of process was followed
by many research groups, worldwide.68−72 In one of these pub-
lications, Zhu et al. have proposed a growth mechanism for
the graphene in PECVD chamber.71 According to their scheme,
atomically thin graphene sheets are synthesized by a balance be-
tween deposition through surface diffusion of C-bearing growth
species from precursor gas and etching caused by atomic hydro-
gen. The verticality of the graphene sheets, produced through
this method, is caused by the plasma electric field direction.
In a slightly modified process, Shang et al. have shown
synthesis of multilayer graphene nanoflake films (MGNF) on
Si substrates, through microwave PECVD (MW-PECVD).73
Graphene produced in this method had highly graphitized
knife-edge structure, with 2 to 3 nm thickness at the sharp
edges. Graphene sheets were roughly vertical to the substrate
(Si) and reported to show excellent bio-sensing capability (for
dopamine). The report also claimed a very high growth rate of
graphene, 1.6 µm min−1 , which was 10 times faster than other
processes. In a very similar way, Yuan et al. have synthesized
high quality graphene sheets, 1 to 3 layers thick, on stainless
steel substrate at 500◦ C, by microwave PECVD.76 The process
used a gas mixture of CH4 and H2 (1:9 ratio, at a total pressure
of 30 Torr and 200 sccm flow rate) and microwave power of
1200W. Graphene, produced in this method, was found to show
better crystallinity, than any other method. Figure 6 and 7 show
SEM and HRTEM images of graphene sheets produced by
PECVD technique.
PECVD method has shown the versatility of synthesizing
graphene on any substrate, thus expanding its field of appli-
cations. Future developments of this method should bring out
better control over the thickness of the graphene layers and large
scale production.
3.4. Other Processing Routes
3.4.1. Chemical Methods
Apart from these main processing routes of exfoliation and
different CVD processes, there have been attempts to produce
graphene through many other techniques. One of them is chem-
ical based techniques, a part of which is already covered in sec-
tion 3.2, as liquid phase exfoliation. Chemical methods have also
been used to chemically extract graphene films from graphite,
without the exfoliation step. Horiuchi et al. first showed the
possibility of this route to produce graphene, when they pro-
duced carbon nano films (CNF) from natural graphite.77 Nat-
 SYNTHESIS OF GRAPHENE AND ITS APPLICATIONS 59

FIG. 6. Graphene sheets synthesized through radio frequency (RF) plasma enhanced chemical vapor deposition (PECVD) tech-
nique, (a) SEM image of graphene directly grown on the curved surface of a Ni wire of a TEM grid, (b) SEM of an enlarged
nanosheets edge with a thickness less than 1 nm, (c) HRTEM image of a single nanosheet with two graphene layers, as indicated
by the two parallel fringes. (Reprinted with permission from Zhu et al.71 Copyright 2004: Elsevier.)

ural graphite was subjected to a series of oxidation and purifi-
cation processes, followed by dilution in methanol and several
centrifugation steps to extract the thinnest sheets from the dis-
persion. The thickness of the CNF was found to be directly
related with the dilution factor and the product had 1 to 6 lay-
ers of graphene. In a different chemical method, sulphuric and
nitric acid were intercalated between the layers of graphite, fol-
lowed by rapid heating to 1000◦ C, so that explosive evaporation
of the acid molecules could produce thin graphitic sheets.76
In a second step intercalation, oleum and tetrabutylammonium
hydroxide (TBA) were used to produce single- and few-layer
graphene, after sonication in a surfactant solution. The choice
of intercalants, in this study, ensured minimum damage of sp2
network in the graphene and thus, a higher quality graphene.
In another attractive study, Choucair et al. have reacted sodium
and ethanol (1:1 molar ratio) to form a graphene precursor,
which was then rapidly pyrolyzed.79 Graphene was found in
the suspended solid, giving a high production yield of 0.1 g
graphene per 1 mol of ethanol (Figure 8a). The process shows
capability to synthesize graphene in large volume. In a totally
different approach, ‘chemical exfoliation’ was used to produce
graphene.78 Graphite oxide was thermally expanded by rapidly
heating it at 1050◦ C, followed by a two-stage reduction, using
hydrogen gas and N-methylpyrolidone. It was also claimed in
the study that the number of layers in the graphene is dictated
by the lateral size and crystallinity of the input graphite. The
study, thus, shows a possible way of controlling the number of
graphene layers, which may have high impact in the electrical
applications. Detailed information about the chemical methods
to produce graphene sheets could be found in a recent review
by Park et al.81
3.4.2. Thermal Decomposition of SiC
One of the highly popular techniques of graphene growth
is thermal decomposition of Si on the (0001) surface plane of
single crystal of 6H-SiC.80 Graphene sheets were found to be
formed when H2 -etched surface of 6H-SiC was heated to tem-
peratures of 1250 to 1450◦ C, for a short time (1 to 20 minutes).
Graphene, epitaxially grown on this surface, typically had 1 to
3 graphene layers; the number of layers being dependent on the
decomposition temperature. In a similar process, Rollings et al.
have produced graphene films, as low as one atom thickness.82
Continued success of this process has attracted attention of the
semiconductor industries, as this process may be a viable tech-
nique in post-CMOS age9,15,82−84 (Figure 8b shows SEM image
of graphene grown epitaxially on SiC surface). J. Hass et al.
have presented a comprehensive review on this topic, covering
the issues of graphene growth on different faces of SiC and
their electronic properties.15 In a significant development to this
technology, continuous films (mm scale) of graphene were syn-
thesized on a Ni thin film coated SiC substrate, at a quite lower

FIG. 8. (a) TEM image of agglomerated graphene sheets pro-

FIG. 7. Graphene sheets produced by microwave plasma en-
hanced chemical vapor deposition technique, (a) SEM and (b)
TEM image of graphene on Cu grid, (c) SAD pattern of the
sheet, showing sharp and clear diffraction, resembling graphene.
(Reprinted with permission from Yuan et al.76 Copyright 2009:
Elsevier.)
duced by chemical route,79 (b), (c) SEM images of the graphene
sheets epitaxially grown on SiC(0001) surface (annealed for 4 h
in vacuum at 1900◦ C); fracture surface in (c) shows that bright
lines in (b) are wrinkles in graphite.84 (Reprinted with permis-
sion from Macmillan Publishers Ltd: Nature Nanotechnol,79
Copyright 2009, and Cambaz et al.84 Copyright 2008: Elsevier.)
60 W. CHOI ET AL.
temperature (750◦ C).85 This process has the added advantage
of continuity of graphene film over the entire Ni-coated surface.
Large area production of graphene makes this route favorable
for industrial application. In a similar process, Emtsev et al.
have shown synthesis of large-size, monolayer graphene films
at atmospheric pressure.86 The method was predicted to produce
wafer-size graphene films.
The process of growing graphene on SiC looks attractive, es-
pecially for the semiconductor industries. However, issues like
controlling thickness of the graphene layers, repeated produc-
tion of large-area graphene have to be solved, before the process
can be adopted at an industrial scale. Analysis of the available
research works on epitaxial growth of graphene film on SiC sur-
face has pointed out several other important issues. Graphene,
grown on SiC(0001) and SiC(0001̄) was found to have different
structures. Unusual rotational stacking observed in multilayer
graphene (up to 60 layers thickness) grown on the SiC(0001) sur-
face could probably explain their behavior like isolated graphene
sheets. Such kind of unusual behavior could not be observed in
graphene grown on SiC(0001). Future research works need to be
directed to understand the mechanisms of both the growth pro-
cesses and apply the knowledge in developing practical devices.
Another important issue is structure and electronic properties of
the interface layer between graphene and substrate, since it is
known to affect the properties of graphene. Till now, the effect
of interface is not well understood and future research should be
concentrated in understanding this issue. With the knowledge
about growth mechanism and interface effects and the ability to
effectively control the number of layers, this method is set to be
used industrially to produce wafer scale graphene.
3.4.3. Thermal Decomposition on Other Substrates
In a similar kind of approach, graphene monolayers were
grown on single crystal Ru(0001) surface at ultra-high vac-
uum condition (4 × 10−11 Torr).87 Before the synthesis pro-
cess, Ru crystal was cleaned by repeated cycles of Ar+ sput-
tering/annealing and exposure to oxygen and heating to high
temperature. Graphene was found to be formed on the crys-
tal surface, either by thermal decomposition of ethylene (pre-
adsorbed on crystal surface at room temperature) at 1000K or
by controlled segregation of carbon from bulk of the substrate.
The single-layered graphene was of high purity, covered large
space (more than several microns) and periodically rippled. A
similar effort by Sutter et al., by thermal decomposition of pre-
absorbed C atoms on Ru(0001) surface, lead to formation of
macroscopic (more than 200 µm) single-crystalline domains
of single- to few-layer graphene.88 The method was proposed
for graphene synthesis on other transition metals also, enabling
them for wide usage in electronics, catalysts or sensing applica-
tions. Following the trend, graphene was synthesized on many
other single crystal transition metal surfaces, including Ir, Ni,
Co, Pt, etc. A comprehensive understanding of all such efforts
can be obtained from a topical review by Wintterlin et al.89
FIG. 9. (a) TEM image of partially unzipped MWCNT struc-
ture, opened by Li intercalation,90 (b) high magnification TEM
image of graphene sheet produced by multistep oxidation-
reduction treatment; the inset is the SAED pattern, which con-
firms the crystalline nature of the graphene sheet.93 (Reprinted
with permission from Cano-Márquez et al.90 Copyright 2009:
American Chemical Society, and Kim et al.93 Copyright 2009:
Elsevier.)
3.4.4. Un-zipping CNTs and Other Methods
A very recent method of graphene synthesis has used multi-
wall carbon nanotubes (MWNT) as the starting material. The
process is popularly known as ‘un-zipping of CNTs’. Three
groups, working independently on this issue, reported their find-
ings in almost same time period. In the earliest of them, it was
claimed that MWNTs can be opened up longitudinally by using
intercalation of Li and ammonia, followed by exfoliation in acid
and abrupt heating90 (Figure 9a). The product, among nanorib-
bons and partially opened MWNTs, also contained graphene
flakes. In another study, graphene nanoribbons were produced
by plasma etching of MWNTs, partially embedded in a polymer
film.91 The etching treatment basically opened up the MWNTs
to form graphene. In a different approach, MWNTs were un-
zipped by a multi-step chemical treatment, including exfoliation
by concentrated H2 SO4 , KMnO4 and H2 O2 , stepwise oxidation
using KMnO4 and finally reduction in NH4 OH and hydrazine
monohydrate (N2 H4 .H2 O) solution.92 This new process route of
unzipping MWNTs to produce graphene creates possibilities of
synthesizing graphene in a substrate-free manner.
In another recent approach of producing multi-layered
graphene sheet, aluminum sulfide (Al2 S3 ) was calcined under
a (CO+Ar) gaseous environment93 (Figure 9b). CO was found
to be reduced by Al2 S3 to form gaseous carbon and α-alumina.
Graphene sheets were later crystallized on the alumina parti-
cles. Though the mechanism of this transformation is not yet
well understood, the process seems to be very interesting due
to its simplicity. In future developments, if the process param-
eters can be controlled efficiently to minimize and effectively
control the number of graphene layers, then bulk production of
graphene can get a big jump.
Highly oriented pyrolytic graphite (HOPG) has been cleaved
by using a micro-cantilever (such as an AFM tip) to form very
thin graphitic sheets.94 The product was 10 to 100 nm thick
 SYNTHESIS OF GRAPHENE AND ITS APPLICATIONS
and hence can not be treated as graphene. However, the effort
has shown a new possibility of producing graphene sheets. In
another recent approach, conducting nano carbon films (thick-
ness ∼1 nm) and membranes were produced through a complex
processing route based on molecular self-assembly, electron
irradiation and pyrolysis.95,96 Though these processes are not
simple enough to be adopted industrially, future research efforts
should be aimed to understand the mechanism of thin carbon
film growth through these techniques and proposing possible
process modifications to synthesize graphene.
Most of the graphene synthesis methods, available to date,
have been discussed in this section. The techniques vary in a
wide range, from mechanical exfoliation and chemical exfo-
liation to fully chemical based oxidation/reduction methods,
epitaxial growth on SiC and on many transition metal single
crystals and CVD/PECVD. Since the discovery of graphene in
2004, the last few years have seen huge progress in terms of
graphene growth, controlling number of layers in the product,
synthesizing larger samples and producing in bulk volume. The
future research efforts on graphene synthesis should be directed
towards wafer-scale graphene growth, with pre-determined con-
trol over number of layers, to bring a new revolution in the
electronics and semiconductor industries.
4. APPLICATIONS OF GRAPHENE
4.1. Graphene Field Emission (FE)
One of the potential applications of graphene is in field emis-
sion (FE) displays. FE is an electron emission process in which
electrons are emitted from a material under the application of
high electric field. The simplest way to create such a field is
by field enhancement at the tip of a sharp object. To take ad-
vantage of high field enhancement, graphene sheets, i.e., sin-
gle or few layers, need to be erected on the substrates. Except
for graphene synthesis by MW-PECVD method,97 almost all
other methods results in flat graphene layers on substrates.2
Eda et al. have recently fabricated a graphene/polymer com-
posite thin film for achieving a field enhancing structure, re-
quired for FE applications.98 The FE cathodes by Eda et al.
were prepared from graphene, synthesized from graphite oxide
(GO) dissolved in polystyrene by spin coating it on to silicon
substrates.98 The detailed process of graphene/polymer com-
posite thin film synthesis could be found in Reference 98. The
orientation of the graphene sheets in the composite thin films
was varied by controlling the spin coating speeds. Relatively
better FE was observed from films prepared at spin coating
speed of 600 rpm; the turn-on electric field (Eto ) in such sam-
ple was ∼4 V/µm and the field enhancement factor (β) was
∼1200. In another work by Wu et al.99 single layer graphene
film was prepared by electrophoretic deposition (EPD) method.
Graphene films, prepared by exfoliation of graphite, were dis-
persed in isoprophyl alcohol and the resulting solution was de-
posited onto indium tin oxide (ITO) coated glass substrates by
EPD (Figure 10a). Graphene cathodes prepared by this method
61
demonstrated an Eto of 2.3 V/µm and a β of ∼3700. Although
these research works98,99 have demonstrated methods to pre-
pare graphene films for FE applications on flexible and other
substrates, these methods may not be suitable to achieve high
FE currents, in the order of few mA-A, required for high current
applications.
This issue may probably be addressed by MW-PECVD me-
thod demonstrated by Malesevic et al.,97 to fabricate vertically
aligned few layer graphene (FLG) FE cathodes on titanium and
silicon (Figure 10b). FLG was synthesized by MW-PECVD with
H2 and CH4 precursor gases, at 700◦ C. The quality of FLG films
was observed to be dependent on the ratio of H2 /CH4 gases; best
quality was achieved when the ratio was 8:1. Graphene cathodes
prepared by this method demonstrated an Eto of 1 V/µm, β
of ∼7500 and a current density of 14 mA/cm2 (Figure 10c).
The advantage of this method is direct synthesis of graphene
on metallic substrates creating ohmic contact, which is essential
for FE applications. Moreover, no further processing is required.
The drawback of this method is the limited scope to control the
FLG density, which can cause field-screening effect. Works by
Watcharotone et al.,100 Masaaki et al.101 and Babenko et al.102
have also theoretically addressed filed emission from graphene
films. The theoretical works describe the importance of field
enhancement factor100,102 and role of defects101 in graphene
field emission. In summary, the enthusiasm for FE of graphene is
justified by its unique properties. However, it might take a while
to demonstrate a real FE device, which can reach the market.
4.2. Graphene Based Gas and Bio Sensors
One of the most promising applications of graphene is in
sensors, including gas and bio sensors. The operational prin-
ciple of graphene based gas or bio electronic sensors is based
on the change of graphene’s electrical conductivity (σ ) due to
adsorption of molecules on graphene surface.23 The change in
conductivity can be attributed to the change in carrier concen-
tration of graphene due to the absorbed gas molecules acting as
donors or acceptors. Furthermore, some interesting properties
of graphene aid to increase its sensitivity up to single atom or
molecular level detection. First, graphene is a two-dimensional
(2D) material and its whole volume i.e., all carbon atoms are
exposed to the analyte of interest.21 Second, graphene is highly
conductive with low Johnson noise (electronic noise generated
by the thermal agitation of the charge carriers inside an electri-
cal conductor at equilibrium, which happens regardless of any
applied voltage), therefore, a little change in carrier concentra-
tion can cause a notable variation of electrical conductivity.21
Third, graphene has very few crystal defects[6,19,26,45,103] en-
suring a low level of noise caused by thermal switching.20 Fi-
nally, four-probe measurements can be made on single crys-
tal graphene device with ohmic electrical contacts having low
resistance.21,104
Since the first report on graphene sensing by Schedin et al.21
in 2007, there have been several reports on graphene based sen-
sors. In the work by Schedin et al.,21 graphene demonstrated
62 W. CHOI ET AL.

FIG. 10. (a) High-magnification SEM image of the graphene film deposited on the ITO-coated glass for I min at an applied field of
160 V by EPD, using a ∼0.1 mg mL−1 graphene suspension as electrolyte,99 (b) SEM image showing top view of FLG synthesized
by MW PECVD,97 (c) Current density as a function of applied electric field for FLG grown on silicon with gas ratio H2 /CH4 = 8/1.
The results are shown for five voltage cycles without exposure to air in between each cycle and maintaining a constant vacuum;
the inset shows the same data, plotted according to the Fowler-Nordheim relation.97 (Reprinted with permission from Malesevic
et al.97 Copyright 2008: American Institute of Physics, and Wu et al.99 Copyright 2009: Wiley-VCH Verlag GmbH & Co.) (d) Diode
schematic circuit with polymer-graphene composite film as cathode and metal plate as anode, d is the inter-electrode distance.

good sensing properties towards NO2 , NH3 , H2 O and CO.21 also demonstrated that chemical doping of graphene by both
Graphene sensing properties were fully recoverable after expo- holes and electrons, in high concentration, did not affect the
sure to the analyte of interest, by vacuum annealing at 150◦ C mobility of graphene.21 In another work by Fowler et al.104
or by illumination to UV for short time.21 Furthermore, it was in addition to NO2 and NH3 , dinitrotoulene (DNT), a volatile
 SYNTHESIS OF GRAPHENE AND ITS APPLICATIONS
FIG. 11. (left) NO2 and (right) NH3 detection using a graphene film. Both the sensors have gold electrodes and measurement
used a four wire method with 500 µA driving current. The NO2 and NH3 concentration is 5 ppm in dry nitrogen. (Reprinted with
permission from Fowler et al.104 Copyright 2009: American Chemical Society.)
compound found in explosives, was also detected. Figure 11
demonstrates the graphene sensors response to NO2 and NH3 .
The sensing mechanism of NO2 was attributed to hole induced
conduction, as it withdraws an electron from graphene and in
NH3 , to electron induced conduction, as it donates an electron to
graphene. By utilizing the four-point electrode system, Fowler
et al. also proposed that the role of electrode electrical contacts
was minimum in the sensing mechanism of graphene. The sens-
ing mechanism was primarily attributed to charge transfer at the
graphene surface.104 DNT sensing mechanism was similar to
that of NO2 i.e., electron-withdrawing and the limit of detection
of DNT was reported to be 28 ppb, which is well below the room
temperature vapor pressure of DNT, i.e., 173 ppb.104 In another
related study by Sundaram et al.105 graphene surface was chem-
ically modified by electrodeposition of Pd nanoparticles. This
procedure may be advantageous, as the attached catalyst parti-
cles are expected to impart sensitivity toward certain analytes,
which cannot be directly detected with unmodified material,
due to insignificant response.105 The electrodeposition of Pd on
graphene was observed to improve the response of graphene
sensors to H2 detection, as Pd has good affinity towards H2
detection.105
In addition to gas sensing, recently Shan et al.106 has demon-
strated biosensing, i.e., glucose properties of graphene. With
glucose oxidase (GOD) as an enzyme model, Shan et al. and
their group constructed a novel polyvinylpyrrolidone protected
graphene/polyethylenimine-functionalized ionic liquid/ GOD
electrochemical biosensor. Through the sensor, they reported
direct electron transfer of GOD, demonstrating graphene’s po-
tential application for fabrication of glucose sensors. A lin-
ear response up to 14 mM of glucose was observed in their
work.106 In addition to biosensing application for glucose de-
tection, recently Alwarappan et al.107 has demonstrated that
graphene based biosensors are more effective than carbon nan-
otubes (CNT) to detect catecholamine neurotransmitters, such
as dopamine and serotonin. They demonstrated that graphene
63
electrodes exhibited a superior biosensing performance than
CNTs toward dopamine detection in the presence of common
interfering agents, such as ascorbic acid and serotonin.107 In
another work by Li et al.,103 a nano composite film sensing
platform, based on the Nafion graphene, was used for deter-
mination of Cd2+ by anodic stripping voltammetry (ASV).104
The nano composite film has demonstrated advantages of
graphene and the cationic exchange capacity of Nafion, which
enhanced the sensitivity of Cd2+ assay. Since exposure to cad-
mium, used in several industries, can cause renal dysfunction,
bone degeneration, lung insufficiency, liver damage and hy-
pertension in humans with both acute and chronic toxicity,
the authors have explored the use of graphene for sensing
cadmium.108
Some researchers have recently observed that inclusion of
lithographic (photo or e-beam) steps in preparation of graphene,
can cause some negative effects on the sensing properties
of graphene, due to presence of residual polymers on the
graphene surface. In a work by Dan et al.,109 a cleaning pro-
cess was demonstrated to remove the contamination on the sen-
sor device structure, allowing intrinsic chemical response of
graphene based sensors. The contamination layer was removed
by a high temperature cleaning process in a reducing (H2 /Ar)
atmosphere.109 For most of the gas and bio electronic sensor ap-
plications, graphene synthesized by various methods21,104−106
was deposited on Si or Si/SiO2 substrates and electrical con-
tacts were prepared with Au/Ti or other metals, which provide
good adhesion and ohmic contact with graphene. In addition
to the experimental studies of graphene based sensors, there
have been numerous theoretical reports110−114 on the sensing
properties of graphene. Most of the theoretical studies provide
an understanding on the effect of absorption of the gas or bio-
molecules and their influence on the mobility of graphene and
the charge transfer between the molecules and the graphene sur-
face. Furthermore, the theoretical reports also analyze the effect
of doping graphene for sensing applications.109−114
64 W. CHOI ET AL.

FIG. 12. (a) SEM picture of GNR devices fabricated on a 200 nm SiO2 substrate. The widths of the GNRs from top to bottom
are 20 nm, 30 nm, 40 nm, 50 nm, 100 nm and 200 nm. (b) AFM image of a single layer graphene before lithographic process,
(c) Cross-section measurement of the AFM, which provides the thickness of the graphene. When accounting the background noise
and interaction between the graphene and substrate, we consider sheets thinner than 0.5 nm to be single layer graphene. (Reprinted
with permission from Chen et al.121 Copyright 2007: Elsevier.)

4.3. Field Effect Transistors (FET)
One of the potential applications of graphene is in FET.3
However, being a zero-gap semiconductor, graphene cannot be
directly utilized for FET applications. The observation of elec-
tric field effect in graphene was first reported by Novoselov
et al. in 2004. In that report, the researchers observed that
graphene based FETs demonstrated ambipolar characteristics
with an electron and hole concentrations of 1013 sq-cm, with mo-
bilites up to ∼10000 sq-cm/V-s at room temperature and ballistic
transport up to sub micrometer distances.3 For the transistor ap-
plications, graphene should be in the form of quasi-one dimen-
sional (1D) structure, with narrow widths and atomically smooth
edges.115−121 Such structures, termed as graphene nanoribbons
(GNRs), are predicted to exhibit band gaps useful for room tem-
perature FET applications, with excellent switching speed and
high carrier mobility.115−122 In addition to the 2D confinement
due to its structure, electrons in graphene are further confined
by the formation of nanoribbons (for example quantizing in ky
direction). The width confinement is expected to result in the
split of original 2D energy dispersion of graphene into a num-
ber of 1D modes. Due to this splitting, some 1D modes may not
pass through the intersection point of the conduction and va-
lence bonds, depending on the boundary conditions. Thus, the
qausi-1D GNRs become semiconductors with finite energy band
gap. 115−121 Band gaps up to 400 meV have been introduced by
patterning graphene into GNRs. 120−122 Figure 12 demonstrates
GNR FETs fabricated on SiO2 /Si substrates.121
Although band gap have been demonstrated in GNRs, these
were observed to be quite different from those of graphene, in
terms of carrier mobility and fabrication challenges. 123 Band
gap has also been achieved through application of electric fields
to bilayer graphene structures.124−126 However, these gaps have
been observed to be less than 400 meV and lead to signifi-
cant tunneling between bands.124−126 For the FET application,
several researchers have demonstrated various methods to fabri-
cate GNRs including chemical and lithographic methods. Litho-
graphic patterning has led to fabrications of GNRs with widths
of 20 to 30 nm.120,127
While chemical routes have produced 10 to 15 nm width
GNRs.122 Figure 13 shows the fabrication process of GNRs
by nanowire etch mask technique. By utilizing this process,
GNRs with widths down to 6 nm were demonstrated.122 Chen
et al.122 have investigated the FET properties of GNRs as a
function of their widths. Their experiments have shown that
resistivity of GNRs increased as their width decreased, which
could be attributed to the edge states. Furthermore, the electrical
current noise of GNR devices at low frequency was found to be
dominated by 1/f noise.121
Since the first experimental demonstration of graphene
based FETs, several theoretical studies have been reported
to predict the performance of GNR FETs as functions of
theirs edge roughness,128 chirality,129 chemical doping,130 car-
rier scattering,131 and contacts.132 In addition, various models
have also been developed to predict the performance of GNR
FETs.133−138 The theoretical studies provide a better understand-
ing about the performance of GNR based FETs characteristics;
furthermore, they can be valuable tools for designing efficient
FIG. 13. (a–f) Schematic fabrication process to obtain GNRs
by oxygen plasma etch with a nanowire etch mask. (Reprinted
with permission from Bai et al.127 Copyright 2009: American
Chemical Society.)
 SYNTHESIS OF GRAPHENE AND ITS APPLICATIONS
FIG. 14. Transmittance of the graphene films on a quartz plate
(with increasing exposure time from bottom to top). The upper
inset shows the ultraviolet (UV)-induced thinning and the con-
sequent enhancement of transparency. The lower inset shows the
changes in transmittance, Tr, and sheet resistance, Rs , as func-
tions of ultraviolet illumination time. (Reprinted with permis-
sion from Macmillan Publishers Ltd: Nature,17 Copyright 2009.)
FETs. Even though the potential of graphene FETs have been
demonstrated, it might take several years to fabricate commer-
cially viable logic devices from graphene, due to its various
intrinsic difficulties.
4.4. Transparent Electrodes
ITO is widely used to make transparent conductive coatings
for liquid crystal displays (LCD), flat panel displays, touch pan-
els, solar cells and EMI shielding. However, high cost, limited
supply and brittle nature of indium restricts its application in
flexible substrate, motivating the search for highly transparent,
high conductivity thin-film alternatives. Graphene is expected
to be one of the mostly sought materials for future optoelec-
tronic devices, including transparent electrodes for solar cells
and LCD displays.139−141 The extraordinary thermal, chemical
and mechanical stability of graphene, combined with its high
transparency and atomic layer thickness, makes it an ideal can-
didate for transparent conducting electrode applications. There-
fore, graphene is considered as a next generation transparent
electrode material. The high hole transport mobility, large sur-
face area and inertness against oxygen and water make graphene
a promising candidate for photovoltaic applications. Monolayer
graphene is highly conductive and highly transparent (absorb
only 2.3% of white light);142 Figures 14 and 15 demonstrate
the transmittance behavior of graphene transparent electrodes.
Recently K. Kim et al. reported 80% transmittance from the
graphene grown on a 300 nm thick nickel layer, corresponding
to 6 to 10 graphene layers.17 The transmittance was increased
up to 93% by further reducing the growth time and nickel thick-
ness, resulting in formation of thinner graphene film. Ultravi-
olet/ozone etching was also suggested to reduce the thickness
65
FIG. 15. (a) HRTEM image of graphene films with correspond-
ing SAED pattern (inset), (b) Transmittance of a ∼10 nm thick
graphene film (almost flat curve), in comparison with that of
ITO (top curve) and FTO (bottom curve), (c) schematic of dye-
sensitized solar cell using graphene film as electrode, the four
layers from bottom to top are Au, dye-sensitized heterojunc-
tion, compact TiO2 , and graphene film. (Reprinted with permis-
sion from Wang et al.141 Copyright 2008: American Chemical
Society.)
of graphene. However, sheet resistance increases with the ultra-
violet/ozone treatment time, in accordance with the decreasing
number of graphene layers.17
Wang et al. have reported application of graphene based
transparent electrodes for dye-sensitized solar cell (DSSC).141
They presented a simple approach for fabrication of graphene
films from exfoliated graphite oxide, followed by thermal reduc-
tion. The transparent electrodes demonstrated a transparency of
70% over 1000 to 3000 nm, with good conductivity of 550 S/cm.
The characteristic of the DSSC, prepared by using graphene
electrode, showed a short-circuit photocurrent density of 1.01
mA/cm2 , open-circuit voltage of 0.7 V, calculated filling factor
of 0.36 and overall power conversion efficiency of 0.26%. The
low efficiency of DSSC was claimed to be due to low quality of
graphene film.
Figure 14 shows the structure of graphene films and
their transmittance properties as a function of wavelength.
Composites of graphene and poly(3,4-ethylenedioxythiophene)
(PEDOT-PSS) were used as a counter electrode to show high
transmittance (>80%) and high electrocatalytic activity, result-
ing in 4.5% overall energy conversion efficiency.143 Transparent
graphene film was also reported to be used for organic solar
cell.144 A graphene-based film was prepared by the thermal
reaction of synthetic nano-graphene molecules of giant poly-
cyclic aromatic hydrocarbons, which were cross-linked with
each other and further fused into larger graphene sheets. The
film showed an ultra smooth surface and outstanding thermal
and chemical stability, but the power conversion efficiency was
comparable with that of the ITO-based cell under low intensity
66 W. CHOI ET AL.

monochromic illumination and relatively lower efficiency under

simulated solar light.
Presently, graphene sheet synthesized on Ni substrates and
through other methods are being transferred on to conductive
substrates for transparent electrode applications.139−141 This
method might be suitable for smaller electrodes and scien-
tific exploration purposes; however, the challenge of large-area
graphene synthesis directly on transparent substrates still exists.
It is known that the energy band gap of armchair GNRs is
inversely proportional to the width. The energy gap of a 15 nm
wide GNR is around 0.2 eV, whereas an epitaxial graphene thin
film on a SiC substrate has a band gap of 0.26 eV.28 Therefore,
graphene were also used as a novel acceptor for bulk heterojunc-
tion polymer photovoltaic cells, showing remarkably reduced
photoluminescence and consequently efficient energy transfer
in P3OT/graphene interface.145
For microelectronic application, high mobility and excellent
mechanical properties of transparent graphene film are useful
to make flexible and stretchable electrodes. Kim et al. evaluated
the foldability of the graphene films, transferred to a polyethy-
lene terephthalate (PET) substrate (thickness, 100 µm) coated
with a thin PDMS layer (thickness, 200 µm), by measuring re-
sistance as a function of bending radii.17 The resistances show
little variation up to the bending radius of 2.3 mm (approximate
tensile strain of 6.5%) and are perfectly recovered after unbend-
ing, (Figure 16). Notably, the original resistance can be restored
even for the bending radius of 0.8 mm (approximate tensile
strain of 18.7%), exhibiting extreme mechanical stability.
FIG. 16. Variation in resistance of a graphene film transferred
to a 0.3 mm-thick PDMS/PET substrate for different distances
between holding stages (that is, for different bending radii).
The left inset shows the anisotropy in four-probe resistance,
measured as the ratio, Ry /Rx , of the resistances parallel and per-
pendicular to the bending direction, y. The right inset shows the
bending process.16 (Reprinted with permission from Macmillan
Publishers Ltd: Nature,17 Copyright 2009.)
FIG. 17. Schematic illustration of synthesis and structure of
SnO2 /GNS for battery application. (Reprinted with permission
from Pack et al.40 Copyright 2009: American Chemical Society.)
4.5. Battery
Li-ion battery has been a key component of hand-held
devices, due to its renewable and clean nature. Graphite is
usually employed as anode material in Li-ion battery, due to
its reversibility and reasonable specific capacity. However, to
meet the increasing demand for Li-ion batteries with higher
energy density and durability, new electrode materials with
higher capacity and stability need to be developed. Among
the carbonaceous materials, graphene-based anode has been
proposed as one of the promising alternatives in Li-ion batteries,
as graphene has superior electrical conductivity than graphitic
carbon, high surface area and chemical tolerance.122,141,146−147
Paek et al. has prepared graphene nanosheets decorated with
SnO2 nanoparticles by dispersing reduced graphene nanosheets
in the ethylene glycol and reassembling in presence of SnO2
nanoparticles, as shown in Figure 17.40 The SnO2 /graphene
exhibits a reversible capacity of 810 mAh/g and its cycling
performance is drastically enhanced in comparison with
that of the bare SnO2 nanoparticle. Wang et al. have shown
self-assembled TiO2 -graphene hybrid nanostructure to enhance
high rate performance of electro-chemical active material.41
They used anionic sulfate surfactants to assist the stabilization
of graphene in aqueous solutions and facilitate self-assembly of
in situ grown nanocrystalline TiO2 with graphene. The specific
capacity was 87 mAh/g, which is more than double the high rate
capacity (35 mAh/g) of the control rutile TiO2 . The specific ca-
pacity of the anatase TiO2 -functionalized graphene at the rate of
30C is as high as 96 mAh/g compare with 25 mAh/g of control
anatase TiO2 . Though few reports on application of graphene as
 SYNTHESIS OF GRAPHENE AND ITS APPLICATIONS
electrode material in batteries are available, future research need
to concentrate more on understanding the mechanism of the
electrochemical process in those systems and focus on applica-
tion of a variety graphene based electrodes in Li-ion batteries.
5. SUMMARY
Single-layer graphene shows room-temperature ambipolar
characteristics, while few-layer graphene shows no energy gap.
The structure becomes increasingly metallic the more layers it
contains. Graphene shows very high surface area, having good
gas adsorption property and hydrogen uptake up to 3 wt% H2 .
Graphene narrow ribbons (GNRs), with zigzag or armchair con-
figuration, show different electrical property; the zigzag GNRs
are metallic and armchairs can be either metallic or semicon-
ductor. The energy band gap of armchair GNRs are inversely
proportional to the width.
The recent achievements in graphene growth by thermal
CVD onto Ni thin film has confirmed reproducibility of good
quality graphene on a centimeter scale substrate and successful
transfer to many other substrates including Si, glass and PDMS.
However, growth of graphene on wafer size substrates, efficient
control of the number of layers and width of graphene has yet
to be demonstrated.
Although graphene has shown exceptional electrical, opto-
electric, and chemical properties and thus, has excellent po-
tential be used as transparent electrode, field effect transistor,
sensors and energy applications, synthesis of graphene films on
arbitrary substrates, with desired energy bandgap, still remained
to be achieved. It is expected that after complete development of
graphene films, on a large scale, with desired electrical proper-
tles, graphene may become more attractive than silicon-based
electronics and thus provide future electric devices with higher
speed, chemical stability, environmental friendliness, and better
functionality.
REFERENCES
1. J. H. Chen, C. Jang, S. Xiao, M. Ishigami, and M. S. Fuhrer,
Intrinsic and extrinsic performance limits of graphene devices on
SiO2 , Nature Nanotech, 3, 206 (2008).
2. A. K. Geim and P. Kim, Carbon wonderland, Scientific American,
298, 90 (2008).
3. K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang,
S. V. Dubonos, I. V. Grigorieva, and A. A. Firsov, Electric field
effect in atomically thin carbon films, Science, 306, 666 (2004).
4. M. I. Katsnelson, Graphene: carbon in two dimensions, Materials
Today, 10, 20 (2007).
5. A. B. Kuzmenko, E. V. Heumen, F. Carbone, and D. V. D Marel,
Universal optical conductance of graphite, Phys. Rev. Lett., 100,
117401 (2008).
6. A. K. Geim, and K. S. Novoselov, The rise of graphene, Nature
Mater., 6, 183 (2007).
7. H. Shioyama, H. Sakakihara, N. Iwashita, K. Tatsumi, and Y.
Sawada, On the generation of fine metallic particles in graphite
matrix. J. Mater. Sci. Lett., 13, 1056 (1994).
67
8. L. M. Viculis, J. J. Mack, and R. B. Kaner, A chemical route to
carbon nanoscrolls, Science, 299, 1361 (2003).
9. C. Berger, Z. Song, T. Li, X. Li, A. Y. Ogbazghi, R. Feng, Z. Dai,
et al., Ultrathin epitaxial graphite: 2D electron gas properties and
a route toward Graphene-based nanoelectronics, J. Phys. Chem,
108, 19912 (2004).
10. T. A. Land, T. Michely, R. J. Behm, J. C. Hemminger, and G.
Comsa, STM investigation of single layer graphite structures pro-
duced on Pt(111) by hydrocarbon decomposition, Surface Sci.,
264, 261 (1992).
11. A. Nagashima, K. Nuka, H. Itoh, T. Ichinokawa, C. Oshima,
and S. Otani, Electronic states of monolayer graphite formed on
TiC(111) surface, Surface Sci., 291, 93 (1993).
12. A. Reina, X. Jia, J. Ho, D. Nezich, H. Son, V. Bulovic, M. S.
Dresselhaus, and J. Kong, Large area few-layer graphene films
on arbitrary substrates by chemical vapor deposition, Nano Lett.,
9, 30 (2009).
13. C. N. R. Rao, K. Biawas, K. S. Subramanyam, and A. Govindaraj,
Graphene, the new nanocarbon, J. Mater. Chem., 19, 2457 (2009).
14. A. H. Castro Neto, F. Guinea, N. M. R. Peres, K. S. Novoselov,
and A. K. Geim, The electronic properties of graphene, Rev. Mod.
Phys., 81, 109 (2009).
15. J. Hass, W. A. de Heer, and E. H. Conrad, The growth and mor-
phology of epitaxial multilayer graphene, J. Phys. Cond. Matter,
20, 323202 (2008).
16. Z. H. Ni, H. M. Wang, J. Kasim, H. M. Fan, T. Yu, Y. H.
Wu, Y. P. Feng, and Z. X. Chen, Graphene thickness determi-
nation using reflection and contrast spectroscopy, Nano Lett., 7,
2758 (2007).
17. K. S. Kim, Y. Zhao, H. Jang, S. Y. Lee, J. M. Kim, K. S. Kim, J.
H. Ahn, et al., Large-scale pattern growth of graphene films for
stretchable transparent electrodes, Nature, 457, 706 (2009).
18. M. I. Katsnelson, K. S. Novoselov, and A. K. Geim, Chiral tun-
neling and the Klein paradox in graphene, Nature Physics, 2, 620
(2006).
19. K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, M. I.
Katsnelson, I. V. Grigorieva, S. V. Dubonos, and A. A. Firsov,
Two-dimensional gas of massless Dirac fermions in graphene,
Nature, 438, 197 (2005).
20. K. S. Novoselov, Z. Jiang, Y. Zhang, S. V. Morozov, H. L. Stormer,
U. Zeitler, J. C. Maan, et al., Room-temperature quantum Hall
effect in graphene, Science, 315, 1379 (2007).
21. F. Schedin, A. K. Geim, S. V. Morozov, E. W. Hill, P. Blake,
M. I. Katsnelson, and K. S. Novoselov, Dtection of individual
gas molecules adsorbed on graphene, Nature Materials, 6, 652
(2007).
22. J. S. Bunch, A. M. van der Zande, S. S. Verbridge, I. W. Frank,
D. M. Tanenbaum, J. M. Parpia, H. G. Craighead, and P. L.
McEuen, Electromechanical resonators from graphene sheets,
Science, 315, 490 (2007).
23. C. Lee, X. Wei, J. W. Kysar, and J. Hone, Measurement of the
elastic properties and intrinsic strength of monolayer graphene,
Science, 321, 385 (2008).
24. A. Sakhaee-Pour, Elastic properties of single-layered graphene
sheet, Solid State Commun., 149, 91 (2009).
25. H. Chen, M. B.Müller, K. J. Gilmore, G. G. Wallace, and D. Li,
Mechanically strong electrically conductive and biocompatible
graphene paper, Adv. Materials, 20, 3557 (2008).
68 W. CHOI ET AL.
26. K. S. Novoselov, E. McCann, S. V. Morozov, V. I. Fal ko, M. I.
Katsnelson, U. Zeitler, D. Jiang, et al., Unconventional quantum
Hall effect and Berry’s phase of 2π in bilayer graphene, Nature
Physics, 2, 177 (2006).
27. E. McCann, Asymmetry gap in the electronic band struc-
ture of bilayer graphene, Physical Review B, 74, 161403
(2006).
28. S. Y. Zhou, G.-H. Gweon, A. V. Fedorov, P. N. First, W. A. de
Heer, D. -H. Lee, F. Guinea, et al., Substrate-induced bandgap
opening in epitaxial graphene, Nature Materials, 6, 770 (2007).
29. J. Hass, F. Varchon, J. E. Millán-Otoya, M. Sprinkle, N. Sharma,
W. A. de Heer, C. Berger, et al., Why multilayer graphene on
4H-SiC(0001) behaves like a single sheet of graphene, Phys. Rev.
Lett., 100, 125504 (2008).
30. D. C. Elias, R. R. Nair, T. M. G. Mohiuddin, S. V. Morozov, P.
Blake, M. P. Halsall, A. C. Ferrari, et al., Control of graphene’s
properties by reversible hydrogenation: evidence for graphene,
Science, 323, 610 (2009).
31. S. Y. Zhou, D. A. Siegel, A. V. Fedorov, and A. Lanzara, Metal
to insulator transition in epitaxial graphene induced by molecular
doping, Phys. Rev. Lett., 101, 086402 (2008).
32. N. M. R. Peres, The electronic properties of graphene and its
bilayer, Vacuum, 83, 1248 (2009).
33. S. V. Morozov, K. S. Novoselov, F. Schedin, D. Jiang, A. A. Firsov,
and A. K. Geim, Two-dimensional electron and hole gases at the
surface of graphite, Phys. Rev. B, 72, 201401 (2005).
34. A. Ghosh, K. S. Subramanyam, K. S. Krishna, S. Datta, A. Govin-
daraj, S. K. Pati, and C. N. R. Rao, Uptake of H2 and CO2 by
graphene, J. Phys. Chem. C, 112, 15704 (2008).
35. S. Niyogi, E. Bekyarova, M. E. Itkis, J. L. McWilliams, M. A.
Hamon, and R. C. Haddon, Soluton properties of graphite and
graphene, J. Am. Chem. Soc., 128, 7720 (2006).
36. K. S. Subrahmanyam, S. R. C. Vivekchand, A. Govindaraj, and
C. N. R. Rao, A study of graphenes prepared by different meth-
ods: characterization, properties and solubilization, J. Materials
Chem., 18, 1517 (2008).
37. R. Muszynski, B. Seger, and P. V. Kamat, Decorating graphene
sheets with gold nanoparticles, J. Phys. Chem. C, 112, 5263
(2008).
38. T. Enoki, Y. Kobayashi, and K. -I. Fukui, Electronic structures
of graphene edges and nanographene, Int. Rev. Phys. Chem., 26,
609 (2007).
39. N. Varghese, U. Mogera, A. Govindaraj, A. Das, P. K. Maiti,
A. K. Sood, and C. N. R. Rao, Binding of DNA nucleobases
and nucleosides with graphene, Chem. Phys. Chem., 10, 206
(2009).
40. S.-M. Paek, E. J. Yoo, and I. Honma, Enhanced cyclic perfor-
mance and lithium storage capacity of SnO/graphene nanoporous
electrodes with three-diemnsionally delaminated flexible struc-
ture, Nano Lett., 9, 72 (2009).
41. D. Wang, D. Choi, J. Li, Z. Yang, Z. Nie, R. Kou, D. Hu,
et al., Self-assembled TiO2 -graphene hybrid nanostructures for
enhanced Li-ion insertion, ACS Nano, 3, 907 (2009).
42. B. Lamg, A LEED study of the deposition of carbon on platinum
crystal surfaces, Surface Sci., 53, 317 (1975).
43. E. Rokuta, Y. Hasegawa, A. Itoh, K. Yamashita, T. Tanaka, S.
Otani, and C. Oshima, Vibrational spectra of the monolayer films
of hexagonal boron nitride and graphite on faceted Ni(755), Sur-
face Sci., 427, 97 (1999).
44. H. Shioyama, Cleavage of graphite to graphene, J. Mate. Sci.
Lett., 20, 499 (2001).
45. K. S. Novoselov, D. Jiang, F. Schedin, T. J. Booth, V. V. Khotke-
vich, S. V. Morozov, and A. K. Geim, Two-dimensional atomic
crystals, PNAS, 102, 10451 (2005).
46. S. S. Datta, D. R. Strachan, S. M. Khamis, and A. T. C. Johnson,
Crystallographic etching of few-layer grapheme, Nano Lett., 8,
1912 (2008).
47. U. Bangert, A. L. Bleloch, P. Wang, R. R. Nair, A. K. Geim, and
M. H. Gass, Free-standing grapheme at atomic resolution, Nature
Nanotechnol., 3, 676 (2008).
48. J. C. Meyer, C. O. Girit, M. F. Crommie, and A. Zettl, Hydrocar-
bon lithography on grapheme membranes, Appl. Phys. Lett., 92,
123110 (2008).
49. V. Huc, N. Bendiab, N. Rosman, T. Ebbesen, C. Delacour, and V.
Bouchiat, large and flat graphene flakes produced by epoxy bond-
ing and reverse exfoliation of highly oriented pyrolytic graphite,
Nanotechnology, 19, 455601 (2008).
50. A. Shukla, R. Kumar, J. Mazher, and A. Balan, Graphene made
easy: high quality large-area samples, Solid State Commun., 149,
718 (2009).
51. S. Stankovich, R. D. Piner, X. Chen, N. Wu, S. T. Nguyen, and
R. S. Ruoff, Stable aqueous dispersions of graphitic nanoplates
via the reduction of exfoliated graphite oxide in the pres-
ence of poly(sodium 4-styrenesulfonate), J. Mate. Chem., 16,
155 (2006).
52. S. Stankovich, D. A. Dikin, R. D. Piner, K. A. Kohlhaas, A.
Lleinhammes, Y. Jia, Y. Wu, et al., Synthesis of grapheme-based
nanosheets via chemical reduction of exfoliated graphite oxide,
Carbon, 45, 1558 (2007).
53. Y. Hernandez, V. Nicolosi, M. Lotya, F. M. Blighe, Z. Sun, S.
De, I. T. Mcgovern, et al., High-yield production of graphene by
liquid-phase exfoliation of graphite, Nature Nanotechnol., 3, 563
(2008).
54. M. Lotya, Y. Hernandez, P. J. King, R. J. Smith, V. Nicolosi,
L. S. Karlsson, F. M. Blighe, et al., Liquid phase production of
graphene by exfoliation of graphite in surfactant/water solutions,
J. Am. Chem. Soc., 131, 3611 (2009).
55. Y. Si, and E. T. Samulski, Synthesis of water soluble graphene,
Nano Lett., 8, 1679 (2008).
56. C. Nethravathi, and M. Rajamathi, Chemically modified graphene
sheets produced by the solvothermal reduction of colloidal dis-
persions of graphite oxide, Carbon, 46, 1994 (2008).
57. V. C. Tung, M. J. Allen, Y. Yang, and R. B. Kaner, High-
throughput solution processing of large-scale graphene, Nature
Nanotechnol., 4, 25 (2008).
58. V. C. Tung, L. Chen, M. J. Allen, J. K. Wassei, K. Nelson, R.
B. Kaner, and Y. Yang, Low-tempersture solution processing of
graphene-carbon nanotube hybrid materials for high-performance
transparent conductors, Nano Lett., 9, 1949 (2009).
59. P. R. Somani, S. P. Somani, and M. Umeno, Planer nano-
graphenes from camphor by CVD, Chemical Physics Letters,
430, 56 (2006).
60. A. N. Obraztsov, E. A. Obraztsova, A. V. Tyurnina, and A. A.
Zolotukhin, Chemical vapor deposition of thin graphite films of
nanometer thickness, Carbon, 45, 2017 (2007).
61. Q. Yu, J. Lian, S. Siriponglert, H. Li, Y. P. Chen, and S. S. Pei,
Graphene segregated on Ni surfaces and transferred to insulators,
Appl. Phys. Lett., 93, 113103 (2008).
 SYNTHESIS OF GRAPHENE AND ITS APPLICATIONS
62. A. N. Obraztsov, Making graphene on a large scale, Nature Nan-
otechnol., 4, 212 (2009).
63. X. Wang, H. You, F. Liu, M. Li, L. Wan, S. Li, Q. Li, et al., Large-
scale synthesis of few-layered graphene using CVD, Chem. Vapor
Deposition, 15, 53 (2009).
64. L. G.de Arco, Y. Zhang, A. Kumar, and C. Zhou, Synthesis trans-
fer and devices of single- and few-layer graphene by chemical
vapor deposition, IEEE Trans. Nanotechnol., 8, 135 (2009).
65. S. J. Chae, F. Günes, K. K. Kim, E. S. Kim, G. H. Han, S. M. Kim,
H.-J. Shin, et al., Synthesis of large-area graphene layers on poly-
nickel substrate by chemical vapor dposition:wrinkle formation,
Adv. Mater., 21, 2328 (2009).
66. X. Li, W. Cai, J. An, S. Kim, J. Nah, D. Yang, R. Piner, et al.,
Large-area synthesis of high-quality and uniform graphene films
on copper foils, Science, 324, 1312 (2009).
67. A. N. Obraztsov, A. A. Zolotukhin, A. O. Ustinov, A. P. Volkov,
Y. Svirko, and K. Jefimovs, DC discharge plasma studies for
nanostructured carbon CVD, Diamond Related Mater., 12, 917
(2003).
68. J. J. Wang, M. Y. Zhu, R. A. Outlaw, X. Zhao, D. M. Manos,
and B. C. Holoway, Free-standing subnanometer graphite sheets,
Appl. Phys. Lett., 85, 1265 (2004).
69. J. J. Wang, M. Y. Zhu, R. A. Outlaw, X. Zhao, D. M. Manos,
and B. C. Holoway, Synthesis of carbon nanosheets by induc-
tively coupled radio-frequency plasma enhanced chemical vapor
deposition, Carbon, 42, 2867 (2004).
70. M. Hiramatsu, K. Shiji, H. Amano, and M. Hori, Fabrication of
vertically aligned carbon nanowalls using capacitively coupled
plasma-enhanced chemical vapor deposition assisted by hydro-
gen radical injection, Appl. Phys. Lett., 84, 4708 (2004).
71. M. Zhu, J. Wang, B. C. Holloway, R. A. Outlaw, X. Zhao, K. Hou,
V. Shutthanandan, and D. M. Manos, A mechanism for carbon
nanosheet formation, Carbon, 45, 2229 (2007).
72. C. Wang, S. Yang, Q. Wang, Z. Wang, and J. Zhang, Super-low
friction and super-elastic hydrogenated carbon films originated
from a unique fullerene-like nanostructure, Nanotechnology, 19,
225709 (2008).
73. A. Malesevic, R. Kemps, L. Zhang, R. Erni, G.van Tendeloo, A.
Vanhulsel, and C. van Haesendonck, A versatile plasma tool for
the synthesis of carbon nanotubes and few-layer graphene sheets,
J. Optoelect. Adv. Mater., 10, 2052 (2008).
74. V. A. Coleman, R. Knut, O. Karis, H. Grennberg, U. Jansson,
R. Quinlan, B. C. Holloway, et al., Defect formation in graphene
nanosheets by acid treatment: an x-ray absorption spectroscopy
and density functional theory study, J. Phys. D: Appl. Phys., 41,
062001 (2008).
75. N. G. Shang, P. Papakonstantinou, M. McMullan, M. Chu, A.
Stamboulis, A. Potenza, S. S. Dhesi, and H. Marchetto, Catalyst-
free efficient growth orientation and biosensing properties of mul-
tilayer graphene nanoflake films with sharp edge planes, Adv.
Functional Mater., 18, 3506 (2008).
76. G. D. Yuan, W. J. Zhang, Y. Yang, Y. B. Tang, Y. Q. Li, J.
X. Wang, X. M. Meng, Z. B. He, et al., Graphene sheets via
microwave chemical vapor deposition, Chem. Phys. Lett., 467,
361 (2009).
77. S. Horiuchi, T. Gotou, M. Fujiwara, T. Asaka, T. Yokosawa, and
Y. Matsui, Single graphene sheet detected in a carbon nanofilm,
Appl. Phys. Lett., 84, 2403 (2004).
69
78. X. Li, G. Zhang, X. Bai, X. Sun, X. Wang, E. Wang, and H.
Dai, Highly conducting graphene sheets and Langmuir-Blodgett
films, Nature Nanotechnol., 3, 538 (2008).
79. M. Choucair, P. Thordarson, and J. A. Stride, Gram-scale produc-
tion of graphene based on solvothermal synthesis and sonication,
Nature Nanotechnol., 4, 30 (2009).
80. Z. Wu, W. Ren, L. Gao, B. Liu, C. Jiang, and H. Cheng, Synthesis
of high-quality graphene with a pre-determined number of layers,
Carbon, 47, 493 (2009).
81. S. Park, and R. S. Ruoff, Chemical methods for the production of
graphenes, Nature Nanotechnol., 4, 217 (2009).
82. E. Rollings, G. H. Gweon, S. Y. Zhou, B. S. Mun, J. L. McCh-
esney, B. S. Hussain, A. V. Fedorov, et al., Sythesis and charac-
terization of atomically-thin graphite films on a silicon carbide
substrate, J. Phys. Chem. Solids, 67, 2172 (2006).
83. T. Ohta, F. El. Gabaly, A. Bostwick, J. L. McChesney, K. V.
Emtsev, A. K. Schmid, T. Seyller, et al., Morphology of graphene
thin film growth on SiC(0001), New J. Phys., 10, 023034 (2008).
84. Z. G. Cambaz, G. Yushin, S. Osswald, V. Mochalin, and Y.
Gogotsi, Noncatalytic synthesis of carbon nanotubes graphene
and graphite on SiC, Carbon, 46, 841 (2008).
85. Z.-Y. Juang, C.-Y. Wu, C.-W. Lo, W.-Y. Chen, C.-F. Huang, J.-
C. Hwang, F.-R. Chen, et al., Syntehsis of graphene on silicon
carbide substrates at low temperature, Carbon, 47, 2026 (2009).
86. K. V. Emtsev, A. Bostwick, K. Horn, J. Jobst, G. L. Kellogg, l.
Ley, J. L. McChesney, et al., Towards wafer-size graphene layers
by atmospheric pressure graphitization of silicon carbide, Nature
Mater., 8, 203 (2009).
87. A. L.Vázquez de parga, F. Calleja, B. Borca, M. C. G. Passeggi
Jr., J. J. Hinarejos, F. Guinea, and R. Miranda, Periodically rip-
pled graphene: growth and spatially resolved electronic structure,
Phys. Rev. Lett., 100, 056807 (2008).
88. P. W. Sutter, J.-I. Flege, and E. A. Sutter, Epitaxial graphene on
ruthenium, Nature Mater., 7, 406 (2008).
89. J. Wintterlin, and M.-L. Bocquet, Graphene on metal surfaces,
Surface Sci., 603, 1841 (2009).
90. A. G. Cano-Márquez, F. J. Rodrı́guez-Macı́as, J. Campos-
Delgado, C. G. Espinosa-González, F. Tristán-López, D. Ramı́re-
González, D. A. Cullen, et al., Ex-MWNTs: graphene sheets and
ribbons produced by lithium intercalation and exfoliation of car-
bon nanotubes, Nano Lett., 9, 1527 (2009).
91. L. Jiao, L. Zhang, X. Wang, G. Diankov, and H. Dai, Narrow
graphene nanoribbons from carbon nanotubes, Nature, 458, 877
(2009).
92. D. V. Kosynkin, A. L. Higginbotham, A. Sinitskii, J. R. Lomeda,
A. Dimiev, B. K. Price, and J. M. Tour, Longitudinal unzipping
of carbon nanotubes to form graphene nanoribbons, Nature, 458,
872 (2009).
93. C.-D. Kim, B.-K. Min, and W.-S. Jung, Preparation of graphene
sheets by the reduction of carbon monoxide, Carbon, 47, 1610
(2009).
94. Y. Zhang, J. P. Small, W. V. Pontius, and P. Kim, Fabrication and
electric-field-dependent transport measurements of mesoscopic
graphite devices, Appl. Phys. Lett., 86, 073104 (2005).
95. A. Turchanin, A. Beyer, C. T. Nottbohm, X. Zhang, R. Stosch,
A. Sologubenko, J. Mayer, et al., One nanometer thin carbon
nanosheets with tunable conductivity and stiffness, Adv. Mater.,
21, 1233 (2009).
70 W. CHOI ET AL.
96. M. J. Schultz, X. Zhang, S. Unarunotai, D.-Y. Khang, Q. Cao,
C. Wang, C. lei, et al., Synthesis of linked carbon monolayers:
Films, balloons, tubes and pleated sheets, Proc. Natl. Acad. Sci.,
105, 7353 (2008).
97. A. Malesevic, R. Kemps, A. Vanhulsel, M. P. Chowdhury, A.
Volodin, and C. V. Haesendonck, Field emission from vertically
aligned few-layer graphene, J. Appl. Phys., 104, 084301 (2008).
98. G. Eda, H. E. Unalan, N. Rupesinghe, G. A. J. Amartunga, and
M. Chhowalla, Field emission from graphene based composite
films, Appl. Phy. Lett., 93, 233502 (2008).
99. Z. S. Wu, S. Pei, W. Ren, D. Tang, L. Gao, B. Liu, F. Li, C.
Liu, and H. M. Cheng, Field emission from single layer graphene
films prepared by electrophoretic deposition, Adv. Mater., 21,
1756 (2009).
100. S. Watcharotone, R. S. Ruoff, and F. H. Read, Possibilities for
graphene for field emission: modeling studies using the BEM,
Physics Procedia, 1, 71 (2008).
101. M. Araidai, Y. Nakamura, and K. Watanabe, Field emission mech-
anisms of graphitic nanostructures, Phys. Rev. B, 70, 245410
(2004).
102. A. Yu. Babenko, A. T. Dideykin, and E. D. Eidelman, graphene
ladder: a model of field emission center on the surface of loose
nanocarbon materials, Phys. Solid State, 51, 435, (2009).
103. M. S. Dresselhaus, and G. Dresselhaus, Intercalation compounds
of graphite. Adv. Phys., 51, 1(2002).
104. J. D. Fowler, M. J. Allen, V. C. Tung, Y. Yang, R. B. Kaner, and B.
H. Weiller, Practical chemical sensors from chemically derived
graphene, ACS Nano, 3, 201 (2009).
105. R. S. Sundaram, C. G. Navarro, K. Balasubramaniam, M.
Burghard, and K. Kern, Electrochemical modification of
graphene, Adv. Mater., 20, 3050 (2008).
106. C. Shan, H. Yang, J. Song, D. Han, A. Ivaska, and L. Niu, Direct
electrochemistry of glucose oxidase and biosensing for glucose
based on graphene, Anal. Chem., 81, 2378 (2009).
107. S. Alwarappan, A. Erdem, C. Liu, and C. Z. Li, Probing the
electrochemical properties of graphene nanosheets for biosensing
applications, J. Phys. Chem. C, 113, 8853 (2009).
108. J. Li, S. Guo, Y. Zhai, and E Wang, Nafion–graphene nanocom-
posite film as enhanced sensing platform for ultrasensitive de-
termination of cadmium, Electrochemistry Commun., 11, 1085
(2009).
109. Y. Dan, Y. Lu, N. J. Kybert, Z. Luo, and A. T. C. Johnson, Intrinsic
response of graphene vapor sensors, Nano Lett., 9, 1472 (2009).
110. O. Leenaerts, B. Partoens, and F. M. Peeter, Adsorption of H2 O,
NH3 , CO, NO2 , and NO on graphene: A first-principles study,
Phys. Rev B, 77, 125416 (2008).
111. Z. M. Ao, J. Yang, S. Li, and Q. Jiang, Enhancement of CO
detection in Al doped graphene, Chem. Phys. Lett., 461, 276
(2008).
112. L. N. Rangel, and J. M. Seminario, Graphene terahertz generators
for molecular circuits and sensors, J. Phys. Chem. A, 112, 13699
(2008).
113. Y. H. Zhang1, Y. B. Chen, K. G. Zhou, C. H. Liu, J. Zeng,
H. L. Zhang, and Y. Peng, Improving gas sensing properties of
graphene by introducing dopants and defects: a first-principles
study, Nanotechnology, 20, 185504 (2009).
114. E. H. Hwang, S. Adam, and S. D. Sarma, Transport in chemically
doped graphene in the presence of adsorbed molecules, Phy. Rev
B, 76, 195421 (2007).
115. Y. W. Son, M. L. Cohen, and S. G. Louie, Energy Gaps in
Graphene Nanoribbons, PRL, 97, 216803 (2006).
116. V. Barone, O. Hod, and G. E. Scuseria, Electronic structure and
stability of semiconducting graphene nanoribbons, Nano Lett., 6,
2748 (2006).
117. D. A. Areshkin, D. Gunlycke, and C. T. White, Ballistic transport
in graphene nanostrips in the presence of disorder: Importance of
edge effects, Nano Lett., 7, 204 (2007).
118. G. C. Liang, N. Neophytou, D. E. Nikonov, and M. S. Lund-
strom, Performance projections for ballistic graphene nanorib-
bon field-effect transistors, IEEE Trans. Electron. Dev., 54, 677
(2007).
119. K. Nakada, M. Fujita, G. Dresslhaus, and M. S. Dresselhaus,
Edge state in graphene ribbons: Nanometer size effect and edge
shape dependence, Phys. Rev. B, 54, 17954 (1996).
120. M. Y. Han, B. Ozyilmaz, Y. B. Zhang, and P. Kim, Energy Band-
Gap Engineering of Graphene Nanoribbons, Phys. Rev. Lett., 98,
206805 (2007).
121. Z. Chen, Y. M. Lin, M. J. Rooks, and P. Avouris, Graphene nano-
ribbon electronics, Physica E, 40, 228 (2007).
122. X. Li, X. Wang, L. Zhang, S. Lee, and H. Dai, Chemically derived,
ultrasmooth graphene nanoribbon semiconductors, Science, 319,
1229 (2008).
123. B. Obradovic, R. Kotlyar, F. Heinz, P. Matagne, T. Rakshit, M. D.
Giles, and M. A. Stettler, Analysis of graphene nanoribbons as a
channel material for field-effect transistors, Appl. Phys. Lett., 88,
142102 (2006).
124. I. Meric, M. Y. Han, A. F. Young, B. Ozyilmaz, P. Kim, and
K. L. Shepard, Current saturation in zero bandgap, top-gated
graphene field-effect transistors, Nature Nanotechnol., 3, 654
(2008).
125. T. Ohta, A. Bostwick, T. Seyller, K. Horn, and E. Rotenberg,
Controlling the electronic structure of bilayer graphene, Science,
313, 951 (2006).
126. J. B. Oostinga, H. B. Heersche, X. Liu, A. F. Morpurgo, and
L. M. K. Vandersypen, Gate-induced insulating state in bilayer
graphene devices. Nature Mater., 7, 151 (2008).
127. J. Bai, X. Duan, and Y. Huang, Rational fabrication of graphene
nanoribbons using a nanowire etch mask, Nanoletters, 9, 2083
(2009).
128. M. Luisiera, and G. Klimeck, Performance analysis of statistical
samples of graphene nanoribbon tunneling transistors with line
edge roughness, Appl. Phys. Lett., 94, 223505 (2009).
129. F. Tseng, D. Unluer, K. Holcomb, M. R. Stan, and A. W. Ghosh,
Diluted chirality dependence in edge rough graphene nanoribbon
field-effect transistors, Appl. Phys. Lett., 94, 223112 (2009).
130. D. B. Farmer, R. G. Mojarad, V. Perebeinos, Y. M. Lin, G.
S. Tulevski, J. C. Tsang, and P. Avouris, Chemical doping
and electron-hole conduction asymmetry in graphene devices,
Nanoletters, 9, 388 (2009).
131. Y. Ouyang, X. Wang, H. Dai, and J. Guo, Carrier scattering in
graphene nanoribbon field-effect transistors, Appl. Phys. Lett.,
92, 243124 (2008).
132. G. Liang, N. Neophytou, M. S. Lundstrom, and D. E. Nikonov,
Contact effects in graphene nanoribbon transistors, Nanoletters,
8, 1819 (2008).
133. V. Ryzhii, M. Ryzhii, and T. Otsuji, Thermionic and tunneling
transport mechanisms in graphene field-effect transistors, Phys.
Stat. Sol. (a), 205, 1527 (2008).
 SYNTHESIS OF GRAPHENE AND ITS APPLICATIONS
134. F. M. Rojas, J. F. Rossier, L. Brey, and J. J. Palacios, Performance
limits of graphene-ribbon field-effect transistors, Phys. Rev. B,
77, 045301 (2008).
135. V. Ryzhii, M. Ryzhii, A. Satou, and T. Otsuji, Current-voltage
characteristics of a graphene-nanoribbon field-effect transistor, J.
Appl. Phys., 103, 094510 (2008).
136. Q. Zhang, T. Fang, H. Xing, A. Seabaugh, and D. Jena, Graphene
Nanoribbon Tunnel Transistors, IEEE Electron Device Lett.,
0741, 3106 (2008).
137. V. Ryzhii, M. Ryzhii, A. Satou, T. Otsuji, and N. Kirova, Device
model for graphene bilayer field-effect transistor, J. Appl. Phys.,
105, 104510 (2009).
138. P. Zhao, J. Chauhan, and J. Guo, Computational study of tunneling
transistor based on graphene nanoribbon, Nano Letters, 9, 684
(2009).
139. K. S Kim, Y. Zhao, H. Jang, S. Y. Lee, J. M. Kim, K. S.
Kim, J. H. Ahn, et al., Large-scale pattern growth of graphene
films for stretchable transparent electrodes, Nature, 457, 706
(2009).
140. J. Wu, H. A. Becerril, Z. Bao, Z. Liu, Y. Chen, and P. Peumans,
Organic solar cells with solution-processed graphene transarent
electrodes, Appl. Phys. Lett., 92, 263302 (2008).
71
141. X. Wang, L. Zhi and K. Mullen, and Transparent, conductive
graphene electrodes for dye-sensitized solar cells, Nanoletters, 8,
323 (2008).
142. R. R. Nair, P. Blake, A. N. Grigorenko, K. S. Novoselov, T. J.
Booth, T. Stauber, N. M. R. Peres, and A. K. Geim, Fine structure
constant defines visual transparency of grapheme, Science, 320,
1308 (2008).
143. W. Hong, Y. Xu, G. Lu, C. Li, and G. Shi, Transparent
grapheme/PEDOT-PSS composite films as counter electrodes
of dye-sensitized solar cells, Electrochem. Commun., 10, 1555
(2008).
144. X. wang, L. Zhi, N. Tsao, Z. Tomovic, J. Li, and K. Muellen,
Transparent carbon films as electrodes in organic solar cells,
Angew. Chem. Int. Ed., 47, 2990 (2008).
145. Z. Liu, Q. Liu, Y. Huang, Y. Ma, S. Yin, X. Zhang, W. Sun, and
Y. Chen, Adv. Mater., 20, 3924 (2008).
146. J. C. Meyer, A. K. Geim, M. I. Katsnelson, K. S. Novoselov, T. J.
Booth, and S. Roth, The structure of suspended graphene sheets,
Nature, 446, 60 (2007).
147. S. Gilje, S. Han, M. Wang, K. L. Wang, and R. B. Kaner, A
chemical route to graphene for device applications, Nano Lett.,
7, 3394 (2007).