Grafeno

Graphene based materials: Past, present and future
Virendra Singh
a,b
, Daeha Joung
a,c
, Lei Zhai
a,d,
, Soumen Das
a,b
,
Saiful I. Khondaker
a,c,e,
, Sudipta Seal
a,b,
a
Advanced Materials Processing Analysis Center and Nanoscience Technology Center, University of Central Florida, Orlando, FL, USA
b
Department of Mechanical, Materials and Aerospace Engineering, University of Central Florida, Orlando FL, USA
c
Department of Physics, University of Central Florida, Orlando, FL, USA
d
Department of Chemistry, University of Central Florida, Orlando, FL, USA
e
School of Electrical Engineering and Computer Science, University of Central Florida, Orlando, FL, USA
a r t i c l e i n f o
Article history:
Received 22 February 2011
Accepted 30 March 2011
Available online 3 April 2011
a b s t r a c t
Graphene, a two dimensional monoatomic thick building block of a
carbon allotrope, has emerged as an exotic material of the 21st cen-
tury, and received world-wide attention due to its exceptional
charge transport, thermal, optical, and mechanical properties.
Graphene and its derivatives are being studied in nearly every eld
of science and engineering. Recent progress has shown that the
graphene-based materials can have a profound impact on
electronic and optoelectronic devices, chemical sensors, nanocom-
posites and energy storage. The aim of this review article is to
provide a comprehensive scientic progress of graphene to date
and evaluate its future perspective. Various synthesis processes of
single layer graphene, graphene nanoribbons, chemically derived
graphene, and graphene-based polymer and nano particle compos-
ites are reviewed. Their structural, thermal, optical, and electrical
properties were also discussed along with their potential applica-
tions. The article concludes with a brief discussion on the impact of
graphene andrelatedmaterials onthe environment, its toxicological
effects and its future prospects in this rapidly emerging eld.
Published by Elsevier Ltd.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1181
2. History of graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1181
0079-6425/$ - see front matter Published by Elsevier Ltd.
doi:10.1016/j.pmatsci.2011.03.003
Corresponding authors at: Advanced Materials Processing Analysis Center and Nanoscience Technology Center, University
of Central Florida, Orlando, FL, USA.
E-mail addresses: Lei.Zhai@ucf.edu (L. Zhai), saiful@ucf.edu (S.I. Khondaker), Sudipta.Seal@ucf.edu (S. Seal).
Progress in Materials Science 56 (2011) 11781271
Contents lists available at ScienceDirect
Progress in Materials Science
j our nal homepage: www. el sevi er . com/ l ocat e/ pmat sci
3. Synthesis of graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1182
3.1. Exfoliation and cleavage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1182
3.1.1. Mechanical exfoliation in solutions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1183
3.1.2. Intercalation of small molecules by mechanical exfoliation . . . . . . . . . . . . . . . . . . . . 1184
3.2. Chemical vapor deposition (CVD). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1186
3.2.1. Thermal CVD. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1186
3.2.2. Plasma enhanced CVD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1188
3.2.3. Thermal decomposition on SiC and other substrates . . . . . . . . . . . . . . . . . . . . . . . . . . 1188
3.3. Chemically derived graphene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1188
3.3.1. Synthesis of graphene oxide and the reduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1188
3.3.2. Surface functionalization of graphene oxide (GO) . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1191
3.3.3. Structural and physical properties of reduced graphene oxide (RGO) . . . . . . . . . . . . 1192
3.4. Other synthesis approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1195
3.4.1. Total organic synthesis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1195
3.4.2. Un-zipping carbon nanotubes (CNTs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1198
4. Graphene: characterization and properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1201
4.1. Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1201
4.1.1. Optical imaging of graphene layers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1201
4.1.2. Fluorescence quenching technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1201
4.1.3. Atomic force microscopy (AFM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1203
4.1.4. Transmission electron microscopy (TEM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1204
4.1.5. Raman spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1206
4.2. Properties. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1207
4.2.1. Electrical transport property . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1207
4.2.2. Quantum Hall effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1211
4.2.3. Optical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1212
4.2.4. Mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1214
4.2.5. Thermal properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1215
5. Chemically derived graphene: properties and applications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1216
5.1. Assembly of GO/RGO for device applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1216
5.2. Electrical characterization of GO/RGO sheet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1218
5.3. Defect density in chemically derived graphene. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1220
5.4. RGO as graphene quantum dot array: Coulomb blockade effect . . . . . . . . . . . . . . . . . . . . . . . 1221
5.5. Hopping conduction in RGO. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1222
5.5.1. Mott variable range hopping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1222
5.5.2. EfrosShklovskii (ES) VRH . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1224
5.6. Application of RGO for photodetector, phototransistor and emitter . . . . . . . . . . . . . . . . . . . . 1224
5.7. Graphene thin film as transparent electrodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1226
5.8. Solar cell using GO/RGO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1228
5.9. Electrochemical sensors and biosensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1230
6. Graphene based composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1232
6.1. Graphenepolymer composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1232
6.1.1. Synthesis of graphene reinforced polymer composite . . . . . . . . . . . . . . . . . . . . . . . . . 1234
6.1.2. Mechanical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1236
6.1.3. Electrical properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1238
6.1.4. Thermal conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1239
6.1.5. Other properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1240
6.1.6. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1241
6.2. Graphenenanoparticles composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1241
6.2.1. Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1241
6.2.2. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1245
7. Toxicity of graphene/graphene oxide/reduced graphene oxide. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1254
8. Future prospects. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1258
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1259
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1259
V. Singh et al. / Progress in Materials Science 56 (2011) 11781271 1179
Nomenclature
Acronyms
AFM atomic force microscopy
APTS 3-aminopropyltriethoxysilane
ATRP atom transfer radical polymerization
CB Coulomb blockade
CCG chemically converted graphene
CNT carbon nanotube
CRG chemically reduced graphene oxide
CVD chemical vapor deposition
DCC N,N-dicyclohexylcarbodiimide
DGU density gradient ultracentrifugation
DMF N,N-dimethylformamide
DMSO dimethyl sulfoxide
DP dirac point
EBL electron-beam lithography
ECL electrogenerated chemiluminescence
EDC 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide
FET eld effect transistors
FQM uorescence quenching microscopy
GNR graphene nanoribbon
GO graphene oxide
GQD graphene quantum dot
HATU 2-(7-aza-1H-benzotriazole-1-yl)-1,1,3,3-tetramethyluronium hexauorophosphate
HRTEM high resolution transmission electron microscopy
ITO indium tin oxide
LB LangmirBlodgett
LED light emitting diode
MOSFET metal oxide semiconductor FET
NMP N-methyl-2-pyrrolidone
NMR nuclear magnetic resonance
NPs nanoparticles
P3HT poly(3-hexylthiophene)
PAH polyacyclic hydrocarbons
PAN Polyacrylonitrile
PEN poly (ethylene-2,6-naphthalate)
PET polyethylene terephthalate
PECVD plasma enhanced chemical vapor deposition
PL photoluminescence
PMMA poly(methylmethacrylate)
PS polystyrene
PSS poly(sodium 4-styrenesulfonate)
PU poly urethane
PVA poly(vinyl alcohol)
PVC poly(vinyl chloride)
QD quantum dot
QHE quantum Hall effect
RGO reduced graphene oxide
SC sodium cholate
SEM scanning electron microscope
SLG single layer graphene
STEM scanning transmission electron microscopy
STM scanning tunneling microscopy
TBA Tetrabutylamomium
1180 V. Singh et al. / Progress in Materials Science 56 (2011) 11781271
1. Introduction
The 5th of October, 2010 was another beautiful day at Partin Elementary School in Oviedo. When
Kaleb, a 6 year old kindergartener, took out his pencil and started writing letters on a piece of paper,
he did not realize that he was using a material that caught the attention of all scientic community
that same day. The Nobel Prize in Physics 2010 was awarded to Andre Geim and Konstantin Novoselov
for ground breaking experiments regarding the two-dimensional material graphene, a layer of
graphite in the pencil. Graphene, one of the allotropes (carbon nanotube, fullerene, diamond) of ele-
mental carbon, is a planar monolayer of carbon atoms arranged into a two-dimensional (2D) honey-
comb lattice with a carboncarbon bond length of 0.142 nm [1]. Electrons in graphene behave like
massless relativistic particles, which contribute to very peculiar properties such as an anomalous
quantum Hall effect and the absence of localization [2,3]. Graphene [2] has demonstrated a variety
of intriguing properties including high electron mobility at room temperature (250,000 cm
2
/Vs)
[4,5] exceptional thermal conductivity (5000 W m
1
K
1
) [6] and superior mechanical properties with
Youngs modulus of 1 TPa [7]. Its potential applications include single molecule gas detection, trans-
parent conducting electrodes, composites and energy storage devices such as supercapacitors and lith-
ium ion batteries [720]. In addition, a distinct band gap can be generated as the dimension of
graphene is reduced into narrow ribbons with a width of 12 nm, producing semiconductive graphene
with potential applications in transistors [810]. There is no doubt that graphene has risen as a shining
star in the horizon on the path of the scientists searching for new materials for future electronic and
composite industry. This review article narrates the brief history of graphene related research, and
presents the synthesis of graphene and its derivatives and various characterization techniques per-
taining to 2D structure. Many extraordinary properties of graphene such as electrical, mechanical,
anomalous quantum Hall effect, thermal, and optical are discussed. These properties have generated
tremendous interest among material researchers. The recent applications in various elds such as in
large scale assembly and eld effect devices, sensors, transparent electrodes, photodetectors, solar
cells, energy storage devices, polymer composites, nanocomposites will be reviewed with a brief up-
date on toxicology. The conclusion and outlook summarizes the research activities and presents the
possible future research directions.
2. History of graphene
Although the usage of graphite started 6000 years ago, when Marican in Europe used it to decorate
pottery, the research about graphene, essentially an isolated single-atom plane of graphite, dates back
to the 1960s when surprisingly higher basal-plane conductivity of graphite intercalation compounds
were discovered compared to that of the original graphite [1113]. While the scientic community
was excited about the discovery that might lead to a lighter, cheaper substitute for existing metal con-
ductors, they were puzzled by the cause of the high conductivity of graphite intercalation compounds
and cautious about the future applications. The research of graphene has grown slowly in late 20th
century with the hope to observe superior electrical properties from thin graphite or graphene layers
while obtaining graphene was considered to be a formidable task in both theoretical and experimental
aspect. In the graphite intercalation systems, large molecules were inserted between atomic planes,
generating isolated graphene layers in a three-dimensional matrix. The subsequent removal of the lar-
ger molecules produced a mixture of stacked or scrolled graphene layers without the control of the
TEM transmission electron microscopy
THF tetrahydrofuran
TRG thermally reduced graphene oxide
TSCuPc tetrasulfonate salt of copper phthalocyanine
VRH variable range hopping
XPS X-ray photoelectron spectroscopy
structure. It was generally believed that, based on both theoretical calculation and experimental
observation, 2D materials did not exist without a 3D base. AB initio calculations showed that a graph-
ene sheet was thermodynamically unstable with respect to other fullerene structures if its size was
less than about 20 nm (graphene is the least stable structure until about 6000 atoms and becomes
the most stable one (as within graphite) only for sizes larger than 24,000 carbon atoms) [14]. Various
attempts were made to synthesize graphene including using the same approach for the growth of car-
bon nanotubes (producing graphite with 100 layers of graphene) [15], chemical vapor deposition on
metal surfaces (a few layers of graphene) [16,17], or the thermal decomposition of SiC [18]. Although
these approaches did not produce perfect monolayer graphene, the studies showed high-charge
mobility of a few layers of graphene and the CVD approach has been optimized and become a major
technique to produce graphene nowadays [1921]. It was until 2004 that Andre Geim and Konstantin
Novoselov used a method to isolate graphene, a method similar to what young Kaleb did, drawing
with a piece of graphite or peeling graphite with adhesive tape till the graphene is found. Such a kin-
dergartner approach can provide high quality graphene with size in hundreds of microns [22]. These
high quality graphene crystals realize the investigation of their amazing properties. Since then, the re-
search of graphene including the control of the graphene layers on substrates, functionalizing graph-
ene and exploring the applications of graphene has grown exponentially. As shown in Fig. 2.1, the
number of publications on graphene (according to ISI Web of Knowledge
SM
) increases dramatically
after 2004.
The term of graphene was recommended by the relevant IUPAC commission to replace the older
term graphite layers that was unsuitable in the research of single carbon layer structure, because a
three-dimensionally (3D) stacking structure is identied as graphite. The recent denition of graph-
ene can be given as a two-dimensional monolayer of carbon atoms, which is the basic building block of
graphitic materials (i.e. fullerene, nanotube, graphite).
3. Synthesis of graphene
3.1. Exfoliation and cleavage
Recent studies showed that graphite nanoplatelets (GNP) or graphene could be used as a viable and
inexpensive ller substitute for carbon nanotubes (CNT) [23] in nanocomposites owing to the
Fig. 2.1. Number of publications on graphene in past 20 years.
excellent in-plane mechanical, structural, thermal and electrical properties of graphite [24]. It is
obvious that these excellent properties are relevant at the nanoscale and the manufacture of the con-
ducting nanocomposites is highly dependent on the exfoliation of the graphite down to single graph-
ene sheet in the matrices. However, the challenge remained to achieve complete and homogeneous
dispersion of individual graphene sheets in various solvents [25]. Like CNT and other nanomaterials,
the key challenge in synthesis and processing of bulk-quantity graphene sheets is aggregation.
Graphene, a one-atom-thick planar sheet of sp
2
-bonded carbon atoms densely packed in a honeycomb
crystal lattice has very large specic surface area. Unless well separated from each other, graphene
tends to form irreversible agglomerates or even restack to form graphite through Van der Waals inter-
actions. The prevention of aggregation is essential for graphene sheets because most of their unique
properties are only associated with individual sheets.
3.1.1. Mechanical exfoliation in solutions
Mechanical exfoliation is a simple peeling process where a commercially available highly oriented
pyrolytic graphite (HOPG) sheet was dry etched in oxygen plasma to many 5 lm deep mesa (Fig. 3.1).
The mesa was then stuck onto a photoresist and peeled off layers by a scotch tape. The thin akes left
on the photoresist were washed off in acetone and transferred to a silicon wafer. It was found that
these thin akes were composed of monolayer or a few layers of graphene. While the mechanical exfo-
liation of graphene used by Geimand coworkers [22] led to numerous exciting discoveries of graphene
electronic and mechanical properties, such approach is limited by its low production.
On the other hand, although chemical oxidation of graphite and the subsequent exfoliation provide
large amount of graphite oxide monolayer, the invasive chemical treatment inevitably generates
structural defects as indicated by Raman spectroscopic studies [26,27]. These structural defects dis-
rupted the electronic structure of graphene and change it to semiconductive. The subsequent chemical
reduction or thermal annealing (up to 1000 C) are virtually impossible to regenerate the graphene
structures as indicated by XPS studies [28]. Therefore, physical exfoliation approaches are desirable
where it is required to maintain the graphene structure. Blake et al. and Hernandez et al. have dem-
onstrated that graphite could be exfoliated in N-methyl-pyrrolidone to produce defect-free monolayer
graphene [29,30]. Such approach utilizes the similar surface energy of N-methyl-pyrrolidone and
graphene that facilitates the exfoliation. However, the disadvantage of this process is the high cost
of the solvent and the high boiling point of the solvent that makes the following graphene deposition
difcult. Lotya and coworkers have used a surfactant (sodium dodecylbenzene sulfonate, SDBS) to
exfoliate graphite in water to produce graphene. The graphene monolayers are stabilized against
aggregation by a relatively large potential barrier caused by the Coulomb repulsion between
surfactant-coated sheets. The dispersions are reasonably stable with larger akes precipitating out
Fig. 3.1. Mechanical exfoliation of graphene using scotch tape from HOPG.
over more than 6 weeks [31]. Similarly, Green and Hersam have used sodium cholate as a surfactant to
exfoliate graphite and moved further to isolate the resultant graphene sheets with controlled thick-
ness using density gradient ultracentrifugation (DGU) (Fig. 3.2). Since the exfoliation of the graphite
yielded a dispersion of monolayer graphene and graphite with a few layers of graphene which have
different buoyant density. DGU separations of such mixture produce graphene sheets with mean
thicknesses that increase as a function of their buoyant density (Fig. 3.3) [32].
3.1.2. Intercalation of small molecules by mechanical exfoliation
Agglomeration in graphite can be reduced appreciably by incorporating small molecules between
the layers of graphite or by non-covalently attaching molecules or polymers onto the sheets, generat-
ing graphite intercalation compounds (GICs). In GICs, the graphite layers remains unaltered with guest
molecules located in the interlayer galleries. When the layers of graphite interact with the guest mol-
ecules by charge transfer, the in-plane electrical conductivity generally increases but when the mol-
ecules form covalent bonds with the graphite layers as in uorides or oxides the conductivity
decreases as the conjugated sp
2
system is disrupted. The rst graphite intercalation compound,
(GIC), or commonly known as expandable graphite was prepared by Schafhautl in 1841 while analyz-
ing crystal ake of graphite in sulfuric acid solution. In the laboratory, ake graphite was subjected to
shear intensive mechanical stirring with ultrasonic solvent in the ultrasonic cleaning bath at room
Fig. 3.2. (A) Schematic illustration of the graphene exfoliation process. Graphite akes are combined with sodium cholate (SC)
in aqueous solution. Horn-ultrasonication exfoliates few-layer graphene akes that are encapsulated by SC micelles. (B)
Photograph of 90 lg mL
1
graphene dispersion in SC 6 weeks after it was prepared. (C) Schematic illustrating an ordered SC
monolayer on graphene. (Reproduced with permission from [32].)
temperature to prepare expandable graphite. Experimental conditions could be tuned by changing
ultrasonic solvent, ultrasonic power (nominal power of 500 W and 250 W) and ultrasonic time. After
the treatment, the mixture was washed thoroughly with water to neutrality and dried below 60 C for
60 min. The expandable graphite was then expanded at 900 C to obtain the expanded graphite (EG).
The choice of ultrasonic solvent depended on the oxidation ability and water content of the solvents,
which affected the volume of expanded graphite. Acetic acid, acetic acid anhydride, concentrated sul-
furic acid and hydrogen peroxide were the examples of few ultrasonic solvents. Among all those, con-
centrated sulfuric acid had been proved to be the best ultrasonic solvent to provide optimum
condition for preparing the expandable graphite with ultrasound irradiation. Such sulfuric acid inter-
calated graphite compound consisted of layers of hexagonal carbon structure within which H
2
SO
4
was
intercalated. EG could be prepared either by oxidation with a chemical reagent or electrochemically in
the intercalating acid [33,34]. Graphite could expand up to a hundred times in volume at high temper-
ature [35] due to the thermal expansion of the evolved gases trapped between the graphene sheets. So
it was reasonably assumed that oxidants and other molecules could enter in the interlayer space of EG
more easily compared to natural graphite. The inuence of ultrasonic solvent and ultrasonic power on
the volume of expanded graphite could be analyzed from the data listed in Table 3.1.
Li et al. reported the exfoliationreintercalationexpansion of graphite to produce high quality sin-
gle layer graphene sheets stably suspended in organic solvents [36]. Commercial expandable graphite
was subjected to brief heating (60s) at 1000 C in forming gas. It was then grounded with NaCl crystals
and reintercalated with oleum. The exfoliated graphite was then dispersed in N,N-dimethylformamide
(DMF) and treated with tetrabutylamomium (TBA). TBA could insert into and increase the distance be-
tween adjacent layers of graphite facilitating the separation of graphene sheets in surfactant solutions.
The reintercalation and the rapid, brief heating of EG enabled the preparation of highly conducting
graphene sheets without functionalizing the graphite.
Fig. 3.3. (A) Photograph of a centrifuge tube following the rst iteration of density gradient ultracentrifugation (DGU). The
concentrated graphene was diluted by a factor of 40 to ensure that all graphene bands could be clearly resolved in the
photograph. Lines mark the positions of the sorted graphene fractions within the centrifuge tube. (B and C) Representative AFM
images of graphene deposited using fractions f4 (B) and f16 (C) onto SiO
2
. (D) Height prole of regions marked in panels B (blue
curve) and C (red curve) demonstrating the different thicknesses of graphene akes obtained from different DGU fractions.
(Reproduced with permission from [32].)
3.2. Chemical vapor deposition (CVD)
3.2.1. Thermal CVD
Besides mechanical exfoliation and chemical reduction methods to produce graphene sheets, sev-
eral promising approaches including epitaxial growth from SiC, and chemical vapor deposition (CVD)
on metal surfaces have been reported. Among them, the CVD growth appears to be the most promising
technique for large-scale production of mono- or few-layer graphene lms. Although the formation of
monolayer graphite was mentioned in early CVD studies on metal single crystals [3739] the rst
successful synthesis of few-layer graphene lms using CVD was reported in 2006 by Somani and
coworkers using camphor as the precursor on Ni foils [40]. This study opened up a new graphene syn-
thesis route with several unsolved issues like controlling the number of layers, and minimizing the
folding of graphene. Since then, much progress has been made to obtain graphene layers on several
types of metal substrates with controlled thickness [26,4147]. After a chemical etching of the metal
substrate, the graphene layers detach and can be transferred to another substrate, providing high
quality graphene layers without complicated mechanical or chemical treatments.
The growth mechanism of graphene on substrates with mediate-high carbon solubility (>0.1 atom-
ic %) such as Co and Ni is through the diffusion of the carbon into the metal thin lm at the growth
temperature and the subsequent precipitation of carbon out of the bulk metal to metal surface upon
the cooling [43,48]. A typical CVD process (i.e. using Ni as a substrate) involves dissolving carbon into
the nickel substrate followed by a precipitation of carbon on the substrate by cooling the nickel. The Ni
substrate is placed in a CVD chamber at a vacuum of 10
3
Torr and temperature below 1000 C with a
diluted hydrocarbon gas. The deposition process starts with the incorporation of a limited quantity of
carbon atoms into the Ni substrate at relatively low temperature, similar to the carburization process.
The subsequent rapid quenching of the substrate caused the incorporated carbon atoms to out-diffuse
onto the surface of the Ni substrate and form graphene layers. Therefore, the thickness and crystalline
ordering of the precipitated carbon (graphene layers) is controlled by the cooling rate and the concen-
tration of carbon dissolved in the nickel which is determined by the type and concentration of the car-
bonaceous gas in the CVD, and the thickness of the nickel layer.
In contrast, the graphene growth on low carbon solubility (<0.001 atomic %) substrate like Cu
mainly happens on the surface through the four-step process described by Li and coworkers as follow-
ing [49]:
1. Catalytic decomposition of methane on Cu to form C
x
H
y
upon the exposure of Cu to methane and
hydrogen. In this process, the Cu surface is either undersaturated, saturated, or supersaturated with
C
x
H
y
species, depending on the temperature, methane pressure, methane ow, and hydrogen par-
tial pressure.
2. Formation of nuclei as a result of local supersaturation of C
x
H
y
where undersaturated Cu surface
does not form nuclear.
3. Nuclei grow to form graphene islands on Cu surface saturated, or supersaturated with C
x
H
y
species.
4. Full Cu surface coverage by graphene under certain temperature (T), methane ow rate (J
Me
), and
methane partial pressure (P
Me
).
Table 3.1
The inuence of ultrasonic solvent and ultrasonic power on the volume of expanded graphite.
Ultrasonic power (W) Ultrasonic solvents Ultrasonic time (min) Expanded volume (ml/g)
500 Acetic acid 60 150
500 Conc. sulfuric acid 60 500
500 Alcohol 60 120
500 Hydrogen peroxide 60 140
250 Acetic acid 60 140
250 Conc. sulfuric acid 60 380
250 Alcohol 60 80
250 Hydrogen peroxide 60 100
If the amount of available C
x
H
y
on the exposed Cu surface is insufcient to expand the C to the is-
land edges, the Cu surface is only partially covered with graphene islands. Otherwise, if there is always
enough methane to form sufcient C
x
H
y
to drive the reaction between the C
x
H
y
at the surface and the
edges of graphene islands, graphene islands would grow until to connect neighboring islands and fully
cover the Cu surface. With the understanding of the graphene growth mechanism, various approaches
were applied to control the graphene growth rate to obtain monolayer graphene. Lee and coworkers
have used SiO
2
/Si substrates, coated with 300 nm thick Ni or 700 nm thick Cu to produce graphene
layers [47]. The average number of graphene layers grown on a Ni catalyst ranged from three to eight,
depending on the reaction time and cooling rates. On the other hand, the mono- and bilayer graphene
grows predominantly on a Cu catalyst. The low solubility of carbon in Cu is believed to induce the self-
limiting graphene growth process [44]. To prevent the formation of multilayer graphene on mediate-
high carbon solubility (>0.1 atomic %) substrates such as Co and Ni, the thin layers of Ni of thickness
less than 300 nm were deposited on SiO
2
/Si substrates to produce graphene monolayer [43]. Recently,
Bae and coworkers reported a roll-to-roll production of 30-inch. graphene lms using the CVD ap-
proach [50]. Their fabrication process including three steps after the synthesis of graphene on copper
substrates: (i) adhesion of polymer supports to the graphene on the copper foil; (ii) etching of the cop-
per layers; and (iii) release of the graphene layers and transfer onto a target substrate (Fig. 3.4). The
obtained graphene monolayer lms have sheet resistances as low as ~125 X/square with 97.4% opti-
cal transmittance, and exhibit the half-integer quantum Hall effect, indicating their high quality. In
addition, a layer-by-layer stacking of doped four-layer lm has sheet resistance as low as ~30 X/
square with ~90% transparency, demonstrating great potential to replace commercial transparent
electrodes such as indium tin oxides.
An interesting feature of the CVD approach to synthesize graphene is the possibility for substitu-
tional doping by introducing other gases, such as NH
3
, during the growth [5153]. The nitrogen atoms
can be doped into graphene as pyridinic, graphitic and pyrrolic forms. These nitrogen doped
graphene (N-graphene) layers have demonstrated interesting properties. For example, Dais group
have used nitrogen doped graphene for oxygen reduction in fuel cells where the N-graphene electrode
demonstrate a steady-state catalytic current to be calculated three times higher than the Pt/C elec-
trode over a large potential range. The long-term stability, tolerance to crossover, and poison effect
of the N-graphene electrode are also better than Pt/C for oxygen reduction in alkaline electrolyte
[52]. Reddy and coworkers have reported that the reversible discharge capacitance of N-graphene
Fig. 3.4. (A) Schematic of the roll-based production of graphene lms grown on a copper foil. The process includes adhesion of
polymer supports, copper etching (rinsing) and dry transfer-printing on a target substrate. A wet-chemical doping can be
carried out using a setup similar to that used for etching. (B) Roll-to-roll transfer of graphene lms from a thermal release tape
to a PET lm at 120 C. (C) A transparent ultralarge-area graphene lm transferred on a 35-in. PET sheet. (D) An assembled
graphene/PET touch panel showing outstanding exibility. (Reproduced with permission from [50].)
in lithium ion batteries is almost double compared to pristine graphene because the surface defects
induced by nitrogen doping [53].
3.2.2. Plasma enhanced CVD
Plasma enhanced chemical vapor deposition (PECVD) offers another route of graphene synthesis
at a lower temperature compared to thermal CVD. Thick graphite structures were observed during
the fabrication of nanostructured graphite-like carbon using a dc discharge PECVD. The rst report
of the production of mono- and few layer of graphene by PECVD involved a radio frequency PECVD
system to synthesize graphene on a various substrates where graphene sheets were produced from a
gas mixture of 5100% CH
4
in H
2
(total pressure 12 Pa), at 900 W power and 680 C substrate tem-
perature [54,55]. Since then, much effort have been devoted to understand the graphene growth
mechanism and to optimize experimental conditions to control the thickness of graphene lms
[5658]. The advantages of the plasma deposition include very short deposition time (<5 min)
and a lower growth temperature of 650 C compared to the thermal CVD approach (1000 C). The
growth mechanism involved a balance between the graphene deposition through the surface diffu-
sion of C-bearing growth species from precursor gas and etching caused by atomic hydrogen. The
verticality of the graphene sheets, produced through this method, is caused by the plasma electric
eld direction [56,58].
3.2.3. Thermal decomposition on SiC and other substrates
Producing graphite through ultrahigh vacuum (UHV) annealing of SiC surface has been an attrac-
tive approach especially for semiconductor industry because the products are obtained on SiC sub-
strates and requires no transfer before processing devices [18,5961]. When SiC substrate is heated
under UHV, silicon atoms sublimate from the substrate. The removal of Si leaves surface carbon atoms
to rearrange into graphene layers. The thickness of graphene layers depends on the annealing time and
temperature. The formation of few-layer graphene (FLG) typically requires few minutes annealing of
the SiC surface at temperature around 1200 C [62]. More recently, vapor phase annealing has been
used to produce FLG on SiC. At the expense of a higher temperature (typically 400 C above UHV tem-
perature), [63] this method leads to the formation of FLG on SiC with an improved thickness homoge-
neity [64]. Although producing graphene on SiC substrates is attractive, several hurdles prevent the
real application. For example, control the thickness of graphene layers in the routine production of
large area graphene is very challenging. Another uncertainty involves the different epitaxial growth
patterns on different SiC polar face (i.e. Si-face or C-face). Unusual rotational graphene stacking were
observed in multilayers graphene grown on the C-face surface but not on Si-face surface. Such mis-
match of graphene growth process has profound effects on the physical and electronic properties of
epitaxial graphene. On the C-face, the twisted interface leads to the decoupling between different
layers of graphene, each of which behaves as a single layer [65]. However, the electronic properties
of graphene multilayers on Si-face remains controversial [59]. Future investigation is required to
understand the mechanisms of the growth processes. The third issue is to understand the relationship
between the structure and electronic properties of the interface layer between graphene and substrate
[61].
The similar approach was applied to other metallic substrates to grow graphene layers. The (0001)
faces of ruthenium (Ru) crystals were used under UHV to produce epitaxial graphene layers where a
very sparse graphene nucleation at high temperatures allowed a linear dimensions growth of macro-
scopic single-crystalline domains [66,67]. It was found that the rst graphene layer coupled strongly
to the Ru substrate, while the second layer was free of the substrate interaction and had the similar
electronic structure to free-standing graphene. Other metal substrates including Ir, Ni, Co, and Pt have
been employed to produce graphene layers and was nicely reviewed by Wintterlin and Bocquet [68].
3.3. Chemically derived graphene
3.3.1. Synthesis of graphene oxide and the reduction
At present, chemical conversion of graphite to graphene oxide has emerged to be a viable route to
afford graphene-based single sheets in considerable quantities [6973]. Graphite oxide (GO) is usually
synthesized through the oxidation of graphite using oxidants including concentrated sulfuric acid, ni-
tric acid and potassium permanganate based on Hummers method [74]. Compared to pristine graph-
ite, GO is heavily oxygenated bearing hydroxyl and epoxy groups on sp
3
hybridized carbon on the
basal plane, in addition to carbonyl and carboxyl groups located at the sheet edges on sp
2
hybridized
carbon. Hence, GO is highly hydrophilic and readily exfoliated in water, yielding stable dispersion con-
sisting mostly of single layered sheets (graphene oxide). It is important to note that although graphite
oxide and graphene oxide share similar chemical properties (i.e. surface functional group), their struc-
tures are different. Graphene oxide is a monolayer material produced by the exfoliation of GO. Suf-
ciently dilute colloidal suspension of graphene oxide prepared by sonication are clear, homogeneous
and stable indenitely. AFM images of GO exfoliated by the ultrasonic treatment at concentrations of
1 mg/ml in water always revealed the presence of sheets with uniformthickness (~1 nm). The pristine
graphite sheet is atomically at with the Van der Waals thickness of ~0.34 nm, graphene oxide sheets
are thicker due to the displacement of sp
3
hybridized carbon atoms slightly above and below the ori-
ginal graphene plane and presence of covalently bound oxygen atoms. A similar degree of exfoliation
of GO was also attained for N,N-dimethylformamide (DMF), tetrahydrofuran (THF), N-methyl-2-
pyrrolidone (NMP) and ethylene glycol [75]. Li et al. showed that the surface charges on graphene
oxide are highly negative when dispersed in water by measuring the zeta potential due to the ioniza-
tion of the carboxylic acid and the phenolic hydroxyl groups [76]. Therefore, the formation of stable
graphene oxide colloids in water was attributed to not only its hydrophilicity but also the electrostatic
repulsion.
The chemical structure of graphene oxide such as the type and distribution of oxygen-containing
functional groups have been studied using NMR
13
C-labelled graphene oxide [77,78] suggesting that
the basal plane of the sheet is decorated with hydroxyl and epoxy (1,2-ether) functional groups with
small amount of lactol, ester, acid and ketone carbonyl groups at the edge. These results are in good
agreement with the model proposed by LerfKlinowski [79,80] and Dkny Models with small mod-
ication [81]. These functional groups provide reactive sites for a variety of surface-modication reac-
tions to develop functionalized graphene oxide- and graphene-based materials. On the other hand,
due to the disruption of the conjugated electronic structure by these functional groups, graphene
oxide was electrically insulating and contained irreversible defects and disorders [26,82], but chemical
reduction of graphene oxide could partially restore its conductivity [26,82,83] at values orders of mag-
nitude below that of pristine graphene.
Chemical reduction of graphene oxide sheets has been performed with several reducing agents
including hydrazine [27,28,73,84], and sodium borohydrate [83,85]. Hydrazine hydrate, unlike other
strong reductants, does not react with water and was found to be the best one in producing very thin
and ne graphite-like sheets. During the reduction process, the brown colored dispersion of graphene
oxide in water turned black and the reduced sheets aggregated and precipitated [26,82]. The reduced
graphene oxide became less hydrophilic due to the removal of oxygen atoms and thus precipitated.
The reason of re-establishment of the conjugated graphene network could be attributed to the reac-
tion pathway proposed by Stankovich et al. (Fig. 3.5) [26]. Hydrazine takes part in ring-opening reac-
tion with epoxides and forms hydrazino alcohols [86]. This initial derivative reacts further via the
formation of an aminoaziridine moiety which undergoes thermal elimination of diimide to form a
double bond. Li and coworkers demonstrated the preparation of stable aqueous suspension of reduced
graphene oxide nanosheets by adjusting the pH (with ammonia solution) of the aqueous solution dur-
ing reduction with hydrazine [76]. The carboxylic acid groups were unlikely to be reduced by hydra-
zine and thus remained intact after hydroxyl reduction. The adjustment of pH with ammonia solution
deprotonated the carboxylic acid groups and thus the electrostatic repulsion among the charged
groups on reduced graphene oxide enabled the formation of well-dispersed graphene colloids in water
without any stabilizers. But, unless stabilized by selected surfactants, reduced graphene in organic sol-
vent tend to agglomerate due to their hydrophobic nature [26,82]. Another possible route to reduce
GO was using sodium borohydride (NaBH
4
) [83] in aqueous solution where sodium borohydride is
more effective than hydrazine as a reductant of graphene oxide although it can be slowly hydrolyzed
by water. Such reduction produced reduced graphene oxide with sheet resistances as low as 59 kX/
square (compared to 780 kX/square for a hydrazine reduced sample, measured in the same study),
and C:O ratios were as high as 13.4:1 (compared to 6.2:1 for hydrazine). The NaBH
4
treatment
eliminated all the parent oxygen containing groups and the resultant solid became IR inactive like
pure graphite. Carbon elemental analysis revealed the evidence for the complete reduction of graph-
ene oxide in this process [83,85]. Other chemical reduction routes including using hydroquinone [87],
gaseous hydrogen (after thermal expansion) [88], and strongly alkaline solutions [89] have also been
investigated. While the reduction by hydrogen proved to be effective (C:O ratio of 10.814.9:1), hydro-
quinone and alkaline solutions were not as effective as hydrazine and sodium borohydride based on
semi-quantitative results.
Thermal reduction is another approach to reduce GO to reduced graphene oxide that utilizes the
heat treatment to remove the oxide functional groups from graphene oxide surfaces. Aksays group
have exfoliate and reduce stacked GO by heating GO to 1050 C where oxide functional groups were
extruded as carbon dioxide [71,90]. The authors reported that the exfoliation took place when the
decomposition rate of the epoxy and hydroxyl sites of graphite oxide exceeded the diffusion rate of
the evolved gases, thus yielding pressures that exceeded the Van der Waals forces holding the graph-
ene sheets together. It was calculated that the pressure of 2.5 MPa was required to separate GO sheets
by numerically evaluating the Hamaker constant while the pressure generated during the exfoliation
was 12 orders of magnitude higher. Although the thermal reduction/exfoliation can produce 80% sin-
gle layer reduced graphene oxide according to the AFM studies, the removal of the oxide groups
caused about 30% mass loss and left behind vacancies and structural defects which may affect the
mechanical and electrical properties of reduced graphene oxide. Nevertheless, the bulk conductivities
O
O
OH
O
O O
O
OH
O
OH
HO
O
O
O
HO
OH
OH
HO HO
OH
OH
HO
OH
O
Oxidation
Reduction by hydrazine
O
H
2
N NH
2
HO
HN
NH
2
N
NH
2
+
-H
2
O -N
2
H
2
a
b
Fig. 3.5. (a) Oxidation of graphite to graphene oxide and reduction to reduced graphene oxide. (b) A proposed reaction pathway
for epoxy reduction by hydrazine. (Reproduced with permission from [26].)
of the products was measured to be 10002300 S/m, suggesting the effective reduction and restora-
tion of electronic structures from GO [71]. Recently, Dubin et al. reported a simple one-step, solvother-
mal reduction method to produce reduced graphene oxide dispersion in organic solvent [91]. The
deoxygenation of GO resulted from both thermal deoxygenation at 200 C when reuxing GO in N-
methyl-2-pyrrolidinone (NMP) along with a concomitant reaction of GO with NMP molecules. The
solvothermally reduced graphene oxide layers remained in a stable dispersion after the reaction.
This approach provides a simple, low-temperature method to produce reduced graphene oxide.
3.3.2. Surface functionalization of graphene oxide (GO)
The surface functionalization of graphene oxide not only plays an important role in controlling
exfoliation behavior of graphene oxide and reduced graphene oxide but also holds the key to the gate
leads to various applications. The surface functionalization has taken two approaches: covalent func-
tionalization and non-covalent functionalization. In covalent functionalization, oxygen functional
groups on graphene oxide surfaces, including carboxylic acid groups at the edge and epoxy/hydroxyl
groups on the basal plane can be utilized to change the surface functionality of graphene oxide. Graph-
ene oxide had been treated with organic isocyanates to give a number of chemically modied GO.
Treatment of isocyanates reduced the hydrophilicity of graphene oxide by forming amide and carba-
mate esters from the carboxyl and hydroxyl groups of graphene oxide, respectively. Consequently, iso-
cyanate modied graphene oxide readily formed stable dispersion in polar aprotic solvents giving
completely exfoliated single graphene sheets with thickness of ~1 nm (Fig. 3.6). This dispersion also
facilitated the intimate mixing of the graphene oxide sheets with matrix polymers, providing a novel
synthesis route to make graphenepolymer nanocomposites. Moreover, modied graphene oxide in
the suspension could be chemically reduced in presence of the host polymer to render electrical con-
ductivity in the nanocomposites [92].
In order to use carboxylic acid groups on graphene oxide to anchor other molecules, the carboxylic
acid groups have been activated by thionyl chloride (SOCl
2
) [9396], 1-ethyl-3-(3-dimethylaminopro-
pyl)- carbodiimide (EDC) [97], N,N-dicyclohexylcarbodiimide (DCC) [98], or 2-(7-aza-1H-benzotria-
zole-1-yl)-1,1,3,3-tetramethyluronium hexauorophosphate (HATU) [99]. The subsequent addition
of nucleophilic species, such as amines or alcohols, produced covalently attached functional groups
O
O
OH
O
O
O
O
OH
O
OH
HO
O
O
RNCO
RNCO
O
O
NHR
O
O
O
O
NHR
O
O
O
CO
2
O
NHR
NHR
O
Fig. 3.6. Isocyanate treatment of GO where organic isocyanate reacts with the hydroxyl and carboxyl groups of the graphene
oxide sheets.
on graphene oxide via the formation of amides or esters. The resultant amine functionalized graphene
oxide has demonstrated various applications in optoelectronics [93,95,96], drug-delivery materials
[97], biodevices [99], and polymer composites [98,100]. The attachment of hydrophobic long, aliphatic
amine groups on hydrophilic graphene oxide improved the dispersability of modied graphene oxide
in organic solvents [94], while porphyrin-functionalized primary amines and fullerene-functionalized
secondary amines introduced interesting nonlinear optical properties [95,96]. The amine groups and
hydroxyl groups on the basal plane of graphene oxide have also been used to attach polymers through
either grafting-onto or grafting-from approaches. To grow a polymer from graphene oxide, an atom
transfer radical polymerization (ATRP) initiator (i.e. a-bromoiobutyrylbromide) was attached to
graphene surfaces [101,102]. The following living polymerization produced graphene oxide with poly-
mers that enhanced the compatibility of solvents and other polymer matrices. Besides the carboxylic
acid groups, the epoxy groups on graphene oxide can be used to attach different functional groups
through a ring-opening reaction. Various amine ending chemicals such as octadecylamine [87], an io-
nic liquid 1-(3-aminopropyl)-3-methylimidazolium bromide [96] with an amine end group and 3-
aminopropyltriethoxysilane (APTS) have reacted with epoxy groups.
The non-covalent functionalization of graphene oxide utilizes the weak interactions (i.e. pp inter-
action, Van der Waals interactions and electrostatic interaction) between the graphene oxide and target
molecules. The sp
2
network on graphene oxide provides pp interactions with conjugated polymers
and aromatic compounds that can stabilize reduced graphene oxide resulted from chemical reduction
and produce functional composite materials. The conjugated polymers and aromatic compounds
include poly(sodium 4-styrenesulfonate) (PSS) [82], sulfonated polyaniline [103], poly(3-
hexylthiophene) (P3HT) [104], conjugated polyelectrolyte [105], 7,7,8,8-tetracyanoquinodimethane
anion [106], tetrasulfonate salt of copper phthalocyanine (TSCuPc) [107], porphyrin [108,109], pyrene
and perylenediimide decorated with water-soluble moieties [110], and cellulose derivatives [111].
During the chemical reduction of graphene oxide, reduced graphene oxide nanosheets are stabilized
via the pp interaction between aromatic molecules and reduced graphene oxide nanosheets. Aro-
matic molecules have large aromatic plane and can anchor onto the reduced graphene oxide surface
without disturbing its electronic conjugation, providing stability for reduced graphene oxide. For
example, the sulfonate groups on TSCuPc introduce negative charges on reduced graphene oxide sheets
and stabilize the RGO dispersion, providing single sheets of TSCuPc functionalized RGO for device fab-
rication. In contrast, irreversible aggregation and precipitation of graphitic sheets occurred upon the
reduction of graphene oxide without TSCuPc (Fig. 3.7B inset). Atomic force microscopy (AFM) study
(Fig. 3.7) of reduced graphene oxide/TSCuPc composites provides detailed information about the indi-
vidual layer of the reduced graphene oxide/TSCuPc composite sheets. The cross section analysis in the
AFMheight image indicates the thickness of the TSCuPc attached RGOsheet to be ~1.9 nmwhereas the
thickness of a single layer RGO was found to be approximately 1 nm. Therefore, the AFM height image
conrmed the non-covalent attachment of the aromatic molecules on the RGObasal plane through pp
interaction. The small dots in the AFM images are aggregates of TSCuPc [107]. Dye-labeled DNA have
also been used to functionalize graphene oxide to detect proteins and DNA [112]. The uorescence
of the dye on the reduced graphene oxide was quenched by the substrate. In the presence of a target,
the binding between the dye-labeled DNA and target molecule will alter the conformation of dye-
labeled DNA, and disturb the interaction between the dye-labeled DNA and graphene oxide. Such inter-
actions will release the dye-labeled DNA from the GO, restoring of dye uorescence.
3.3.3. Structural and physical properties of reduced graphene oxide (RGO)
The optical and electrical properties of reduced graphene oxide depend on the spatial distribution
of the functional groups and structural defects. For example, the electron mean free path is limited by
the distance between two defective sites represented either by CAO or a vacancy [113]. A giant-
infrared-absorption band was observed in reduced graphene oxide attributed to the coupling of elec-
tronic states to the asymmetric stretch mode of a structure consisting of oxygen atoms aggregated at
the edges of defects [114]. Therefore, understanding the molecular structure evolution of the GO
structure during reduction is the key to obtain reduced graphene oxide with desired optical and
electrical properties. The structures of RGO have been studied both theoretically [115] and experimen-
tally [78,114118].
Bagri and coworkers used molecular dynamics (MD) simulation to study the atomic structure evo-
lution from graphene oxide to RGO during the thermal annealing process [115]. As the author summa-
rized in the paper, the carbonyl and ether groups on RGO formed from the hydroxyl and epoxy groups
on graphene oxide during thermal annealing. Hydroxyl groups desorb at low temperature without
altering the graphene basal plane. In contrast, isolated epoxy groups are relatively more stable, and
substantially distort the graphene lattice on desorption. The removal of carbon from the graphene
plane (generating structural defects) is more likely to occur when the initial hydroxyl and epoxy
groups are close to each other. The reaction pathway during thermal annealing between two nearby
functional groups leads to the formation of carbonyl and ether groups, which are thermodynamically
very stable. These theoretical results are corroborated by FTIR spectroscopy and X-ray photoelectron
spectroscopy (XPS) experiments.
A systematic investigation of the electrical and chemical structure evolution was performed on the
reduction process via thermal treatment in UHV and in an Ar/H
2
reducing atmosphere on pristine GO
thin lms and those that were previously treated with hydrazine vapor [116]. The progressive loss of
oxygen functional groups after each step of the reduction process was investigated by in situ XPS to
reveal the change of carbon and oxygen bonds. It was found that the amount of carbon sp
2
bonding
increased with the loss of oxygen during the annealing process, reaching a maximum value of
~80% at an oxygen content of ~8% (C:O ratio 12.5:1). This suggests that the remaining oxygen is
Fig. 3.7. Tapping mode AFM image of the RGO/TSCuPc composite on mica. Inset shows (A) Reducing of GO in the presence of
TSCuPc forms stable RGO/TSCuPc composite ink. (B) Precipitate formed when GO was reduced without TSCuPc.
responsible for ~20% sp
3
bonding and annealing up to 1100 C is not sufcient to completely remove
the oxygen from GO. Raman spectroscopy was also employed to reveal the structural evolution where
the area ratio of the D and G bands was used as measure of the size of sp
2
ring clusters in a network of
sp
3
and sp
2
bonded carbon. Using the empirical TuinstraKoenig relation [119] to obtain the lateral
dimension of sp
2
ring clusters, an average graphitic domain size of ~2.5 nm in pristine GO was calcu-
lated. After chemical (with hydrazine vapor) reduction and thermal annealing up to 500 C, the change
in the D/G peak area ratio was found to be negligible. A slight decrease in the full width half maxima
(FWHM) of the D peak was observed only after annealing at 1100 C, resulting in an increase in the
size of the sp
2
cluster to ~2.8 nm. This observation suggests that even when the sp
2
carboncarbon
bonds are restored by de-oxidation, their spatial distribution in the honeycomb graphene lattice does
not generate an expansion of a continuous sp
2
phase. This may be due to the fact that the sp
2
sites are
isolated by disordered domains, which is indicated by the TEM studies [117,118]. The conductivity
was also measured vs. the sp
2
fraction. The data indicated that the presence of residual oxygen
(~8%) signicantly hampered the carrier transport among the graphitic domains, and transport at
the initial stages of reduction was dominated by hopping or tunneling amongst the sp
2
clusters. At lat-
ter stages of reduction, newly formed smaller sp
2
domains connected the original sp
2
clusters so that
charge could transport through percolation network. However, carrier transport above the percolation
threshold was limited by those clusters that are not perfect graphene crystals.
Erickson et al. have investigated the local chemical structures on graphene oxide and reduced
graphene oxide using the TEAM 0.5 TEM (a monochromated aberration-corrected instrument oper-
ated at 80 keV) [117]. GO was produced via a modied Hummers method and drop cast onto lacey
carbon TEM grids. For RGO specimens, GO-containing grids were reduced in a hydrazine atmosphere
and then slowly heated to 550 C under owing N
2
. The TEM image of graphene oxide (Fig. 3.8) clearly
shows the oxidized area (A and B) and unoxidized graphene crystal area (Fig. 3.8c). As explained in the
gure caption, hydroxyl groups and epoxy were presented on the graphene oxide basal plane, in good
agreement with LerfKlinowski [79,80] and Dkny Models [81].
On the other hand, the TEMimage of RGO shows the disordered regions (Fig. 3.9A) that are believed
to result from the oxidized area being reduced by hydrazine and thermal annealing, and the unoxi-
dized graphene regions.
Similarly, Gomez-Navarro and coworkers have used high resolution transmission electron micros-
copy (HRTEM) to investigate the structure of reduced graphene oxide monolayers produced from
chemical oxidation/reduction of graphite in atomic scale. Defect free graphene domains with sizes
of a few nanometers were mixed with defect areas dominated by clustered pentagons and heptagons
[120]. The atomic structure of the RGO layers obtained from HRTEM is shown Fig. 3.10 with different
regions of the image marked by colors in Fig. 3.10b. The largest portion of the RGO layer is comprised
of clean well crystallized graphene areas where the hexagonal lattice is clearly observed (light gray
color in Fig. 3.10b). The average size of the visible well-crystallized areas is from 3 to 6 nm, covering
~60% of the surface. The formation of larger holes is caused by electron irradiation, similar to the TEM
images of mechanically exfoliated graphene. In contrast to mechanically exfoliated graphene, RGO has
a large amount of topological defects within the clean areas. These defects was classied into isolated
topological defects (pentagonheptagon pairs, green), and extended (clustered) topological defects
that appear as quasi-amorphous single layer carbon structures (marked in blue in Fig. 3.10b). The ex-
tended topological defects cover ca. 5% of the surface and exhibit typical sizes of 12 nm in diameter.
According to the TEM studies, it is believed that isolated highly oxidized areas (few nm in size) are
formed upon oxidation, while major graphene surface remains undisturbed. Upon reduction, the oxi-
dized areas are restored to sp
2
-bonded carbon networks, which however lack the perfect crystallinity
of intact graphene. The reduced disordered areas, which are best described as clustered topological
defects, induce strain as well as in-plane and out-of-plane deformations in the surrounding RGO. Iso-
lated topological defects, mostly dislocations, are also present and may have formed as a result of
strain. The effects of these defects will have to be taken into account for any comprehensive study
of the properties of RGO [120].
Gao et al. have investigatedthe structural change fromgraphene oxide to RGOusing
13
C NMR[78]. In
their studies, RGOwas producedfromgrapheneoxidethrougha two-stepreductionprocessdeoxygen-
ation with NaBH
4
(chemically converted graphene, CCG1), followed by dehydration with concentrated
sulfuric acid(CCG2) andannealing of CCG2inAr/H
2
at 1100 Cfor 15 min(CCG3). The authors suggested
that this process produced graphene with a very lownumber of remaining functional groups, high con-
ductivity, larger crystallite size and good solubility. The
13
C NMR studies of graphene oxide illustrated
the functional groups, as discussedin previous sectionwhile the
13
CNMRof different reducedmaterials,
indicated that NaBH
4
reduction removed the epoxy groups on the basal plane with the regeneration of
C@C bonds, the concentrated sulfuric acid treatment dehydrate hydroxyl groups to C@C bonds and the
thermal annealingextrudes the carboxylic acidgroups at the edge withthe regenerationof C@C. Bymea-
suring the electric conductivity of the materials, the authors demonstrated the increased electrical con-
ductivity (GO: 4.08 10
1
S/m, CCG1: 8.23 10
1
S/m, CCG2: 1.66 10
3
S/m, CCG3: 2.20 10
4
S/m)
attributed to the restoration of conjugated electronic structures on RGO.
3.4. Other synthesis approaches
3.4.1. Total organic synthesis
Total synthesis of graphene-like polyacyclic hydrocarbons (PAHs), explored decades ago, has
caught much attention as a possible alternative route to synthesize graphene. Although PAHs have
some advantages including synthesis versatility and the capability of grafting aliphatic chains at the
edge to modify solubility, the major challenge lies in preserving dispersibility and a planar geometry
for large PAHs. While different PAHs synthesis routes are nicely reviewed by Mullen et al. [121], it is
Fig. 3.8. Aberration-corrected TEM image of a single sheet of suspended GO. The scale bar is 2 nm. Expansion (A) shows, from
left to right, a 1 nm
2
enlarged oxidized region of the material, then a proposed possible atomic structure of this region with
carbon atoms in gray and oxygen atoms in red, and nally the average of a simulated TEMimage of the proposed structure and a
simulated TEM image of another structure where the position of oxidative functionalities has been changed. Expansion (B)
focuses on the white spot on the graphitic region. This spot moved along the graphitic region, but stayed stationary for three
frames (6 s) at a hydroxyl position (left portion of expansion (B)) and for seven frames (14 s) at a (1, 2) epoxy position (right
portion of expansion (B)). The ball-and-stick gures below the microscopy images represent the proposed atomic structure for
such functionalities. The simulated TEM image for the suggested structure agrees well with the TEM data. Expansion (C) shows
a 1 nm
2
graphitic portion from the exit plane wave reconstruction of a focal series of GO and the atomic structure of this region.
important to note that Mullens group has made a major break-through in synthesizing two-
dimension graphene ribbons with the size of 12 nm through the SuzukiMiyaura coupling of 1,4-
diiodo-2,3,5,6-tetraphenylbenzene with 4-bromophenylboronic acid [122]. The same group recently
reported a bottom-up method to fabricate graphene nanoribbons (GNR) on gold surfaces from
10,10
/
-dibromo-9,9
/
-bianthryl precursor monomers [123]. In the fabrication process, thermal deposi-
tion of the monomers onto a gold surface removes the halogen substituents from the precursors, and
provides the molecular building blocks for the targeted graphene ribbons (with a width of seven ben-
zene molecules) in the form of surface-stabilized biradical species. During a rst thermal activation
step, the biradical species diffuse across the surface and undergo radical addition reactions to form lin-
ear polymer chains as imprinted by the specic chemical functionality pattern of the monomers. In a
second thermal activation step, a surface-assisted cyclodehydrogenation establishes an extended fully
aromatic system (Fig. 3.11).
Fig. 3.9. Aberration-corrected TEM image of a monolayer of RGO. The scale bar is 1 nm. Expansion (A) shows, from left to right,
an enlarged region of the micrograph, then a proposed possible structure for the region where oxygen (indicated in red) and
nitrogen (blue) remain as functionalities on the sheets, and nally a simulated TEM image for this proposed structure.
Expansion (B) shows the structure of a graphitic region. (Reproduced with permission from [117].)
Fig. 3.10. Atomic resolution, aberration-corrected TEM image of a single layer reduced graphene oxide membrane. (a) Original
image and (b) with color added to highlight the different features. The defect free crystalline graphene area is displayed in the
original light gray color. Contaminated regions are shaded in dark gray. Blue regions are the disordered single-layer carbon
networks, or extended topological defects, identied as remnants of the oxidation reduction process. Red areas highlight
individual ad-atoms or substitutions. Green areas indicate isolated topological defects, that is, single bond rotations or
dislocation cores. Holes and their edge reconstructions are colored in yellow. Scale bar 1 nm. (Reproduced with permission from
[120].)
Fig. 3.11. Bottom-up fabrication of atomically precise GNRs. Basic steps for surface-supported GNR synthesis, illustrated with a
ball-and-stick model of the example of 10,10
/
-dibromo-9,9
/
-bianthryl monomers (1). Grey, carbon; white, hydrogen; red,
halogens; underlying surface atoms shown by large spheres. Top, dehalogenation during adsorption of the di-halogen
functionalized precursor monomers. Middle, formation of linear polymers by covalent interlinking of the dehalogenated
intermediates. Bottom, formation of fully aromatic GNRs by cyclodehydrogenation. (Reproduced with permission from [123].)
The product of each reaction was monitored by scanning tunneling microscopy (STM) and the
graphene nanoribbon was characterized by Raman spectroscopy (Fig. 3.12). The STM image taken after
surface assisted CAC coupling at 200 C but before the nal cyclodehydrogenation step shows a poly-
anthrylene chain (Fig. 3.12b left) with a periodicity of 0.86 nm which is in good agreement with the
periodicity of the bianthry core of 0.85 nm. Fig. 3.12b, right shows a DFT-based simulation of the
STM image with partially overlaid model of the polymer (blue, carbon; white, hydrogen). The fully
aromatic system has an N = 7 armchair ribbon (Fig. 3.12c) with half the periodicity of the polymeric
chain (0.42 nm) and a markedly reduced apparent height of 0.18 nm. STM simulations are in perfect
agreement with experimental images (Fig. 3.12e), conrming that the reaction products are atomically
precise N = 7 GNRs with fully hydrogen-terminated armchair edges. The peak at 396 cm
1
in Raman
spectrum is characteristic for the 0.74 nm width of the N = 7 ribbons. The inset in Fig. 3.12d shows
the atomic displacements characteristic for the radial-breathing like mode at 396 cm
1
. In addition,
the authors also demonstrated the fabrication of the straight N = 7 GNRs and the chevron-type
N = 6/N = 9 GNRs having been grown sequentially on a Ag(111) surface. These achievements suggest
that total synthesis is a versatile approach to make GNR with precise control of the composition and
structure. Studies on the electrical, optical and mechanical properties of these GNR are expected to
direct interesting applications.
3.4.2. Un-zipping carbon nanotubes (CNTs)
One of the graphene research goals is to introduce an energy band gap to realize the application in
semiconductor devices since pristine graphene is a zero-gap material. The graphene materials with an
energy gap can be produced through two approaches: controlled oxidation of a few layers of graphene
and fabrication GNR. Currently, it is very difcult to oxide a few layers of graphene in a controlled
Fig. 3.12. Straight GNRs from bianthryl monomers. (Reproduced with permission from [123].)
manner. GNRs with narrow widths (<~10 nm) and atomically smooth edges, are predicted to have
band gaps useful for room temperature transistor operations with excellent switching speed and high
carrier mobility (potentially even ballistic transport) [124127]. Yan et al. predicted that eld effect
transistors (FETs) made from intrinsic semiconductor zigzag ribbons can exhibit very high levels of
performance, with ON/OFF ratio up to 10
4
, subthreshold swing as low as 60 meV per decade, and
transconductance of 9.5 10
3
S/m [127]. The most straight forward method to produce GNRs is
through e-beam lithography which can generate wide GRNs with a width of 20 nm from graphene
sheet. However, such approach is limited by poor scale resolution and large edge roughness [128].
A chemical sonication route developed by Dai group produced sub-10 nm GNR semiconductors from
intercalated and exfoliated graphite but with low GNR yield and broad width distribution [8].
Dai and coworker recently have taken a unique approach to fabricate GNRs with well controlled
dimension. Based on concept that carbon nanotubes (CNTs) are considered to be GNRs rolled up into
seamless tubes and the fact that the size of CNTs have been well controlled, Dais group developed a
method to produce GNRs through controlled unzipping of CNTs using by an Ar plasma etching method
[129]. In their approach, dispersed multiwalled carbon nanotubes (MWCNTs) were embedded in a
poly (methyl methacrylate) (PMMA) layer (an etch mask) on a Si substrate. After baking, the
PMMAMWCNT lm was peel off in a KOH solution, leaving a narrow strip of MWCNT sidewall ex-
posed to a 10 W Ar plasma treatment. The exposed MWCNT area was etched faster than the other area
covered by PMMA, leading to unzipped CNTsgraphene nanoribbons. This approach could produce
single-, bi- and multilayer GNRs and GNRs with inner CNT cores, depending on the diameter and num-
ber of layers of the starting MWCNT and the etching time. The PMMA lm was removed using acetone
vapor followed by calcination at 300 C for 10 min to remove polymer residue to produce GNRs on the
substrate. The AFM images of the obtained GNRs show smooth edges and uniform width of 1020 nm
corresponding to half of the circumference of the starting MWCNTs (diameter ~8 nm) (Fig. 3.13). The
Raman spectroscopic studies provided the ratio of D band and G band (I
D
/I
G
= 0.38, 0.30 and 0.28 for
single-, bi- and trilayer GNRs with 1020 nm widths). Because defect density on the pristine MWCNTs
was low, the D-band Raman signal of the GNRs was mainly due to the open edges. The I
D
/I
G
values
a b
c d e f g h i j
MWCNT
10nm
GNR
Fig. 3.13. Images of GNRs converted from MWCNTs. (a) An AFM image of raw MWCNTs dispersed on a Si substrate. (b) An
image of the substrate after the GNR conversion process, showing coexistence of MWCNTs and GNRs. Scale bars, 1 mm. (cj)
Single- or few-layer GNRs of different widths and heights: respectively 7 and 1.8 nm (c), 8 and 1.8 nm (left, d), 13 and 2.0 nm
(right, d), 15 and 0.9 nm (e), 17 and 1.0 nm (f), 25 and 1.1 nm (g), 33 and 1.4 nm (h), 45 and 0.8 nm (i) and 51 and 1.9 nm (j).
Scale bars, 100 nm. The height scale for all the AFM images is 10 nm. In (e) an arrow points to a leftover MWCNT. (Reproduced
with permission from [129].)
were lower than those for GNRs obtained by lithographic etching of pristine graphene sheets (I
D
/I
G
~ 2
for a bilayer GNR of 28 nm width obtained by lithographic patterning), indicating the high quality of
the GNRs obtained through this approach.
On the other hand, the electrical properties of the fabricated FET devices using these GNRs were not
as good as the predicted value. A 7 nm-wide GNR device had an I
on
/I
off
ratio of >10 and a 6 nm-wide
GNR device had I
on
/I
off
> 100. These GNRs had quantum-conned semiconducting characteristics,
rather than those of bulk graphene, with much weaker gate modulation of conductance. The mobility
of the GNRs was similar to those fabricated by lithography with values 10 times lower than those of
large two-dimensional graphene sheets, most likely because of the edge scattering in the GNRs.
Shimizu and coworkers produced GNRs through the oxidization and longitudinal unzipping of
MWCNTs in concentrated sulphuric acid, followed by treatment with KMnO
4
(Fig. 3.14) [130]. The oxi-
dative unzipping generated the graphene nanoribbons that are initially oxidized. The authors used a
three-step annealing treatment to completely remove the oxygen from the bulk and edges of the
nanoribbons and also effectively dope charge carriers. The rst step annealed freshly deposited nano-
ribbons on substrates at 800 C to remove the bulk of the oxygenation. The second step was carried
out at 750 C in a H
2
atmosphere to produce edge termination and charge carrier doping before the
fabrication of the FET electrodes using electron-beam lithography (EBL). The third step, annealing
was performed at 300 C to clean the surface immediately before the formation of the electrodes.
The obtained GNRs were examined by AFM, HRTEM and Raman Spectroscopy. The AFM height anal-
ysis of monolayer GNRs showed a thickness of 0.8 nm while the HRTEM studies indicated the presence
of small amount of structural defects associated with the oxidation and uncompleted removal of oxi-
dized groups which was supported by the investigation of electrical properties. The ratio of D band
and G band (I
D
/I
G
) was found to be ~0.45, suggesting a good quality of the obtained GNRs.
Although the GNRs, obtained by various new unzipping methods [130136], have inferior elec-
tronic properties compared to those of wide, mechanically peeled sheets of graphene, these pioneer
work has paved a way leading to a large-scale production of GNRs with controlled structure and qual-
ity and tunable properties. The future research will focus on understanding the mechanism of the pro-
cess and optimizing the experimental parameters to prepare highly ordered sub-10 nm GNRs for
potential applications in room temperature transistors.
A
B
Fig. 3.14. (A) Field-emission SEM image of an ensemble of the as-grown nanoribbons, which were dispersed on a SiO
2
substrate
in a water droplet containing a suspension of nanoribbons. The nanoribbons are entangled and not sufciently exfoliated. Inset
(right): AFM images of individual nanoribbons spread by applying a strong air ow to the droplet. Inset (left): height of the
nanoribbon measured along the longitudinal direction. The thickness of ~0.8 nm indicates a single-layer nanoribbon. (B) FET
fabricated using a nanoribbon end-bonded by two metal electrodes, which eliminates single-electron charging effects. The
thickness of the SiO
2
layer on the gold/titanium backgate electrode was 300 nm, and the spacing of source and drain electrodes
was 500 nm in all samples. (Reproduced with permission from [130].)
4. Graphene: characterization and properties
4.1. Characterization
4.1.1. Optical imaging of graphene layers
Various techniques are being used to image single layers, bi-layers and few layers of graphene such
as optical microscope, atomic force microscopy (AFM), scanning electron microscopy (SEM) and high
resolution transmission electron microscopy (TEM). Often, a combination of two or more techniques
completes imaging of different layers of graphene. After the discovery of graphene, the optical micro-
scope was primarily used to image various layers since it is the cheapest, non-destructive, and readily
available in laboratories. However, this requires graphene layers mounting on silicon dioxide sub-
strate for good contrast imaging. Over the past few years, the substrate designing has been given a
considerable attention to enhance the visibility of thin sheets [137139]. The mechanism behind such
contrast is explained in terms of FabryPerot interference in the dielectric surface layer that governs
the uorescence intensity that allows contrast between graphene layers and substrate. The visibility of
sheets can be dened by the Michelson contrast (C) relation [140]:
C =
R
material
R
dielectric
R
material
R
dielectric
(4:1)
where R
material
is the reected intensity from the material and R
dielectric
is the intensity without the
material. If C = 0, the material is not detectable, C = 0 to +1 material is brighter than the substrate,
and C = 0 to 1 the sample will be darker than the substrate.
SiO
2
and Si
3
N
4
are the most commonly overlay materials on silicon for enhancing the contrast of
graphene layers which are dielectric in nature [141]. Another governing factor that modulates contrast
is the wavelength of the incident light. Blake et al. [141] demonstrated the contact variation using dif-
ferent narrow band lters to detect sheets for any thickness of SiO
2
support. They found that under
normal white light illumination sheets were invisible on 200 nm SiO
2
, while thick and thin sheets
were visible on 300 nm SiO
2
when green light was used, whereas sheets were visible on 200 nm
SiO
2
by blue light.
Fig. 4.1 shows the optical image of the different layers of the micromechanically exfoliated graph-
ene on silicon substrate with 300 nm SiO
2
over-layer. The number of layers was identied by color
contrast and AFM [142]. So far the detection technique demonstrated is dependent on the substrate
thickness and incident light wavelength. More research is needed to facilitate graphene-based sheets
visualization independent of support material without any modication of the graphene.
4.1.2. Fluorescence quenching technique
Recently, a uorescence quenching microscopy (FQM) technique was used to image graphene,
RGO and GO for immediate sample evaluation and manipulation so that the synthesis process can
be improved [143]. They have demonstrated the low cost and time saving method of visualizing
GO and RGO using substrate independent uorescence quenching microscopy (FQM). The imaging
mechanism involves quenching the emission from a dye coated GO and RGO; the dye can be re-
moved by rinsing without disrupting the sheets. The contrast arises due to the chemical interaction
between the GO and the dye molecule on the molecular scale because of the charge transfer from
dye molecule to GO that causes quenching of uorescence [144]. The contrast measured in the uo-
rescence images was achieved 0.78 for 300 nm SiO
x
layer. Furthermore, higher contrast was
achieved when GO sheets were deposited on 100 nm SiO
x
, quartz and glass substrates which gave
the contrast ~0.52, 0.2 and 0.07 respectively. These values were sufcient for a clear visualization
[144]. The image obtained by FQM is shown in Fig. 4.2 and compared to the AFM image of the same
area. The technique has the capability to see the microstructures of the GO/RGO lm even on plastic
substrate. However, this technique is limited to the micron sized layers because it is based on light,
and the lateral resolution of FQM is diffraction limited. This technique relies on dye addition on
graphene surface, which prohibits further use of the same sample due to the attachment of un-
wanted functional groups.
Fig. 4.1. Optical microscopy image of single-, double- and triple- layer graphene on Si with a 300 nm SiO
2
over-layer, labeled in
the paper as 1L, 2L and 3L, respectively. (Reproduced with permission from [142].)
Fig. 4.2. (A) AFM image showing G-O single layers deposited on a SiO
2
/Si wafer before applying a 30 nm thick uorescein/PVP
layer for FQM. (B) A FQM image of the same area of the wafer, showing good correlation to the AFM view. (C) After washing off
the dye coating, no residues can be detected by AFM. (D) Line scan data on a folded sheet show no signicant deviation in
thickness before and after FQM imaging (all scale bars ~10 lm). (Reproduced with permission from [143].)
4.1.3. Atomic force microscopy (AFM)
This technique of imaging can successfully determine the layer thickness at the nanometer scale.
However, this is cumbersome for imaging large area graphene. Moreover, AFM imaging gives only
topographic contrast, which cannot distinguish between the graphene oxide and the graphene layers
in normal operation. However, phase imaging is one of the attractive features of tapping-mode AFM;
this facilitates to distinguish between a defect free pristine graphene and its functionalized version.
One of the reasons behind is the difference in the interaction forces between the AFM tip and the at-
tached functional group. Paredes et al. [145] demonstrated the inuence of attractive mode of AFM to
determine the thickness of the sheet. They found that the repulsive mode induces deformation causing
error in the height measurement. They observed thickness ~1.0 nm for the unreduced graphene oxide
and 0.6 nm for the chemically reduced GO. The difference in the thickness and the phase contrast was
reported due to hydrophilicity difference resulting from distinct oxygen functional group in the reduc-
tion process as shown in Fig. 4.3. Besides imaging and thickness detection, AFM has been explored for
mechanical characterization of graphene as it can resolve the small forces involved in the deformation
Fig. 4.3. Height (a and c) and corresponding phase (b and d) tapping-mode AFM images of unreduced (a and b) and chemically
reduced (c and d) graphene oxide nanosheets deposited from aqueous dispersions onto freshly cleaved HOPG. The images were
recorded in the attractive regime of tip sample interaction. Superimposed onto each image is a line prole taken along the
marked red line. (Reproduced with permission from [145].)
process. Different AFM modes allowed the study of mechanical [7], frictional, electrical, magnetic and
even elastic properties of graphene akes.
4.1.4. Transmission electron microscopy (TEM)
In general, TEM is frequently used to image nano size materials to the atomic scale resolution
where a transmitted electron beam passes through the ultra thin sample and reaches to the imaging
lenses and detector. As graphene and reduced graphene oxide (RGO) are an atom thick layer, it seems
that the TEM is the only tool which can resolve atomic features of the graphene. However, the use of
traditional TEMs is limited by their resolution at low operating voltage, whereas the operation at high
voltage damages the monolayer. Recently, few researches have used a new class of TEM which is an
aberration corrected in combination with monochromator that can provide 1 resolution at an accel-
eration voltage of only 80 kV [120,146]. For the rst time Mayers group has shown direct high reso-
lution images of the graphene lattice depicting every single carbon atom arranged in hexagonal
fashion [147]. This clearly reveals the ball-and-stick model where bright and dark contrast in the im-
age corresponds to the atoms and the gaps respectively shown in Fig. 4.4. Researchers have also
Fig. 4.4. (A) Direct image of a single layer graphene membrane. (B) Contrast prole along the dotted line in panel a (solid) along
with a simulated prole (dashed). The experimental contrast is a factor of 2 smaller: Panel (C) shows the same experimental
prole with the simulated contrast scaled down by a factor of 2. (D and E) Step from a monolayer (upper part) to a bilayer
(lower part of the image), showing the unique appearance of the monolayer. Panel (E) shows the same image with an overlay of
the graphene lattice (red) and the second layer (blue), offset in the Bernal (AB) stacking of graphite. (F) Numerical diffractogram,
calculated from an image of the bilayer region. The outermost peaks, one of them indicated by the arrow, correspond to a
resolution of 1.06 . The scale bars are 2 . (Reproduced with permission from [147].)
demonstrated that the imperfection and topological peculiarities in graphene affected the electronic
and mechanical properties, which can be determined using such aberration corrected low voltage
TEM.
In another imaging technique, Gass et al. have shown atomic lattice, defects and surface contam-
ination in high angle annular dark-eld (HAADF) images using scanning transmission electron micros-
copy (STEM). The technique involves focusing an electron beam onto monoatomic region and further
scanning [148]. This technique easily detects the arrangement of atomic scale defects and contami-
nant atoms using Z contrast. Fig. 4.5 shows the HRTEM bright eld and HAADF image of mono layer,
revealing a clean graphene monolayer surrounded by the contaminants, and a mono- and di-vacancy
defect due to missing C-atoms. It is also worth mentioning here that due to the transparent nature of
the graphene and its oxide, these are used as a support for imaging and dynamics of light atoms and
molecules under TEM [149151]. They have demonstrated that even conventional TEM can be utilized
to observe the smallest atom and molecule using graphene as a membrane to support other sample in
TEM. As graphene is one atom thick; this provides the thinnest possible continuous support unlike
other amorphous TEM support. Its crystallinity and high conductivity facilitate back ground
subtraction and charging reduction.
Fig. 4.5. High-resolution images of monolayer graphene. Bright-eld (a) and HAADF (b) images of the monolayer, showing a
clean patch of graphene surrounded by a mono-atomic surface layer; individual contaminant atoms of higher atomic number
can be seen in (b). The inset FFT shows the lattice in the HAADF image and, by applying a band pass lter, the atomic structure is
apparent. HAADF lattice images of defects: showing a mono-vacancy (c) and a di-vacancy (d). Inset showing the FFT of the raw
image. (Reproduced with permission from [148].)
As mentioned in the previous section, RGO has superior conductivity than GO but inferior to the
pristine graphene. It is supposed that during the reduction process, many defects generate in the car-
bon 2D lattice (point defect or incomplete removal of epoxy/oxygenated functional groups). These de-
fects and foreign functional groups remarkably affect the electronic and thermal conductivity. So it is
important to identify the most dominant defects in graphene before incorporating in the technologi-
cally important electronic devices. In combination of other spectroscopy techniques HRTEM has
unraveled the atomic structure of GO and RGO. Recently, the local chemical structure and defect struc-
ture of RGO and GO have been given more attention at atomic level [117,120]. It has been found that
after reduction, layers consisted of the defect free nano size graphene region inter dispersed with de-
fect areas dominated by clustered pentagons and heptagons as shown in Fig. 3.10 in Section 3.
4.1.5. Raman spectroscopy
Carbon allotropes show their ngerprints under Raman spectroscopy mostly by D, G, and 2D peaks
around 1350 cm
1
, 1580 cm
1
and 2700 cm
1
respectively due to the change in electron bands. Iden-
tication of these features allows characterization of graphene layers in terms of number of layers
present, and their effect of strain, doping concentration, and effect of temperature and presence of de-
fects. The G band is associated to the doubly degenerated E
2g
phonon mode at the Brillouin zone cen-
ter. This band (near 1580) arises due to the in plane vibration of the sp
2
carbon atoms, whereas the 2D
band is at almost double the frequency of the D band and originates from second order Raman scat-
tering process. The D band appears due to the presence of disorder in atomic arrangement or edge ef-
fect of graphene, ripples and charge puddles. Comparison of Raman spectra between graphite, single
and few layer graphene are shown in Fig. 4.6 [152]. The Raman spectra at the center of the graphene
Fig. 4.6. (a) Comparison of Raman spectra at 514 nm for the graphite and single layer graphene. (b and c) Evolution in 2D band
as a function of layers at 514 and 633 nm excitations (d and e) Comparison of the D band at 514 nm at the edge of bulk graphite
and single layer graphene. The t of the D1 and D2 components of the D band of bulk graphite is shown. (e) The four
components of the 2D band in 2 layer graphene at 514 and 633 nm. (Reproduced with permission from [152].)
layers do not show D peak that conrms the absence of defects. Instead, the signicant change in
shape and intensity was observed for 2D band of graphene and graphite. Ferrari el al. [152] have
shown that the 2D band splits into two components for bulk graphite and in four components for
bi-layer graphene (Fig. 4.6 c and d). An increase in the number of layers reduces the relative intensity
of 2D and increases its FWHM and makes it blue shifted [142,152,153]. The single sharp 2D peak was
reported for mono layer that is four times more intense than the G peak. Effect of various factors on
Raman spectra are summarized in Table 4.1. As the properties of graphene crucially depend on the
number of layers and purity thus various researchers have used Raman spectra as a non-destructive
tool to characterize and quality control of mono and few layers of graphene. Various effects on graph-
ene have also been studied by following trends in Raman spectra including thickness determination,
strain in graphene layers, defects and doping.
4.2. Properties
In the past few years many fascinating properties were discovered through the investigation of
pristine graphene including extremely high charge (electrons and holes) mobility (230,000 cm
2
/Vs)
with 2.3% absorption of visible light [159,160], thermal conductivity (3000 W/mK), and the highest
strangth (130 GPa), and the highest theoretical specic surface area (2600 m
2
/g), and half integer
quantum Hall effect even at ambient temperature (minimum Hall conductivity ~4e
2
/h, even at carrier
concentration is zero), which has lled the research community with great enthusiasm. This section
will focus on the graphene properties that lay foundation for their wider scope of applications. The
elaborate discussion on graphene properties is beyond the scope of this article that can be found in
some of the recent review articles. However, it is worth mentioning the important properties of graph-
ene with single layer, bi-layers and few layers.
4.2.1. Electrical transport property
Pristine graphene, a two-dimensional honeycomb carbon lattice is a zero gap semiconductor. The
sp
2
hybridized carbon atoms are arranged in hexagonal fashion in 2-dimensional layer. A single hex-
agonal ring comprises of three strong in-plane sigma bonds P
z
orbitals perpendicular to the planes.
Different graphene layers are bonded by weak p
z
interaction while strong in-plane bonds keep hexag-
onal structure stable and facilitate de-lamination of 3D structure (graphite) into individual graphene
sheet just by applying mechanical stress. As described earlier, the scotch tape method micromechan-
ically creates single layer of defect free graphene and provides a 2-D platform, to investigate many
fundamental properties of this 2-D crystal.
One of the most interesting aspects of the graphene is its highly unusual nature of charge carriers,
which behave as massless relativistic particles (Dirac fermions). Dirac fermions behavior is very
abnormal compared to electrons when subjected to magnetic elds for example, the anomalous inte-
ger quantum Hall effect (QHE) [2,161]. This effect was even observed at room temperature [3]. Graph-
ene has distinctive nature of its charge carriers, which mimic relativistic particles, considered as
electrons those have lost their rest mass, can be better described with (2 + 1) dimensional Dirac equa-
tion [162]. The band structure of single layer graphene exhibits two bands intersecting at two in
Table 4.1
Effect on various factors on Raman peak position, shape and splitting.
Factors Peak G Peak 2D References
Graphene layers Blue shift [152]
Tensile strain Red shift Red shift with stain [154,155]
Compressive strain (micromechanically
Cleaved graphene)
Red shift with strain and splitting at
higher strain
Red shift with strain no
splitting
[156]
Compressive strain (epitaxial graphene on
SiC)
Blue shift, no splitting Blue shift, no splitting [157]
Temperature Red shift with temperature No change [153]
Doping Blue shift with doping [158]
equivalent point K and K
/
in the reciprocal space. Near these points electronic dispersion resembles
that of the relativistic Dirac electrons. K and K
/
are referred as Dirac points where valence and conduc-
tion bands are degenerated, making graphene a zero band gap semiconductor (Fig. 4.7).
The high electronic conductivity in single layer is due to very high quality, i.e. low defect density of
its crystal lattice. Defects in general act as scattering sites and inhibit charge transport by limiting the
electron mean free path. There are evidences that pristine graphene is defect free, thus its conductivity
must be affected by some extrinsic source. Various factors have been proposed which affect the con-
ductivity such as, interaction with the under laying substrate while measurement, surface charge
traps [164,165], interfacial phonons [166] and substrate ripples [167]. Kim and coworkers [159] re-
ported the mobilities in excess of 200,000 cm
2
/Vs at carrier density of 2 10
11
cm
2
for mechanically
exfoliated suspended layer of graphene above a Si/SiO
2
gate electrode (Fig. 4.8). Substrate induced
Fig. 4.7. Bandgap in graphene. Schematic diagrams of the lattice structure of (A) monolayer and (B) bilayer graphene. The green
and red colored lattice sites indicate the A (A1/A2) and B (B1/B2) atoms of monolayer (bilayer) graphene, respectively. The
diagrams represent the calculated energy dispersion relations in the low-energy regime, and show that monolayer and bilayer
graphene are zero-gap semiconductors. (C) When an electric eld (E) is applied perpendicular to the bilayer, a band gap is
opened in bilayer graphene, whose size (2D) is tunable by the electric eld. (Reproduced with permission from [163].)
Fig. 4.8. (A) Measured four-probe resistivity q
xx
as a function of gate voltage V
g
before (blue) and after (red) current annealing;
data from traditional high-mobility device on the substrate (gray dotted line) shown for comparison. The gate voltage is limited
to 5 V range to avoid mechanical collapse. (B) Mobility, l = 1/enq
xx
as a function of carrier density n for the same devices. (C)
AFM image of the suspended before the measurements. (Reproduced with permission from [159].)
scattering was minimized by using single layer graphene (SLG) in completely suspended condition.
Importantly, study showed how absorbed impurities on graphene surface, and trapped in between
the graphene and substrate, even in the suspended situation affected the electron mobility. Electric
current induced annealing improved mobility up to 230,000 cm
2
/Vs.
Another important characteristic of SLG is its ambipolar electric eld effect at room temperature,
that is charge carriers can be tuned between electrons and holes by applying a required gate voltage
[5,162]. In positive gate bias the Fermi level rise above the Dirac point which promote electrons pop-
ulating into conduction band, whereas, in negative gate bias the Fermi level drop below the Dirac
point promoting the holes in valence band in concentrations of n = aV
g
(where a, coefcient depending
on the SiO
2
layer used as a dielectric in the eld effect devices, V
g
~ gate voltage).
Graphene is a potential material for the future generation electronic devices suffers from zero en-
ergy band gap even at the charge neutrality point, which is one of the hurdle for graphene to be useful
as an electronic material, for example, in graphene-based FET. The zero band gap does not allowits use
in logic applications, which require frequent on/off switching. However, band structure of the graph-
ene can be modied by lateral quantum connement by constraining the graphene in nanoribbons
[124,128,168] and in graphene quantum dots [169], and by biasing bi-layer [21,170,171] graphene.
Bandgap opening in both zigzag and armchair nanoribbons was observed and proven experimentally
and theoretically which vary with the width of the ribbons and disorderness in the edges [172]. Dop-
ing and edge functionalization also change the band gap in nanoribbons [173].
It is important to note that the most of the primary work on graphene has been related to FET. A
schematic of the graphene-based FET is shown in Fig. 4.9 consisting of the gate, a graphene channel
connecting source and drain electrodes, and a dielectric barrier layer (SiO
2
) separating the gate from
the channel. In most of the studies ~300 nm SiO
2
layer is used, under the graphene acted as a dielec-
tric layer and silicon acted as a back gate. Due to large parasitic capacitance of the 300 nm SiO
2
layer, it
nds difculty in integration with other electronic components. Thus, top gated graphene-based de-
vice have been developed in 2007 [174]. Top gated graphene-based MOSFETs have been prepared
using exfoliated graphene [174177], CVD grown graphene on Ni and Cu substrate [44] and epitaxial
graphene [178,179], whereas, Al
2
O
3
, SiO
2
and HfO
2
dielectric materials have been used for top gate
[171].
Recently, large area epitaxial graphene has attracted much interest due to its scalability for elec-
tronics, and even few layer graphene lms grown on SiC show electronic properties similar to the iso-
lated graphene sheet. However, the charge transport properties are lower than the pristine graphene
by an order of one. Mixed opinion exists on band gap opening in large area epitaxial graphene. Some
reports suggest a zero band gap in graphene layer just above the carbon buffer layer [180] and the
other found around 0.26 eV [181,182].
De Heer group has developed a method of epitaxially growing graphene on SiC substrate. It was
found that the mobility of the graphene grown on carbon terminated face was greater than the graph-
ene grown on Si terminated face [183] due to the difference in the structure, and this can be gated.
They have demonstrated the energy gap of ~0.26 eV which decreases with increasing thickness and
approaches zero when number of layers exceeds four [181]. The energy gap, in single layer
(0.26 eV), bilayer and triple layer (0.14 eV) was induced as a result of symmetry breaking due to
the interaction with substrate.
Fig. 4.9. (a) Schematic diagram of back gated and (b) top gated graphene eld effect devices. The perpendicular electric eld is
controllable by applied back-gate voltage (V
g
) and the top gate voltage (V
top
).
Seyller and coworkers [64] have achieved high electronic mobilities in wafer size graphene layers
prepared in ex situ atmospheric pressure graphitization of SiC in Ar atmosphere which reached up to
2000 cm
2
/Vs at 27 K and to 930 cm
2
/Vs at 300 K for Si terminated face.
Whereas, other study showed the mobility variation for multilayer epitaxial graphene lms
from 600 to 1200 cm
2
/Vs for Si-face measured in ambient condition and could reached up to
5000 cm
2
/Vs for the carbon terminated face with on/off ratio up to seven, the difference was
attributed to the different crystallographic domain size of graphene on the two faces [178]. The
signicantly larger single crystalline domain size was reported for C face graphene than Si-face
[184] which provides structural coherency for longer mean free path to charges, and thus, provides
high mobility.
Chemical vapor deposition is another method envisioned for large scale synthesis of graphene lay-
ers. Growth of monolayer and few layers on various substrates have been demonstrated in earlier sec-
tions. Reina et al. [48], showed single and few layer graphene (20 lm lateral size) growth at ambient
pressure on Ni substrate using CVD. A large variation in eld effect mobility ~1002000 cm
2
/Vs for
both electrons and holes was reported due to ineffective gate modulation caused by the inhomoge-
neous thickness of graphene lms and grain boundary scattering inside the lms. Recently, the charge
mobility of large area graphene lm grown on Ni by CVD and transferred to SiO
2
substrate was mea-
sured greater than 3700 cm
2
/Vs which exhibited the half-integer quantumHall effect similar to micro-
mechanically cleaved layer, conrming the monolayer characteristic of graphene [185]. It is worth to
notice that nickel is the most commonly used metal substrate and studied well for large area, high
quality mono and few layer of the graphene [41,43,48,186,187]. However, graphene grown on this
substrate suffers from the small grain size, multilayer deposition at grain boundaries, and carbon sol-
ubility in nickel. Ruoff and coworkers [44] have used a copper foil, as carbon has low solubility in cop-
per and grown predominantly single layer graphene with less than 5% area of few layer graphene. The
lms have achieved mobility as high as 4050 cm
2
/Vs. Another study [41] has also revealed the poten-
tial of CVD technique of depositing graphene lm on large wafer (up to 3 in.) of copper substrate at
ambient pressure. This study has shown the ambipolar eld effect mobilities up to ~3000 cm
2
/Vs with
on/off ratio ~4 and half integer QHE of the lms.
Difculties of graphene single layer scale up for applications, have led researchers to extend graph-
ene study to bi-layer and few layers (<10).
Bilayer graphene also exhibits an anomalous QHE, different fromthat of the single layer. The charge
carriers in bi-layer graphene have parabolic energy spectrum near the K point, which indicates bilayer
graphene is also gapless (Fig. 4.7) [188]. Bilayer graphene remains metallic at the neutrality points
[188]. In the case of bi-layer, the charge particles are chiral, similar to massless Dirac fermions, but
have a nite mass (0.05 m
o
) called massive Dirac fermions.
Though, the bi-layer graphene is gapless, its electronic band gap can be controlled by an electric
eld perpendicular to the plane [163]. The double gated approach was used to demonstrate the con-
trolled induction of an insulating state with large suppression of the conductivity in bi-layer graphene.
The size of the gap is proportional to the voltage drop between the two graphene planes and value can
be as high as 0.10.3 eV. In contrast, group at IBM Thomas J. Watson research center [189] has shown
bi-layer graphene FET with high on/off current ratio of around 100 and 2000 at room temperature and
20 K respectively in dual-gated bi-layer graphene FETs. The measured band gap was more than
0.13 eV. In another study [190], it was reported that the electronic band gap of the bi-layer graphene
can be tuned by applying electric eld, which provide an opportunity to use graphene bi-layer as a
tunable energy band gap semiconductor for many electronic applications like photodetectors, tera-
hertz technology [191], infrared nanophotonics [192], pseudospintronics [193], and laser. They have
also shown the band gap can be tuned to values larger than 0.2 eV.
Finally, processable graphene sheets in large quantities are also desirable for applications like
graphene reinforced composites, transparent electrical conductive lms, energy storage, etc. [194].
A promising approach including chemical and thermal reduction of graphene oxide can provide graph-
ene in scalable amount [26,76]. Researchers have been making continuous effort to improve electrical
transport properties of RGO in order to use in electrical applications. Graphene oxide has very high
electrical resistance (4 MX/square) due to presence of oxygenated functional groups. Removal of at-
tached functional group from 2-D carbon lattice by chemical and thermal reduction partially restores
the electronic conductivity however; these processes introduce structural imperfections in carbon lat-
tice and degrade the electrical properties compare to the pristine graphene.
The conductivity and mobility of RGO were reported to be lesser by 3 and 2 orders of magnitude
respectively than pure graphene. The reduced conductivity is due to lattice vacancies which cannot
heal during reduction process. Presence of intact nano meter size domain in RGO results in hopping
conduction has been suggested. The eld effect mobilities of 2200 cm
2
/Vs and conductivity of
0.052 S/cm were measured for RGO [195]. Moreover, graphene sheets obtained from hydrazine
reduction behave as a P-type semiconductor [196]. In contrast, Chhowalla and coworkerss [197] study
exhibited the ambipolar characteristics of RGO lms when measured at low temperature, which is
comparable to graphene. The scattering at the junction of the overlapping sheets caused lower mobil-
ity (1 cm
2
/Vs for holes and 0.2 cm
2
/Vs for electrons). They have observed the RGO sheet resistance as
low as 43 KX/square prepared by chemical reduction. Whereas, the lower resistance of 10
2
10
3
X/
square and electrical conductivity ~100 S/cm were observed for thermally reduced GO (RGO) [28]
in comparison to GO (~4 MX/square) [72] which was due to high temperature deoxygenation. Re-
cently, a graphene paper of chemically converted graphene was prepared with electrical conductivity
of 72 S/cm at room temperature [76]. This can have potential applications in membranes, anisotropic
conductors, transparent electrodes, and super capacitors.
Furthermore, interested readers can refer article by Neto et al. [198] and Nilsson et al. [170] for
more information on electronic properties of single, bilayer and few layer graphene.
4.2.2. Quantum Hall effect
The charge particles behave as massless Dirac fermion in a 2D lattice which exhibit interesting ef-
fect on energy spectrum of the landau levels produced in the presence of magnetic eld perpendicular
to the graphene sheets.
The Landau level energies are given by
E
j
=
j
1
2
heB
_ _
m
e
(4:2)
where j (=0, 1, 2, 3, . . .) are the indices for the Landau index and = h/2p.
Due to disorder, the Hall conductivity (r
xy
) of the two-dimensional electron gas (2DEG) shows the
plateaus at jh/2eB and is quantized, can be expressed by r
xy
= j (2e
2
/h) which leads to integer quan-
tum Hall effect (IQHE).
In contrast to 2DEG, the energy of Landau levels for graphene is expressed by E
j
=
v
F
2ehB[j[
_
; [j[ = 0; 1; 2; 3; . . . is the Landau index and B is the magnetic eld applied perpendicular
to the graphene plane. Since, the Landau levels are doubly degenerated for the K and K
/
points at
j = 0, these levels are shared equally between electrons and holes. This leads to the anomalous IQHE,
where the Hall conductivity is given by
r
xy
=
4 j
1
2
_ _
e
2
h
(4:3)
The Hall conductivity for the single layer graphene shows a plateau when plotted as a function of
carrier concentration, n, at a xed magnetic eld. Novoselov et al., have rst observed anomalous
IQHE (shown in Fig. 4.10), measured at B = 14 T and temperature of 4 K [161]. It is interesting to note
that at the zero energy level (j = 0) a nite value (r
xy
= 2e
2
/h) of conductivity is observed. The QHE
plateaus occur at the half integer for high energy level. This gives a ladder of equidistant steps in the
Hall conductivity. This QHE, in monolayer of graphene, is the distinctively different for both the
holes and electrons than the conventional QHE as quantization condition is shifted by a half integer.
This abnormal quantization was attributed to the topologically exceptional electronic structure of
graphene [2].
In general QHE is observed at low temperatures typically below the boiling point of the liquid he-
lium. Novoselov et al. [3] observed QHE in graphene at room temperature caused by very high concen-
tration of carriers (up to 10
13
/cm
2
), with single 2D subband, important to occupy the lowest Landau
level even in ultra high magnetic eld. Moreover, high mobility (l ~ 10,000 cm
2
/Vs) allows the move-
ment of massless Dirac fermions with minimal scattering under ambient conditions.
In the case of bilayer graphene, charge carriers have parabolic energy spectrum which are chiral
with nite mass [188]. The Landau quantization of these massive Dirac fermions results in plateaus
in Hall conductivity which appears at standard integer positions. The Hall conductivity is given by
r
xy
= j4e
2
/h, where j is an integer other than zero. The rst plateau occurs at j = 1 however, the plateau
at zero r
xy
is absent unlike the conventional QHE (Fig. 4.11). Moreover, the Hall conductivity under-
goes a double-sized step across this region.
4.2.3. Optical properties
Many reports conrmed that single layer graphene absorbs 2.3% of incident light over a broad
wavelength range in spite of being just a monolayer (Fig. 4.12) [50,160]. Graphene transmittance
can be well described in terms of ne structure constants [160,199]. The absorption of light was found
to be increasing with the addition of a number of layers linearly, each layer absorption
A = 1 T = pa = 2.3%, where a ~ 1/37 is the ne structure constant. The graphene can be imaged by
optical image contrast on Si/SiO
2
substrate due to interference, and the contrast increases with the
number of layers. The absorption for monolayer graphene is at from 300 to 2500 nm, the peak at
~250 nm in UV region is attributed to the inter band electronic transition from the unoccupied p
+
states (Fig. 4.12) [199].
In addition, their optical transition can be modied by changing the Fermi energy considerably
through the electrical gating [192,200]. The tunability, provided by the electrical gating and charge
injection in graphene-based optoelectronics devices, have been predicted to develop tunable IR detec-
tors, modulators, and emitters [192]. The exceptional electrical transport properties in conjunction
with optical properties have fueled lot of interests in novel photonic devices. It has also been sug-
gested that the zero band gap, large area monolayer and few layer graphene FET can be used as ultra-
fast photodetectors [201]. The absorption of light on the surface generates electronhole pairs in
graphene which would recombine very quickly (Picoseconds) depending upon the temperature as
well as electrons and holes density [202]. When an external eld is applied these holes and electrons
can be separated and photo current is generated. Similar behavior occurred in the presence of internal
eld. This eld has formed near the electrode and graphene interface [201,203,204]. Xia et al. [201],
Fig. 4.10. QHE for massless Dirac fermions in single layer graphene. Hall conductivity (r
xy
) and longitudinal resistivity (q
xx
) of
graphene as a function of their concentration at B = 14T and T = 4 K. The plateau occur half integer for high energy level results
in a ladder of equidistant steps in Hall conductivity. Inset shows the r
xy
in two-layer graphene where the quantization sequence
is normal and occurs at integer j. (Reproduced with permission from [4].)
showed that the unique properties of graphene enabled very high bandwidth (>500 GHz) light detec-
tion, very wide wavelength detection range, zero current operation and good quantum efciency.
Another property of graphene is photo luminescence (PL). It is possible to make graphene lumines-
cent by inducing a suitable band gap. Two routes have been proposed, the rst method involves cut-
ting graphene in nanoribbons and quantumdots. The second one is the physical or chemical treatment
with different gases to reduce the connectivity of the p electron network [205207]. For example it is
shown that PL can be induced by oxygen plasma treatment of graphene single layer on substrate
[208]. This gives an opportunity of making hybrid structures by etching just the top layer, while keep-
ing the underlying layer unaffected. Broad PL from solid GO and liquid GO suspension was also ob-
served and the progressive chemical reduction quenched the PL of GO. Whereas, oxidation
produced a disruption of the p network and open a direct electronic band gap [209].
Fluorescent organic compounds are very important for the development of low cost optoelectronic
devices [210]. Particularly blue uorescence from aromatic or olenic molecules and their derivatives
are important for display and lighting applications [211]. The blue PL was observed for GO thin lms
deposited from thoroughly exfoliated suspensions [212]. The PL characteristic and its dependence on
the reduction of GO originate from the recombination of electronhole pairs, localized within small
sp
2
carbon clusters embedded within the GO sp
3
matrix [212].
Fig. 4.11. Quantum Hall effect in bilayer graphene. (a) Hall conductivity (r
xy
) and (b) Longitudidinal (q
xx
) are plotted as
functions of n at a xed B and temperature T = 4 K. r
xy
allows the underlying sequences of QHE plateaus to be seen more clearly.
r
xy
crosses zero without any sign of the zero-level plateau as expected in conventional 2D system. The inset shows the
calculated energy spectrum for bilayer graphene, which is parabolic at low e. (Reproduced with permission from [188].)
Moreover, the combined optical and electrical properties of graphene have opened new avenues for
various applications in photonics and optoelectronics. Numerous applications using graphene as a
promising candidate have been suggested, which includes photodetectors, touch screens, light emit-
ting devices, photovoltaics, transparent conductors, terahertz devices and optical limiters.
4.2.4. Mechanical properties
Unwanted strain can affect the performance and life of the electronic devices. Generally, applica-
tion of external stress on crystalline material can alter inter atomic distances, resulting in the redistri-
bution, in local electronic charge. This may introduce a band gap in electronic structure and modify
the electron transport property signicantly. After carbon nanotubes, graphene has been reported
to have the highest elastic modulus and strength. Several researchers have determined the intrinsic
mechanical properties of the single, bilayer and multiples layer of graphene are summarized in
Table 4.2.
A single defect free graphene layer is predicted to show the highest intrinsic tensile strength with
stiffness similar to graphite. One method to determine the intrinsic mechanical properties is to probe
the variation of the phonon frequencies upon the application of tensile and compressive stress
[154,157,215]. The Raman spectroscopy is one of the techniques which can monitor phonons
Fig. 4.12. Representative of transmittance of different graphene layers. UVvis spectra roll-to-roll layer-by-layer transferred
graphene lms on quartz substrates. The inset shows the UV spectra of graphene lms with and without HNO
3
doping. The right
inset shows optical images for the corresponding number of transferred layers (1 1 cm
2
). (Reproduced with permission from
[50].)
Table 4.2
Mechanical properties of graphene.
Method Material Mechanical properties References
AFM Mono layer graphene E = 1 0.1 TPa [7]
r
int
= 130 10 GPa at e
int
= 0.25
Raman Graphene Strain ~1.3% in tension [213]
Strain ~0.7% in compression
AFM Mono layer E = 1.02 TPa; r = 130 GPa [214]
Bilayer E = 1.04 TPa; r = 126 GPa
Tri-layer E = 0.98 TPa; r = 101 GPa
Graphene
frequency under uniaxial tensile and hydrostatic stress [155]. It has been observed that the tensile
stress results in the phonon softening due to decreased vibrational frequency mode whereas compres-
sive stress (hydrostatic) causes the phonon hardening due to increased vibrational frequency mode.
Thus in graphene, studying the vibration of phonon frequency as a function of strain can provide use-
ful information on stress transfer to individual bonds (for suspended graphene) and atomic level inter-
action of graphene to the underlying substrate (for supported graphene).
Compressive and tensile strain in graphene layer was estimated using Raman spectroscopy by
monitoring change in the G and 2D peaks with applied stress. The splitting of the G peak and red shift
was observed with increase in strain whereas the 2D peak also red shift without splitting for small
strains ~0.8% [156]. Ni et al. have observed the opposite behavior for epitaxial graphene on SiC sub-
strate [157]. They found, the blue shift in all the Raman bands for the epitaxial graphene, in compar-
ison to that of the micromechanically cleaved graphene due to the compressive stress in grown
graphene. Besides, the strain on graphene may change electronic band structure which indicates that
the energy band gap can be tuned by introduction of the controlled strain. Recently, the band gap tun-
ing was reported under uniaxial strain [155]. A layer of graphene was deposited on exible polyeth-
ylene terephthalate (PET) so that uniaxial tensile strain (up to ~0.8%) can be applied on the single/
three-layer graphene by stretching the PET in one direction. The band gap of 0.25 eV was detected un-
der the highest strain (0.78%) for the single layer graphene. It was also suggested that the uniaxial
strain affected the electronic properties of graphene much more signicantly as it breaks the bonds
of CAC lattice.
4.2.5. Thermal properties
Application of the graphene has been envisioned for electronic devices. Where, thermal manage-
ment is one of the key factors for better performance and reliability of the electronic components. Con-
siderable amount of heat generates during the device operation needs to be dissipated. Carbon
allotropes such as graphite, diamond, and carbon nano tubes have shown higher thermal conductivity
due to strong CAC covalent bonds and phonon scattering. Earlier carbon nanotubes are known for the
highest thermal conductivity with room temperature value ~3000 W/mK for MWCNT [216] and
3500 W/mK for single wall CNT [217]. However, a large thermal contact resistance is the main issue
with CNTs based semiconductor. Recently the highest room temperature thermal conductivity ~ up
to 5000 W/mK for the single layer graphene has been reported (pure defect free graphene) [6] whereas
for supported graphene conductivity is ~600 W/mK. Conductivity of the graphene on various supports
are not studied much but their effect was predicted by Klemens [218]. Table 4.3 shows the compar-
ative thermal conductivity values for graphene determined by various methods. A new approach of
determining thermal conductivity of a thin atomic layer of graphene is shown in Fig. 4.13 [219]. In this
method a suspended graphene layer is heated by laser light (488 nm), the heat propagated laterally
towards the sinks on side of the corner of the akes. The temperature change was determined by mea-
suring the shift in the graphene G peak using confocal micro-Raman spectroscopy which acts as a ther-
mometer. The thermal conductivity is affected by factors such as defects edge scattering [220] and
isotopic doping [221]. In general, all these factors are detrimental to the conductivity due to phonon
scattering at defect and phonons modes localization due to the doping.
Table 4.3
Thermal properties of graphene and graphene oxide based materials.
Method Material Thermal conductivity References
Confocal micro-Raman
spectroscopy
Single layer graphene 48405300 W/mK at RT [6]
Confocal micro-Raman
spectroscopy
Suspended graphene ake 41004800 W/mK at RT [219]
Thermal measurement method Single layer (suspended) 30005000 W/mK at RT (suspended) [222]
Thermal measurement method Single layer (on SiO
2
support)
600 W/mK at RT (on a silicon dioxide
support)
[222]
Electrical four-point
measurement
Reduced graphene oxide
ake
0.140.87 W/mK [223]
5. Chemically derived graphene: properties and applications
The pristine graphene has attracted a great deal of attention due to its unique electronic properties,
making them model systems for the observation of novel quantum phenomenon and building blocks
for future nano electronic devices. However, in practical point of view it is necessary, (i) to create
graphene nanostructures in large quantities and (ii) to integrate them at selected positions of the cir-
cuits with high yield. The solution processing provides an attractive approach to produce GO/RGO
sheets in large quantities at low cost. The easy processibility of GO/RGO and compatibility with var-
ious substrates make them an attractive candidate for high yield manufacturing of graphene based
electronic and optoelectronic devices such as eld effect transistors, chemical/bio sensors, organic so-
lar cells, and transparent electrodes in photovoltaic devices. This chapter summarizes the recent pro-
gress of GO/RGO in device applications and their properties.
5.1. Assembly of GO/RGO for device applications
It has been discussed in previous sections that GO and RGO can be synthesized in large quantities
through solution routes. Several approaches have been demonstrated in this regard which involve
drop cast [71,195], dip coating [224], spraying [196], spin coating [28,225228], LangmuirBlodgett
(LB) lm [36,229], and vacuum ltrations deposition [116,197,230]. The GO/RGO can be deposited
either on prefabricated electrode patterns or the electrodes can be dened after deposition of GO/
RGO. Using these processes, the devices using single layer, few layers (<10 nm) and thin lm have
been fabricated. For single layer and few layer devices, the throughput can be low since the processes
involve random placement of GO/RGO sheets. On the other hand, thin lm deposition can improve the
throughput. The drop cast, dip coating, and spray depositions on the substrate are convenient ways to
build GO/RGO devices, however, these techniques often result in non-uniform lm thickness on sub-
strate, due to aggregation of GO/RGO sheets. In spin coating, the thickness of layer can be tuned by
varying the concentration of the graphene dispersion and can result in minimal wrinkling. LB assem-
bly exploits the electrostatic repulsive forces between the individual GO sheets [36,229]. In brief, a
suspension of GO in a mixture of water and methanol carefully spreads over the water surface to ob-
tain the oating GO sheets trapped at the water/air interface. The oating GO lm is then deposited
onto a substrate as it is slowly raised from the solution. The aggregation of RGO sheets is prevented
by repulsive negative charge between the ionized edge functional groups of the sheets leading to a
uniform monolayer thick lm. This process can be repeated to make layer by layer deposition of
RGO lm of desired thickness. The ltration technique involves ltration of the suspension containing
the GO sheets through porous membrane [116,197,230]. The as-ltered GO sheets are then transferred
from the lter membrane to the substrate surface. The thickness of each graphene oxide paper sample
can be controlled by adjusting the volume of the colloidal GO suspension. This technique allows good
Fig. 4.13. (a) High-resolution scanning electron microscopy image of the suspended graphene akes. (b) Schematic of the
experimental setup for measuring the thermal conductivity of graphene. (Reproduced with permission from [219].)
control of uniform lm thickness on the substrate, however sometimes it can produce winkling of the
sheets. All the above mentioned assembly techniques can provide a convenient route to produce large
quantity RGO thin lm devices. However, in these techniques, if many circuits need to be made on the
wafer, additional materials outside of the electrode area need to be etched away, which increases the
processing steps.
Techniques that promote directed assembly at the selected position of the circuit can be advanta-
geous in this regard. Several studies have been shown for large scale assembly of GO/RGO devices at
selected positions of the circuit. Molecular template is one of the method for producing the directed
assembly of RGO based devices [231] using single layer as well as few layers. The concept of this tech-
nique is to transfer individual GO sheets from solution on to the predened patterned areas (often
referred as templates). The molecular templates are generated using micro-contact printing on
mica-peeled gold substrates as shown in Fig. 5.1a. Then such templates are immersed into GO solu-
tion. The electrostatic interactions between the template and GO sheets make the sheets to assemble
onto the template. The distribution of the GO sheets depends on the surface functionalization, back-
ground passivation, pH, immersion time, and the concentration of the GO dispersion The longer
immersion time generates more GO sheets on the templates (Fig. 5.1b). After GO sheets attaching
to the template, they can be treated either by hydrazine vapor or high temperature thermal annealing
to produce conducting RGO devices. Another convenient route to assemble large scale GO/RGO device
between prefabricated electrodes is via dielectrophoresis (DEP) [232240]. In this technique, an AC
voltage gives rise to a time averaged DEP force given by
F
DEP
= (p \)E (5:1)
Fig. 5.1. (A) A scheme of the templating process that shows the formation of the amino-terminated template on mica-peeled
gold, followed by immersion in a dispersion of graphite oxide to the reduction of the captured GO to form reduced graphite
oxide. (B) (14) Friction images of an 11-amino-1-undecanethiol (AUT)-patterned Au following 5 s (1), 30 s (2), 10 min (3), and
17 h (4) immersion times in GO dispersions, respectively. All images are 10 lm wide and show the bright (high friction) AUT
being covered with the lower friction GO [231]. (C) A cartoon of DEP setup. (D) Demonstration of high yield assembly Top: SEM
of an active area of a chip containing after DEP assembly of the RGO sheets. The chip contained 18 pairs of electrodes numbered
as E1E18. The gap size between each electrode pairs is 500 nm. Bottom: Magnied SEM images of all 18 electrode pairs for a
clearer picture. (Reproduced with permission from [235].)
where p is the induced dipole moment of the polarizable object and E is the non-uniform electric eld.
The strong electric eld gradient causes the GO/RGO sheets to align along the eld direction and to
assemble between the pre-fabricated sources and drain electrodes as shown in schematic of the setup
in Fig. 5.1c. DEP assembly of GO and RGO has been demonstrated by several groups which shows the
device yield is almost 100% [232240]. Fig. 5.1d shows the actual assembly of RGO sheets prepared by
Joung et al. [235].
5.2. Electrical characterization of GO/RGO sheet
The electrical characterization of the as-synthesized GO and RGO, both in chemical and thermal
route has been conducted using two-probe current (I)voltage (V) measurement as well as three ter-
minal eld effect transistor (FET) devices. As-fabricated GO is found to be insulating due to the pres-
ence of oxidized functional group. The controlled reduction (thermal or chemical) process results in
the removal of oxidized group causing GO to be electrically conducting. Although many of the oxidized
groups were removed during reduction process, remaining oxidized groups still limits electron trans-
port properties of the RGO sheets. The transport properties can be characterized by comparing the
conductivity values and eld effect mobility values for various reduction techniques.
The conductivity values can be calculated using the following expression:
r = (Rt)
1
(5:2)
where R is the total resistance and t is the sheets thickness. It has been shown that the conductivity of
RGO can vary from 0.05 to 500 S/cm depending on the degree of reduction which is related to the ratio
of the graphitic regions (sp
2
) to oxidized regions (sp
3
). Single or few layered RGO sheets (<5 nm) has
been studied in this regard. For example, Jung et al. compared conductivity with different reduction
processes including thermal, chemical, and a combined chemical/thermal approach [241]. The sam-
ples treated by a combined chemical/thermal reduction displays ve times higher conductivity
(~300 S/m) compared to the chemical or thermal reduction (Fig. 5.2a). In another work, Mattevi
et al. investigated the role of graphitic domain (sp
2
) fraction on the conductivity of RGO sheets using
thermal reduction process (Fig. 5.2b) [116]. It can be concluded that the conductivity can be tuned
Fig. 5.2. (a) Conductivity of single sheets of graphene oxide reduced by three different reduction methods: red, thermal
reduction; blue, chemical reduction; purple, combined chemical/thermal reduction [241]. (b) Conductivity of thermally reduced
GO as a function of the sp
2
carbon fraction. The vertical dashed line indicates the percolation threshold at sp
2
fraction of ~0.6.
Fitting of the experimental data reveals two different regimes for electrical transport with sp
2
fraction. Tunneling and/or
hopping (straight dashed line) mechanisms dominate at sp
2
fractions below 0.6 while percolation amongst the sp
2
clusters
dominates above the percolation threshold. The 100% sp
2
materials are polycrystalline (PC) graphite and graphene. The two
conductivity values are for doped by gating (upper triangle) and intrinsic graphene (lower triangle). (Reproduced with
permission from [116].)
over 12 orders of magnitude by tuning the sp
2
fraction through oxidation and reduction process. It can
be also seen from here that if sp
2
fraction can be increased to more than 0.9, the conductivity of RGO
sheets can be close to that of pristine graphene [116]. For RGO thin lm (>5 nm), the thermal reduc-
tion is effective for only top few layers of GO lm [197]. This indicates that chemical reduction process
may be more effective for achieving high electrical conductivity of RGO thin lm followed by thermal
treatments.
Another important characteristic of a semiconductor device is its eld effect mobility (l). The l can
be calculated from IV
g
curve with constant bias voltage using the formula:
l = (L=WC
ox
V)=(DI=DV
g
) (5:3)
where L is channel length, W is channel width and C
ox
is capacitance per unit area of the gate insulator.
Gomez-Navarro et al. rst reported the ambipolar eld effect transistor (FET) device using single layer
RGO with hole and electron mobilities of 2 and 0.5 cm
2
/Vs [195]. Eda et al. also reported hole and elec-
tron mobilites of 1 cm
2
/Vs and 0.2 cm
2
/Vs respectively in their single layer RGO FET [197]. In both of
these cases, the measurements were done at room temperature at ambient condition and the device
showed prominent p-type behavior. However, when measured at low temperature in vacuum, the de-
vice showed more symmetric V shape ambipolar characteristics. This suggests that dominant p-type
behavior in air was due to O
2
and moisture. Indeed, Jung et al. demonstrated high sensitiveness of the
GO to air by measuring FET properties [242]. When the sample was exposed to air, there was a large
hysteresis effect on p-type FET. However, when the measurement was performed in vacuum, the hys-
teresis disappeared and FET showed more V shape ambipolar behavior as shown in Fig. 5.3a. The
moisture effect can also be mitigated by annealing in Ar and H
2
atmosphere [235]. The large scale
assembled chemically reduced GO FET via DEP showed high yield FETs with holes and electrons
mobility of 4 and 1.5 cm
2
/Vs respectively [235]. This study also found that the dominant p-type
behavior can be removed upon mild thermal annealing. In addition to the chemical reduction, high
temperature thermal annealing (~1000 C) in presence of hydrazine is also a common technique used
by several groups which shows electrical conductivity of ~100 S/cm and mobilities ~1.2 for holes and
0.6 cm
2
/Vs for electrons [87]. However, the high temperature is often results in a larger amount of
topological defects [241,243]. Some recent reports on larger sized RGO sheets claimed to have higher
mobilities (1004000 cm
2
/Vs) than discussed above. Although, such high mobility was claimed due to
larger sheet size, however, a closer examination revealed sp
2
/sp
3
ratio and domain size (calculated
from Raman) to be of the same order as reported by other authors [244,245]. In addition to pure
RGO, Eda et al. showed that RGO-polystyrene (PS) composite can also show ambipolar FET device with
hole and electron mobilities of 0.7 and 0.2 cm
2
/Vs respectively [246]. The solution of GO in an organic
Fig. 5.3. (a) Resistance-gate voltage dependence representative RGO device in vacuum and after exposure to air (Reproduced
with permission from [242]). (b) Normalized channel conductance as a function of gate voltage for ~1.5, ~2.5, and ~4 layer RGO
lm at T = 4.2 K. The channel conductance (G(V
g
)) is normalized to its minimum value (G
min
), which occurs at the charge
neutrality point. (Reproduced with permission from [247].)
solvent paved the way to produce good dispersion in the PS matrix. The chemical reduction of the GO
using hydrazine in the presence of the PS avoids aggregation of the GO sheets in solution.
The thin lm (>5 nm) of RGO sheets showed slightly different FET properties compared to single
layer devices. Fig. 5.3b shows G
max
/G
min
for FET with different layers of RGO, where G
max
/G
min
is the
ratio between maximum and minimum conductivities respectively. The single layer RGO shows high-
er G
max
/G
min
compared to multilayered devices consistent with what has been reported for single layer
and multilayered graphene [247].
It is clear from the above discussions that the conductivity and mobility values of RGO are low
compared to that of pristine graphene (200,000 cm
2
/Vs). There are several reasons for poor perfor-
mance in RGO sheets: (1) the charge percolation is limited by disconnected network of p delocalized
tracks in the sheets due to remaining oxidized functional groups and (2) defects in the sheets, mainly
produced during reduction process. The trapped state retards charge carrier dissociation on defect
sites. Therefore, controlling the initial stages of reduction and oxidation of RGO sheets are very impor-
tant to move forward in producing high quality RGO devices.
5.3. Defect density in chemically derived graphene
As discussed above, the electrical conductivity and eld effect mobility of RGO based device is not
as good as pristine graphene. Structural characterization and theoretical calculation show that this is
due to the large number of defects present in the RGO sheet. Typically 60% of the area contains gra-
phitic domains with size varying from 3 to 10 nm. The rest lies in the structural disorder of oxygen
groups and topological defects. The systematic studies indicate that increased charge percolation oc-
curs with increasing sp
2
(graphitic regime) fraction which leads to the increase in the conductivity of
the materials [116].
The degree of orderness in the materials can be identied by Raman spectroscopy where the G
band (sp
2
) corresponds to the ordered structure and the D band to the disordered structure (sp
3
) of
the material. All RGO lms exhibit the D-band peak at ~1346 cm
1
and the G-band peak at
~1604 cm
1
(Fig. 5.4a) [248]. The broader D-band with higher relative intensity compared to that
of G-band indicates the higher disorderness in the RGO sheets. This relatively higher intensity of
the D peak in RGO shows 23 orders of magnitude higher than that of pristine graphene. In addition,
the ratio of I
2D
:I
G
is correlated with the hole mobility of the RGO devices. The labels M0.4, M1.0, M4.6,
M6.9, and M12 represent the devices with mobility ratio (I
2D
:I
G
, cm
2
/Vs) of 0.4/0.13, 1.0/0.22, 4.6/0.26,
6.9/0.25, and 12/0.34, respectively in Fig. 5.4a. This shows that when the I
2D
:I
G
ratio increases, the
mobility also increases. The average domain size of graphene (sp
2
) was estimated by the intensity
of D and G bands of the RGO sheets using empirical Tunistra-Koening relation [119] and was found
Fig. 5.4. (a) Raman spectra for ve selected transistor devices with various values of effective mobility. The labels M0.4, M1.0,
M4.6, M6.9, and M12 represent the devices with mobility 0.4, 1.0, 4.6, 6.9, and 12 cm
2
/Vs, respectively [248]. (b) Current density
(J) vs. V plotted in a loglog scale for different temperatures. The symbols are the experimental points while the solid lines are
ts to J V
m
. Two regions are separated by V
th
. For V < V
th
, m = 1 and the conduction is Ohmic. V > V
th
the conduction is due to
SCLC with exponentially distributed trap states. (c) Extrapolation of the JV curves at low temperatures plotted in loglog scale
for device A. From this plot, we determine the temperature independent crossover voltage V
c
= 10 V was determined.
to be about 2.56 nm [116,195,238,239]. This calculated domain sizes of graphitic domain size are in
good agreement with the domain size obtained from the TEM study (see Fig. 3.10 in Section 3).
The XPS also characterizes the defects in RGO/GO and provides the qualitative information of the
defects. Ruoffs group reported that the nonconjugated sp
3
carbon in RGO sheets mostly consists of de-
fects. Therefore, in XPS the ratio of C
1s
to O
1s
peak related to the estimation of the defect density in
RGO sheets. The higher ratio values corresponds to better reduction with lower defects [116].
Quantitative information about the defects can be obtained from electron transport measurements.
It has been shown by Joung et al. that the defects in RGO sheets leads to the space charge limited con-
duction (SCLC) [238]. SCLC occurs in low mobility semiconductor,s when injected charge density ex-
ceeds the intrinsic free carrier density of the material. Analysis of the current density (J)voltage (V)
characteristics using the SCLC model is one of the experimental methods for the detection of charge
trap states in disordered semiconductors. In the absence of any trap states or when trap states do
not dominate the transport, the JV characteristics can be described by
J = 9e
0
e
r
lV
2
=8d
3
(5:4)
where e
0
is the permittivity of free space, e
r
the dielectric constant of the RGO, l is the charge carrier
mobility, d is the spacing between electrodes. Whereas, in presence of trap states those are exponen-
tially distributed in energy, the JV relationship is given by
J = lN
v
=q
l1
_ _
(2l 1)=(l 1) ( )
1=l
ee
0
=N
t
( ) l=(l 1) ( ) ( )
l
V
l1
=d
2l1
_ _
(5:5)
where l is an exponent and should be greater than 1, q is the electronic charge, N
v
is effective density of
states, and N
t
is the trap density. By plotting J and V in loglog scale one can determine the value of
exponent m. For trap free (TF-SCLC) regime, m = 2 while for exponentially distributed trap (EDT-SCLC)
regime m = l + 1 > 2. Fig. 5.4b shows temperature dependent current density (J)voltage (V) character-
istics curve of a DEP assembled RGO device. The solid lines are t to J V
m
[249,250]. At low bias, the
conduction is Ohmic with m = 1, while at higher bias voltages m increases from 2 to 3 with reducing
temperature, signifys space charge limited conduction (SCLC) with a transition from trap free SCLC re-
gime at room temperature to exponentially distributed trap SCLC regime at low temperatures. An
exponential distribution of trap in energies is expected from the originated surface defects and struc-
tural disorders. Defect density can be calculated by extrapolating JV curve to nd a temperature inde-
pendent critical voltage V
c
which is related to the defect density through V
c
= qN
t
d
2
/2e
r
e
o
, where N
t
is
defect density, d is the spacing between electrodes, e
r
dielectric constant of RGO, and e
o
is permittivity.
The V
c
for RGO device was about 10 V as shown in Fig. 5.4c, from which one obtain an average trap
density of ~1.75 10
16
cm
3
. The large trap density indicates the presence of large number of defects
and structural disorder, which cause lower transport properties.
5.4. RGO as graphene quantum dot array: Coulomb blockade effect
The structural characterization through TEM, XPS, scanning tunneling Microscopy (STM) and Ra-
man spectra show that the RGO consists of ordered graphitic (nanocrystalline) regions surrounded
by areas of oxidized carbon atoms, point defects, and topological defects [116,117,120,195,251]. The
graphitic regions were estimated to be of 310 nm from the TEM, STM and Raman studies
[116,117,120,195,251]. Optical studies of RGO also showed blue light emission [212] and infrared
absorption [114,252], determined by the size, shape and edge conguration sp
2
graphitic domain.
All these studies suggest that RGO can be modeled as a two-dimensional array of graphene quantum
dots (GQD) [239], where graphitic domains act like QDs while oxidized domain behave like tunnel bar-
riers. This has been veried by Joung et al., in the low temperature electrical conduction in few layers
RGO. Fig. 5.5a shows currentvoltage (IV) characteristics of one of their device. As the temperature is
lowered to less than 15 K, a complete suppression of the current below a threshold voltage (V
t
) was
observed. Such current suppression was explained due to Coulomb blockade (CB) of charges, as at
low temperatures there is not enough energy for the charges to overcome Coulomb charging energies
of the QD array formed by graphitic domains. It is expected from theory that for a QD array, the IV
curves should follow a relation I ((V V
t
)/V
t
))
a
for V > V
t
, where a is the scaling exponent that
depends on the dimensionality of the arrays [253]. This is also shown to be the case in RGO (Fig. 5.5b)
where a was estimated to be ~3.4. For a two-dimensional array of nanoparticles, the theoretical value
of a was predicted as 1.6 while numerical simulations yielded as 2.0 [253]. However, experimental
studies of two dimensional metal nanocrystal arrays, the exponent a was reported to vary from 2
to 2.5 which depends on size distribution, while for quasi 2D system with multilayered nanoparticles
the value was 2.63.0 [254258]. Therefore, the experimental results in RGO which showed a ~ 3.4 is
higher than 2D array system. However, recent experimental and computer simulations involve gold
nanoparticles array with strong topological inhomogeneity show large scaling exponents a ~ 4.0
[259,260]. Since RGO has a lot of topological defects which came from oxidation and reduction pro-
cess, the high value of a is in agreement with charge transport in an inhomogeneous quasi 2D QD ar-
ray network. Fig. 5.5c shows a schematic of RGO as a GQD array with strong topological hetrogeneity.
The light gray areas represent GQDs, the white regions represent oxidized carbon groups and topolog-
ical defects. This shows that the GQDs are isolated (or localized) by oxidized carbon atoms and topo-
logical defects and there is strong size distribution of GQDs. The lines between GQDs indicate tunnel
barriers.
5.5. Hopping conduction in RGO
Since RGO contains a lot of disorder consisting of localized graphene domains along with oxidized
areas, the low temperature resistance measurements show hopping transport phenomenon. Both
Mott variable range hopping (VRH) [261,262] and Efrosshklovskii VRH [239] have been reported
in RGO.
5.5.1. Mott variable range hopping
Mott described that at very low temperatures, when there is not enough thermal energy for the
charge to go from valance band to conduction band, the charge conduction occurs via hopping among
-200
-100
0
100
200
4.2 K
I

(
p
A
)
V (V)
30 K
-0.5 0.0 0.5
0.1 1
10
100
1000
10000 4.2 K
I

(
p
A
)
(V-V
t
) / V
t
15 K
5
a
b
c
Fig. 5.5. (a) Current(I)voltage(V) characteristics of a representative RGO device at temperatures 30, 25, 20, 15, 10 and 4.2 K.
Below 15 K, the current is zero for V < V
t
due to coulomb blockade of charges. (b) I vs. (V V
t
)/V
t
curves plotted in a loglog
scale. Slope of the curves gives the value of exponent a = 3.1, 3.3, and 3.4 at 4.2 K, 10 K, and 15 K respectively. (c) Schematic of
RGO as GQD array. The light gray areas represent GQDs, the white regions represent oxidized carbon groups and topological
defects. The lines between GQDs represent tunnel barriers. (Reproduced with permission from [239].)
the localized states [263]. When the energy is low, the carrier will hop longer distance. This is called
variable range hopping. According to Mott, the conductivity of such a system can be described as,
r = Aexp
T
0
T
1=(d1)
_ _
(5:6)
where A is a constant, T
0
is critical temperature and d is the dimensionality of the system. So for a 2D
system, the relation became r ~ T
1/3
. However, it should be noted that in Mott VRH, the Coulomb
interaction among localized states is neglected and there is no minimum energy needed for the car-
riers to hop. Since, RGO has a lot of defects which localizes charge carriers, it is expected that low tem-
perature transport properties of the RGO can be explained using VRH model.
Kern and coworkers, rst applied Mott VRH model to describe the temperature dependence of cur-
rent for various back-gate voltages [261]. They showed that lnI followed linear relation with T
1/3
as
shown in Fig. 5.6a. From the slope of these curves, the obtained values for T
0
which in 2D is given by
T
0
=
3
N(E
F
)k
B
L
2
i
_ _1
3
(5:7)
where L is the localized length and N(E
F
) is the density of state near the Fermi level.
Applying negative V
g
leads to the lower value of T
0
(same as B) indicate higher localization length
(Fig. 5.6b). However, the values of T
0
for positive gate voltages are considerably larger than those for
the negative gate voltages, indicating shorter localization lengths (L
i
). Eda et al. also reported Mott
VRH model for their study of transport properties of RGO with various reduction process with temper-
ature ranging from 78 to 300 K (Fig. 5.6c) [262]. Lightly reduced GO device (10 min and 30 min reduc-
tion) showed linear trend in whole temperature ranges, while well reduced GO devices (16 h, HG-A,
and HG-B) showed transition from Mott VRH (T
1/3
) to Arrhenius-type (T
1
) hopping above 240 K.
Fig. 5.6. (a) Natural logarithm of the measured current I vs. T
1/3
tted to representing 2D variable range hopping in parallel
with a temperature-independent term, for different values of the gate voltage V
g
as indicated, for bias voltages. (b) Parameters
for the ts in gure (a), plotted as a function of gate voltage V
g
for different values of bias voltage V
ds
(Hopping parameter B)
[261]. (c) Temperature and electric eld dependence of the RGO device properties. Minimum conductivity r
min
of RGO as a
function of T
1/3
. The linear ts show agreement with the VRH transport. For samples 16 h, HG-A, and HG-B, deviation to
thermally activated transport is observed at temperatures indicated by the arrows. (Reproduced with permission from [262].)
5.5.2. EfrosShklovskii (ES) VRH
Efros and Shklovskii [264266] pointed out that for certain systems, the Coulomb energy between
localized states near the Fermi level must be overcome for a carrier to hop from one site to another. In
other words, there is a Coulomb gap near the Fermi level where the density of states vanishes. Under
such circumstance, the conductivity is independent of dimension and should follow, ES VRH
R = Aexp
T
0
T
_ _1
2
(5:8)
where T
0
is a constant related to the disorderness of the material. And the T
0
is described as
T
0
=
2:8e
2
4pee
0
kn
_ _
(5:9)
for a 2D system, where e dielectric constant of RGO and n is localized length [264266]. ES VRH model
was successfully applied for granular metals and QD array systems with signicant size and structural
disorders.
Joung et al. noted that the structural information strongly suggests that RGO can be modeled as an
array of QDs with signicant size and structural disorder (polydispersed QD array), which has been
veried in low temperature IV curve [239]. In addition, recent study of individual 10 nm sized graph-
ene quantum dots show room temperature Coulomb blockade (CB) [162,267]. This suggests that Cou-
lomb interaction should be important in the transport study of RGO. Moreover, it was also noted that
for a polydisperesed QD array, the temperature dependent resistance data should follow ES VRH. This
was experimentally veried by obtaining resistance data (calculated from the linear part of the IV
curve), which vary by three orders of magnitude for temperature ranges of 30295 K. Since, tting
the resistance data with different behavior can be tricky and the same data can often t with several
behaviors (such as T
1
, T
1/2
, and T
1/3
), the behavior was determined by considering a generalized
formula R(T) = R
0
exp(T
0
/T)
p
and then calculating the value of p from lnW = A plnT, where
W = @lnR(T)/@ lnT = p(T
0
/T)
p
is the reduced activation energy and A is a constant [268,269].
Fig. 5.7a shows lnW plot vs. lnT. From the slope (indicated by red line) of this curve, p = 0.48 0.05
was obtained over the whole temperature range which is consistent with ES VRH. From the plot of
R verses T
1/2
in a semi-log scale (Fig. 5.7b) the value of T
0
= 4200 K was calculated. The localization
length n was calculated to be 3.5 nm which is comparable to the graphitic domain size suggesting
strong localization of wave functions inside each GQDs.
5.6. Application of RGO for photodetector, phototransistor and emitter
It is clear from different characterization and transport studies that RGO contains a lot of defects
and they do not have the same extraordinary electrical properties as pristine grapheme. However,
Fig. 5.7. Temperature dependence of the RGO device properties. (a) Reduced activation energy W = @lnR(T)/@lnT = p(T
0
/T)
p
plotted vs. T on a loglog scale. From the slope of this plot we obtained p = 0.48 0.05 corresponding to the ES VRH. For a
comparison we also show lines with p = 1 (activated hopping) and p = 1/3 (Mott VRH). (b) R in log scale as a function of T
1/2
.
From the slope, T
0
= 4200 K was obtained [239].
considering their high throughput processing ability, they may nd many useful applications where
extraordinary electrical characteristics are not required including sensors, transparent electrodes, so-
lar cells, eld emitters, etc. In addition, their graphitic domain nature may also be of great use for opto-
electronic applications.
Photoconductivity of bulk RGO thin lm has been studied using various intensities of light, external
eld, and photon energies [270]. The study showed higher photocurrent under same photon energy
with the increase of incident light intensity and external electric eld. This indicates that the charge
carrier generation is inuenced by the number of photons and the external eld intensity in RGO
sheets. Higher photoconductivity has also been observed with higher photon energy under same
intensity and electric eld. The time dependent photocurrent decay results show extra time required
to recombine charge carriers upon increase of external eld and light intensity. It can be concluded
that the RGO lm generates more charge carriers per unit volume upon irradiation of higher photon
energy. In comparison with SWNT, the RGO lm shows high photocurrent generation efciency [270].
Position dependent RGO thin lm photo-detector has been reported by using near-infrared (wave
length of ~800 nm) light [252]. Fig. 5.8a shows a schematic diagram of the device and electron trans-
port measurements setup. L corresponds to illumination on the left electrode/lm interface, R corre-
sponds to illumination on the right electrode/lm interface, and M corresponds to the middle position
of the lm. Fig. 5.8b shows the photocurrent with different laser spot positions. The photocurrent
either increases and decreases or remains almost zero depending on the position of the laser spot with
respect to the electrodes. In detail, the IV curves for position M and in dark lie on top of the one an-
other and pass directly through the origin. Whereas, when the light illuminated at position L and R, the
IV curve is shifted above or below the origin respectively. A large enhancement of photocurrent as
well as a nite photo-voltage at the interface indicates that there is an existence of locally generated
electric eld at the metal-RGO lm interface. This mechanism of the local electric eld generation was
explained using Schottky barrier (SB) model. In schematic diagram (Fig. 5.8c), the black lled and open
circles inside the dotted oval region represent the photogenerated excitons (bound electronhole pair)
due to absorption of NIR source (curved red arrow). Solid line is the potential variation within the
graphene channel and dashed lines are the Fermi levels (E
F
) of the two electrodes. When NIR is illu-
minated on the left electrode/RGO lm interface, excitons are generated and dissociated into free
charge carriers at the interface. Since RGO thin lm has a lot of defects, it will also help in dissociation
of excitons into free carriers. Some of the free carriers (holes) might have sufcient energy to over-
come the SB and enter into the metal electrode leaving the electron in the lm. This causes a hole
electron separation at the interface creating a positive photo-voltage. In addition, the time constant
of the dynamic photo response was ~2.5 s which is much larger compared to the single sheets of pris-
tine graphene, possibly due to the disorder from the chemical synthesis and interconnection of sheets.
RGO FET phototransistor also has been studied based on their energy band gap values [271]. In this
case, RGO FET, in which few layer RGO sheets serves as the semiconducting channel and is designed to
conduct positive and negative charge carriers (holes and electrons, respectively). The band gap, which
Fig. 5.8. (a) Schematic diagram of the device and electron transport measurement setup. L, M, and R are three different
positions of NIR illumination. (b) Currentvoltage characteristics of the device at three different illumination positions. (L, R,
and M) and under dark condition. (c) A cartoon for photo-voltage generation at the metallic electrode/RGO interface.
ranges from 2.2 eV to 0.5 eV, can be made tunable by reduction treatments. These results also indicate
that the photosensitivity is strongly related to the number of oxidized functional group. The rough
estimation of the photosensitivity of RGO FET was calculated to be around 0.85 A W, three orders low-
er than that of the pristine graphene [272].
In addition to RGO thin lm, the optical properties of individual GO/RGO sheet was also studied.
Semiconducting GO/RGO shows absorption from ultraviolet (UV) to infrared (IR), wavelength of from
10 to 2500 nm [97,114,209,212,273]. Acik et al. reported that the single layer GO and RGO have dif-
ferent response of infrared absorption band due to their different functional groups on the edge region
(Fig. 5.9a and b) [114]. If the GO is well reduced, oxygen-containing functionalized groups get re-
moved and the infrared spectra of RGO become strong due to the in-phase electron band population
with mobile electrons localized at the edge resulting in stronger absorption. In another study, Eda
et al. [212] demonstrated that RGO thin lms emitted near-UV blue light, when excited with UV radi-
ation. The blue photoluminescence (PL) was observed for the RGO sheets. By appropriately controlling
the reduction process, the PL intensity increased by a factor of 10 compared to the as-synthesized GO
sheets. The results indicated that RGO offers tunable optoelectronic device via controlling the reduc-
tion process through chemical and/or thermal route.
5.7. Graphene thin lm as transparent electrodes
It has been demonstrated that thin lm (<30 nm) of RGO is semi-transparent to visible and NIR re-
gion while thick lms are opaque. The transmittance and conductivity of the GO/RGO lm can be
tuned by tuning the thickness of the lm and the degree of reduction [28]. Fig. 5.10 shows how the
transparency of RGO varies with lm thickness. The leftmost lm is 9 nm thick GO while rest of the
lms are RGO (annealed in 1100 C for 3 h) with thickness 6, 8, 27 and 41 nm (from left to right).
As it can be seen that, as the lm gets thicker, the transmittance gets reduced. While the conductivity
of the RGO thin lm increases with the degree of reduction and transmittance decrease. Therefore, the
optimization of lm thickness and reduction parameters is the key in achieving high performance
transparent and conducting RGO thin lm. Table 5.1 summarizes the recent progress on optoelec-
tronic properties of graphene-based thin lms in terms of their reduction and fabrication methods.
Optical and mechanical properties of RGO thin lm were also studied on exible substrates. For
example, Yin et al. [278] studied the effect bending on the properties of RGO for lm thickness of
421 nm. After applying tensile stress (tensile strain of 2.9%) on the device, the performance was mon-
itored by resistance change with the number of bending cycles. The device showed an excellence sta-
bility of resistance, even when bending cycles reached about 1000 times.
Fig. 5.9. (a) Transmission infrared-absorbance spectrum of GO-1L. (b) Transmission infrared absorption spectra of thermally
reduced GO-1L after annealing at 850 C. (Reproduced with permission from [114].)
Due to their transparency, conducting and exible nature, RGO thin lm is considered to be a
promising electrode material for organic electronic and optoelectronic applications. Presently, indium
doped tin oxide (ITO) is widely used as transparent and conducting electrodes in optoelectronic appli-
cation. However, the ITO based materials are expensive [279] and their limitation of mechanical ex-
ibilities [280] makes them un-attractive for exible display and solar cell applications. In this respect,
RGO electrodes provide several advantages; (i) possibilities on one phase reaction without additional
surfactant due to water soluble properties, (ii) the homogeneity and composition of the lms are sim-
ply determined by the composition of the parent suspension and surface modication of the substrate,
(iii) relatively inexpensive starting materials, and (iv) low temperature and high throughput process-
ing. In addition, the work function of RGO (4.24.6 eV) matches with the HOMO level of most of the
organic materials, and pp interaction exists between RGO and organic material [276,278].
Several research groups successfully used RGO electrode for the fabrication of organic light emit-
ting diodes (OLED) and solar cells. Efcient RGO-based OLEDs have been rst demonstrated by Wu
Table 5.1
Progress in graphene-based transparent electrodes and their properties.
Materials Reduction Fabrication
method
Film
thickness
Sheet
resistanc
(X/square)
Wave
length
(nm)
Transmittance
(%)
References
RGO Hydrazine
solution/
annealing
Spray coating ~1 nm 20 M 6001000 96 [194]
RGO Hydrazine vapor/
annealing
Vacuum
ltration
~3 nm 0.16 M 550 90 [197]
RGO Hydrazine vapor LB 13 nm 8 K 1000 83 [36]
RGO Hydrazine vapor/
annealing
Spin coating 1 10
2
10
3
4001800 80 [28]
RGO Acetylene-assisted
thermal
Spin coating 1.1 1425 500 70 [274]
RGO SOCl
2
treatment Vacuum
ltration
~10 nm 40 K 300900 64 [230]
RGO/SWNT Hydrazine
solution/
annealing
Spin coating 5 nm 240 UV visible 86 [275]
RGO Hydrazine
solution/
annealing
Spin coating 58 0.419 K 1000 6080 [276]
RGO (OLED
device)
Vacuum
annealing
Spin coating ~7 0.8 K 550 82 [277]
Fig. 5.10. Optical and electrical characterization of spin coated GO lms on quartz. (A) Photograph of an unreduced (leftmost)
and a series of high-temperature reduced GO lms of increasing thickness. Black scale bar is 1 cm. (B) Optical transmittance
spectra of the lms in (A) with the lm thickness indicated. (Reproduced with permission from [28].)
et al. [277]. The RGO-based OLED performance nearly matches with that of the ITO based device, even
though higher resistance (800X/square) and different work function of the RGO anodes. Wang et al.
reported that RGO lms can be employed for fabrication of dye-sensitized solar cells [224]. In this
application, Spiro-OMeTAD was used as a hole transport material, and porous TiO
2
used for electron
transport materials. The solar cell was fabricated using RGO as an anode and Au as cathode (Fig. 5.11a).
Fig. 5.11b shows the energy level diagram of a RGO (4.42 eV)/TiO
2
/dye/spiro-OMeTAD/Au (5.0 eV) de-
vice. The electrons are rst injected from the excited state of the dye into the lowest unoccupied
molecular orbital (LUMO) level of TiO
2
and then reached the RGO electrode via a percolation mecha-
nism inside the porous TiO
2
structure. Meanwhile, the photo-oxidized dyes are regenerated by the
spiro-OMeTAD hole conducting molecules (highest occupied molecular orbital (HOMO)) and then hole
injecte into Au cathode. Fig. 5.11c shows IV curve of the solar cell using RGO (black curve) as anode
and the comparison with uorine tin oxide (FTO) (red curve) electrode. Lower short-circuit current in
RGO electrode lead to low power conversion efciency (0.26%) compared to FTO (0.84%). This may be
due to the series of resistance of the device, lower transmittance of the materials (70.7%), and space
charge limited conduction on contact between active materials and RGO electrodes.
To overcome the contact problem, Yin et al. [276] suggested the use of hole transport interlayer
(ZnO nanorod) between RGO electrodes and active polymeric materials by electrochemical deposition.
The structures of the device was RGO/ZnO/P3HT/PEDOT:PSS/Au. The observed higher power conver-
sion efciency of 0.31% was demonstrated, compared to ZnO-free interlayer. As can be seen, the solar
cell fabricated with RGO electrode suffers from low efciency and more work is needed to make RGO
as an efcient electrode material.
5.8. Solar cell using GO/RGO
As mentioned in the previous section, RGO transparent electrodes can be used for solar cell elec-
trode. Several studies suggest that GO/RGO can also be used as hole transport layer as well as a part
of active material. In vertical bulk heterojuntion (BHJ) devices, both the donor and acceptor phases are
in the direct electrical contact with the cathode and anode electrodes. Most vertical organic solar cells
are composed of ITO/P3HT:PCBM/Al conguration. The polymeric donor and acceptor materials often
results in recombination of carriers and current leakage. To minimize such detrimental effects, elec-
tron blocking and hole transport layers (HTLs) are deposited on top of the transparent and conducting
ITO anode (Fig. 5.12a) [281]. The most common HTL in polymer solar cells is PEDOT:PSS. However,
PEDOT: PSS combination has been made from highly acidic aqueous suspensions that corrodes the
ITO at high temperatures and contributes water/moisture into the active layer, which leads poor de-
vice performance [281]. To overcome this issue, ITO/GO/P3HT:PCBM/Al conguration was introduced
for more efcient collection of holes and the band energies of the conguration are 4.44.5/4.9/
4.9:4.2/4.2 eV respectively. Interestingly the power efciency values are dependent on GO lm thin-
ness. GO thickness of 2 nm has shown best efciency performance compared to higher thickness
(>4 nm) due to the increase in serial resistance and the slightly lower transmittance of the lms with
thickness.
Fig. 5.11. (A) Illustration of dye-sensitized solar cell using graphene lm as electrode, the four layers from bottom to top are Au,
dye-sensitized heterojunction, compact TiO
2
, and graphene lm. (B) The energy level diagram of graphene/TiO
2
/dye/spiro-
OMeTAD/Au device. (C) IV curve of graphene-based cell (black) and the FTO-based cell (red), illuminated under AM solar light
(1 sun). (Reproduced with permission from [224].)
Other studies have shown the use of RGO as acceptor materials in the BHJ photovoltaic devices. For
instance, Liu et al. reported the organic solution-processable RGO as an acceptor material in organic
photovoltaic devices with P3HT as an electron-donor materials [282]. Fig. 5.12b shows a schematic
diagram of a solar cell using RGO as an active material. The RGO was well dispersed in P3HT with
10 wt% doping. The properties of the materials induce quenching of the photoluminescence (PL) of
the P3HT and lead to strong electron/energy transfer from the P3HT to the RGO. Power-conversion
efciency ~1.1% was achieved by using RGO as an active material. Table 5.2 shows the role of graph-
ene-based materials in solar cell and their photovoltaic properties including RGO as an active materi-
als as well as an electrode.
Fig. 5.12. (a) Schematic of the photovoltaic device structure consisting of the following: ITO/GO/P3HT:PCBM/Al. (b) Energy
level diagrams of the bottom electrode ITO, interlayer materials (PEDOT:PSS, GO), P3HT (donor), and PCBM (acceptor), and the
top electrode Al (Reproduced with permission from [281].) (c) The schematic chemical structure of SPF Graphene and P3HT. (d)
Schematic structure of the devices with the P3HT/SPF graphene thin lm as the active layer; ITO (~17 Xsq
1
)/PEDOT:PSS
(40 nm)/P3HT:SPFGraphene (100 nm)/LiF (1 nm)/Al (70 nm). (Reproduced with permission from [282].)
Table 5.2
GO/RGO in solar cell and their photovoltaic properties.
Active
material
Electrode
material
Reduction Deposition Thickness
(nm)
Fill
factor
(FF)
Power-
conversion
efciency
(%)
Role of
GO/RGO
References
P3HT:PCBM RGO/PET Thermal Spin
coating
16 0.32 0.78 Electrode [278]
TiO
2
lm
(RGO/TiO
2
composite
interlayer)
FTO Photocatalytically
by UV irradiation
Spin
coating
~15 N/A 5.26 Interfacial
layer
[283,284]
P3HT:graphene/
PEDOT:PSS
Al:LiF/
ITO
Thermal Spin
coating
100 with
P3HT
0.3 1.1 Acceptor [285]
PEDOT:PSS/P3HT/
ZnO nanorods
Au/RGO Hydrazine vapor/
thermal
Spin
coating
513 0.33 0.31 Electrode [276]
TiO
2
/dye/spiro-
OMeTAD
Au/RGO Thermal Dip
coating
10 0.36 0.84 Electrode [224]
5.9. Electrochemical sensors and biosensors
RGO is highly promising for electrochemical and biological sensors due to their different function-
alities on the edge [286288] which are very sensitive to change in chemical and biological environ-
ment. The responses have been analyzed by changes in conductivities, capacitances, and doping
effects on FETs made with RGO. Table 5.3 summarizes the sensors fabricated with RGO based-
materials.
Table 5.3
Graphene based chemical/biosensors.
Active
material
Reduction
method
Sensor type Analyte Measurement Detection
limits
References
RGO Thermal Gas NO
2
, NH
3
I vs. t ~100 ppm [289]
RGO + Pd Chemical Gas H
2
R vs. t N/A [290]
RGO Thermal Molecular HCN, CEES DMMP,
DDT
G vs. t ~ppb [226]
RGO Chemical Gas NO
2
, NH
3
, DNT R vs. T ~ppm [287]
RGO Chemical Electrochemical/
chemical
Electroactive compound
(potassium ferricyanide,
free bases of DNA),
neurotransmitter
(dopamine),
biological molecule
(ascorbic acid, uric
acid, acetaminophen)
I vs. E/V ~lM [291]
RGO + DNA Chemical Bio DNA, bacterium G ~single-
stranded
DNA,
molecule
~single
bacterium
[99]
RGO + Au Electrochemical Bio DNA I vs. E/V ~lM/L [292]
SDBS
functionalized
graphene
(RGO + HRP
a
)
Chemical Bio H
2
O
2
I vs. t ~30 lM [293]
RGO + Au
antibody
Thermal Bio R vs. t ~ng/ml [294]
GO N/A Bio DNA, Protein Fluorescence
intensity
change
~nM [295]
GO/MNO
2
N/A Bio H
2
O
2
I vs. E/V and
I vs. t
~lM [296]
RGO Thermal Gas NO
2
I vs. t ~ppm [297]
RGO Thermal,
chemical
Gas Water vapor R vs. t N/A [241]
RGO, RGO/
Naon,
Fatigued-
RGON
Chemical Bio Organo Phosphate
(OPH)
I vs. E/V
and I vs. t
1.39 lM,
0.137 lM,
0.360 lM
[298]
RGO (inkjet
printer)
Chemical Gas (Vapor) NO
2
, Cl
2
R vs. t ~ppm [299]
RGO Chemical Molecule
(Redox species)
Ru(NH
3
)
6
3+/2+
, Fe
(CN)
6
3/4
, Fe
3+/2+
I vs. E/V ~mM [300]
GO-CdTe
(NPs or QDs)
N/A Molecule Thiole-containing
compound
I vs. E/V ~lM [301]
Pt/RGO/SiC Thermal Gas H
2
I vs. t N/A [302]
a
HRP: Horseradish peroxide a type of enzyme, current (I), conductivity (G), resistance (R), potential E/V, time (t), ppm: part
per million, ppb: part per billion, SDBS: sodium dodecyl benzene sulphonate.
The sensitivity of the gas (or vapor phase) sensor depends on the charge carrier transfer on GO/RGO
surfaces caused by the adsorption of gases and vapors such as NO
2
, NH
3
, H
2
O, CO, dinitrotoluene
(DNT), Iodine, and ethanol and hydrazine hydrate [226,286288,303,304]. For example, the as-
synthesized GO transistor showed little response to chemical gases such as NO
2
[287]. In contrast,
the RGO was highly responsive to NO
2
and showed a typical p-type transistor behavior most likely
due to the recovery of many graphitic carbon atoms as active sites for NO
2
adsorption, which leads
to enhancing charge concentration. This leads to a decrease in resistance as a function of time
(Fig. 5.13a). The NH
3
makes n-type RGO transistor behaviors [289,297] since oxygen groups in RGO
were responsible for reactions with NH
3
and CAN bond [243]. This reaction decreases device conduc-
tivity (Fig. 5.13b) as a function of time [287].
High temperature (~1000 C) reduced GO shows faster chemoresistive (or resistance changes in
time) response than the hydrazine and low temperature reduction upon exposure to water vapor. This
is attributed to the presence of larger number of defects during the high temperature reduction pro-
cess [241]. These results indicate that the gaseous vapor may respond with both structural defects,
such as vacancies and/or small holes generated during reduction treatments, and functionalized
groups. Therefore, the sensitivity of RGO based sensors can be modied by controlling of reduction
treatment process [226,241].
Besides chemical (by hydrazine) and thermal reduction, the ascorbic acid (vitamin C) has also been
used as a mild and green reduction agent for RGO based chemical sensors [299]. The exible RGO
chemical sensor, using inkjet-printed lms of poly-(ethylene terephthalate) (PET) decorated RGO
sheets reversibly detect NO
2
and Cl
2
vapors at parts per billion level. This demonstrates the use of
ascorbic acid as an effective alternative to hydrazine to reduce GO into RGO.
Graphene based composite materials have been studied for gas sensor. For example, Pt/RGO/SiC
based devices for hydrogen gas sensing [302]. The electrical characteristics and hydrogen gas sensing
mechanism of the device were described by analyzing the effect of hydrogen interaction at the graph-
ene/SiC and Pt/graphene interfaces. High work function of Pt leads to a weak interaction energy at the
interface and preserves the electronic structure of RGO and electrons transfer from RGO to Pt to equil-
ibrate the Fermi level. Upon exposure of hydrogen gas, the carrier concentration is increased due to
dissociation of hydrogen molecules, which occurs on the Pt surface.
Several studies have been demonstrated RGO based biosensors as well. Mohanty and Berry [99]
reported on the fabrication and functioning of a novel RGO-based (i) single-bacterium device, (ii)
label-free DNA sensor, and (iii) bacterial DNA/protein and polyelectrolyte transistor. The bacteria/
RGO bio-device was highly sensitive with a single bacterium with a p-type FET property. The presence
of DNA on RGO increased both the conductivity and the mobility (Fig. 5.14 a and b) due to the inter-
action between the charged amine group and the RGO. Similarly, single-stranded DNA when tethered
on graphene, hybridizes with its complementary DNA strand which reversibly increases the hole den-
sity by 5.61 10
12
cm
2
. Also the bending-insensitive RGO FETs were able to detect the presence and
Fig. 5.13. (a) NO
2
detection and (b) NH
3
detection using a graphene lm. The sensor has gold electrodes and measurement used
a four wire method with 500 lA driving current. The NO
2
concentration is 5 ppm in dry nitrogen. (Reproduced with permission
from [287].)
dynamic cellular secretion of biomolecules. The specicity of the demonstrated detection is realized in
the dened biological context. The RGO FETs can also specically detect biomolecules with high sen-
sitivity using specic antibodies [305].
The fabrication and characterization of a highly sensitive and selective FET biosensor using Au NP-
antibody conjugates decorated with GO sheets have been reported [294]. The study demonstrates a
GO-based immuno-biosensor for detecting a rotavirus as a pathogen model. The sensor showed high
sensitivity and selectivity by using GO. CdTe/RGO composite also exhibited the chemicalbiological
sensing where graphene worked as an amplied electrogenerated chemiluminescence (ECL) of QDs
platform [301]. The study opens avenues for glutathione drug detection with graphene-based elec-
tronics glutathione drug detector or sensor.
6. Graphene based composites
Various polymers and nano particles (metal, metal oxide, semiconductor) composites have been
developed based on the unique properties of the graphene. Graphene possesses similar mechanical
properties as CNTs but has superior electrical and thermal properties, and larger surface area
(2620 m
2
/g) [306] because of its 2-dimensional crystal structure. The mechanical exfoliation of graph-
ite is not suitable for large scale production, while chemical oxidation of graphite into graphite oxide
offered an easy path to obtain graphene oxide in a large quantity that can be reduced chemically, elec-
trochemically [290] or thermally into graphene. The bulk production of GO and RGO has given oppor-
tunities to explore this at structure of carbon with polymer and nano particles in composites.
6.1. Graphenepolymer composites
Graphene and its derivatives as llers for polymer matrix composites have shown a great potential
for various important applications. In the past few years, researches have made successful attempts
for GO and graphenepolymer composites similar to CNT-based polymer composites. 2-D graphene
has better electrical, thermal and mechanical properties as well as higher aspect ratio and larger sur-
face area than other reinforced materials such as CNTs, bers of carbon and Kevlar. Its reinforcement
can offer exceptional properties in composites and applications in the eld of electronics, aerospace,
Fig. 5.14. (a) The conductivity of the p-type graphene-amine (GA) device increases upon attachment of a single bacterial cell on
the surface of GA (inset 1). LIVE/DEAD confocal microscopy test on the bacteria deposited on GA conrmed that most of the
bacteria were alive after the electrostatic deposition (inset 3). (A) alive and (D) dead. The LIVE/DEAD test conducted
immediately after the electrical measurements on the GA-gold-bacteria device (inset 2 and inset 4) showed that the bacterial
cells on GA atop silica remain alive, while the bacteria deposited on the GA atop gold electrodes die after electrical
measurements (inset 4 (right)). (b) DNA transistor: ss-DNA tethering on GO increases the conductivity of the device. Successive
hybridization and dehybridization of DNA on the G-DNA device results in completely reversible increase and restoration of
conductivity. Inset shows a G-DNA(ds) sheet with wrinkles and folds clearly visible. (Reproduced with permission from [99].)
automotive and green energy. The recent advancement in bulk synthesis processes of graphene and
RGO has generated great interest to incorporate such unique material into various polymer matrices.
Several challenges need to be overcome to realize graphene or graphene oxide based polymer
composites,
1. Functionalization of graphene sheets
2. Homogeneous dispersion of materials with minimal restacking
3. Effective mixing of graphene oxide and graphene with polymer
4. Understanding of the interfacial structure and properties
5. Controlling the folding, crumpling and bending of graphene materials
This section is devoted to only graphene and graphene oxidepolymer composites and highlights
their properties and applications.
Two potential approaches are commonly used to produce a single layer of graphene with high
yield: (1) chemical and (2) thermal reduction of exfoliated sheets of graphene oxide, as explained
in earlier sections. Both the methods disrupt the conjugated electrical structure of graphene and re-
duce the electrical conductivity. On the other hand, the functional groups introduced by these invasive
approaches can be used to achieve good dispersion of derived graphene in different solvents. Numer-
ous efforts have been made to improve the dispersion of GO and RGO by functionalizing the use of
organic molecules compatible with the polymer matrix to enhance interfacial interaction with matrix.
For example, GO has carboxylic, hydroxyl and epoxy groups on the surface which improve its disper-
sion in water and keep individual layers separated from each other [26,307]. However, these func-
tional groups and defects on GO make it electrically insulating and thermally unstable, and the
removal of these functional groups during reduction makes RGO hydrophobic and increases tendency
to agglomerate irreversibly in an aqueous medium unless stabilized by polymers and surfactants [82].
The dispersion behavior of GO in different organic solvents has been demonstrated in Fig. 6.1, which
can guide the selection of compatible polymer matrix for bulk synthesis [75].
The dispersion of graphene oxide and reduced graphene against their agglomeration in organic sol-
vents, after complete exfoliation of graphitic layers, has been achieved by surface functionalization
through non-covalent and covalent bonding [75,308,309]. Various organic functional groups such as
polystyrene [69,308], 1-pyrenebutyrate [310], dopamine [311], 7,7,8,8-tetracyanoquinodimethane
[312], coronene carboxylate [313] have been used to produce stable aqueous and organic solvent dis-
persion and facilitated nanocomposite synthesis to induce desirable properties.
Non-covalent functional groups including 1-pyrenebutyrate [310] and 7,7,8,8-tetracyanoquinodi-
methane [312] have strong afnity with the basal plane of graphite through pp interactions, while
covalent functional groups attach to the surface through the reaction between the functional groups
(AOH, ACOOH, ACO) present on the GO and RGO surfaces and edges. For example, Xu et al. have dem-
onstrated the covalently functionalized GO through the coupling amine-functionalized prophyrin
(TPP-NH
2
) and carboxylate groups [93]. The covalent polymer functionalization of graphene
Fig. 6.1. Digital pictures of as-prepared graphite oxide dispersed in water and 13 organic solvents through bath ultrasonication
(1 h). Top: dispersions immediately after sonication. Bottom: dispersions 3 weeks after sonication. The yellow color of the o-
xylene sample is due to the solvent itself. (Reproduced with permission from [75].)
nanosheets via atom transfer radical polymerization (ATRP) initiator was recently reported
[100,101,314] to achieve the dispersion of graphene sheets in polymer matrix and precise interface
control (Fig. 6.2). The ATRP initiator covalently immobilized on the surface of the graphene was sub-
sequently used for grafting polymer brushes from the sheets surface. Such controlled polymerization
allows the control of the molecular structure of the grafted polymer, providing an effective approach
to tune the properties of the hybrids.
In this approach, the initiator molecules were covalently attached to the graphene surfaces via dia-
zonium addition. The subsequent atom transfer radical polymerization linked ATRP compatible poly-
mer chains (i.e. polystyrene, polymethyl methacrylate) to the graphene sheets. Another example of
the covalent functionalization of graphene sheets with polymers is through grafting-to process by
the esterication of carboxylic groups in GO. The covalent functionalization of sheets with polyvinyl
alcohol (PVA) via the esterication provided a facile way of producing water and DMSO soluble, sim-
ilar to PVA [315].
6.1.1. Synthesis of graphene reinforced polymer composite
The method of solution blending, melt mixing, and in situ polymerization are the most common
synthesis strategies of the polymer matrix composites. These methods will be summarized in this
section.
6.1.1.1. Solution blending. Solution blending is the most common technique to fabricate polymer-based
composites provided the polymer is readily soluble in common aqueous and organic solvents, such as
water, acetone, DMF, chloroform, DCM and toluene. This technique involves the solubilization of the
polymer in suitable solvents and mixing with the solution of the dispersed graphene suspension. The
polar polymers including PMMA, PAA, PAN and polyesters have been successfully mixed with GO in
solution blending where the GO surface was usually functionalized by isocyanates, alkylamine, alkyl-
chlorosilanes, etc., to improve its dispensability in organic solvents. For instance, estericated GO was
mixed with PVA dissolved in DMSO to fabricate the PVAGO nano composite [315].
To homogenize the dispersion of graphene sheets, ultrasonic power can be used to produce meta-
stable suspension. It is important to note that long time exposure to high power ultrasonication can
induce defects in graphene sheets which are detrimental to the composite properties. Functionaliza-
tion of graphene sheets may help in obtaining a higher loading of sheets and allow dispersion in water
and other organic solvents. During the blending, the polymer coats the surface of the individual sheet
and interconnects each sheet after the solvents are removed. Solution blending of GO and RGO sheets
tend to agglomerate during slow solvent evaporation, resulting in inhomogeneous distribution of
sheets in polymer matrix. The distribution can be controlled by controlling the evaporation time using
spin coating or drop casting. Various polymer composites such as graphenePVA [316], GOPVA [317],
Fig. 6.2. Synthesis route of polystyrene functionalized graphene nanosheets. (Reproduced with permission from [101].)
graphenePVC [318], PVAGO layer by layer assembly [319], and PVDF-thermally reduced graphene
[320] have been prepared using this technique.
6.1.1.2. Melt mixing. Melt mixing technique uses a high temperature and shear forces to disperse the
reinforcement phase in the polymer matrix. The process avoids the use of toxic solvents. The high
temperature liquees the polymer phase and allows easy dispersion or intercalation of GO and re-
duced graphene sheets. The melt mixing is less effective in dispersing graphene sheets compared to
solvent blending due to the higher viscosity of the composite at increased sheets loading. The process
can be applicable to both polar and non-polar polymers. However, this technique is more practical for
thermo plastic manufacturing composite in large scale. Varieties of graphene reinforced composites
such as, exfoliated graphitePMMA [321], graphenepolypropylene (PP), GO-poly (ethylene-2,6-
naphthalate) (PEN) [322] and graphenepolycarbonate [323], are prepared by this method. Low
throughput of chemically reduced graphene restricts the use of graphene in the melt mixing process.
However, graphene production in bulk quantity in thermal reduction can be an appropriate choice for
industrial scale production. The loss of the functional group in thermal reduction may be a hurdle in
obtaining homogeneous dispersion in polymeric matrix melts especially in non-polar polymers. Kim
and Macosko [323] have not observed signicant improvement in mechanical properties due to the
elimination of the oxygen functional groups, which affected the interfacial bonding in graphene
composite with polycarbonate and PEN, and the defects caused by high temperature reduction.
6.1.1.3. In situ polymerization. This fabrication technique starts with the dispersion of GO or RGO in
monomer followed by the polymerization of the monomers. Like solution blending, functionalized
graphene and GO sheets can improve the initial dispersion in the monomer liquid and subsequently
in the composites. The in situ polymerization technique enables the covalent bonding between func-
tionalized sheets and polymer matrix through various condensation reactions. On the other hand,
non-covalent bonded composites such as PMMAGO [324], PPGO [325] and PE-graphite [326] have
also been prepared by this technique. Extensive research has been performed on producing epoxy-
based nano composites using in situ polymerization where sheets are rst dispersed into resin fol-
lowed by curing by adding hardener [284]. Recently, graphene oxide sheets have been used for Mg/
Ti catalysis support for in situ ZieglerNatta polymerization of PP, process are shown in Fig. 6.3 [325].
The prepared composite showed a good exfoliation of GO and homogeneous dispersion in PP ma-
trix (Fig. 6.4), leading to high electrical conductivity. In situ polymerization has also been explored
Fig. 6.3. Fabrication of PP/GO nanocomposites by in situ ZieglerNatta polymerization. (Reproduced with permission from
[325].)
widely for the high level of dispersion of graphite-based layered structure in a polymer matrix, such as
expanded graphite and graphite oxide [326328]. The in situ polymerization increases interlayer spac-
ing and exfoliates the layered structure of graphite into graphite nano plates by the intercalation of
monomers that generate polymers after polymerization, producing well-dispersed graphene in a poly-
mer matrix. This approach has produced a variety of composites, such as PANIGO/PANIgraphene
[329], graphene nanosheet/carbon nanotube/polyaniline [330], and PANIGO [331].
6.1.2. Mechanical properties
Higher mechanical properties (elastic modulus and tensile strength) of graphene sheets have at-
tracted the attention of researchers. The polymer reinforced with graphene has been employed to
explore intrinsic strength (125 GPa) and elastic modulus (1.1 TPa) of nanosheets to bulk polymer
composites. Similar to other composites, the mechanical properties are dependent on the reinforce-
ment phase concentration and distribution in the host matrix, interface bonding, and reinforcement
phase aspect ratio, etc. For example, an increase in tensile strength of the composite (graphenePS)
with reinforcement concentration is shown in Fig. 6.5, representing an increase in the mechanical
properties of the composite attributed to effective load transfer between graphene and polymer
[101].
Fig. 6.4. (A) PP/GO nanocomposites powder as obtained after coagulation in ethanol (containing 0.1 M HCl). (B) SEM images
obtained from fracture surface of neat PP without GO. (CE) SEM images obtained from fracture surface of composite samples of
0.42, 1.52, and 4.90 wt%, respectively, GO loadings. (F) TEM image of sample PP1 with 0.96 wt% of GO (the inset showing the
measured electron diffraction pattern). (G) TEM image of sample PP3 with 1.52 wt% of GO. (H) TEM image of sample PP4 with
4.90 wt% of GO. (Reproduced with permission from [325].)
Although the pristine graphene has the highest theoretical strength, the presence of functional
groups on the GO surfaces has the additional benets of its high level of dispersion in polar solvents
and water. The improved GO/polymer interaction facilitates high molecular level dispersion and en-
hanced interfacial interaction, leading to high mechanical properties. For example, GOPVA composite
showed enhancement in mechanical properties by 76% and 62% in elastic modulus and strength,
respectively, with 0.7 wt% GO sheets [317]. Xu et al. have also observed a similar trend for GOPVA
composite lms with a layered structure prepared by vacuum ltration [332]. Whereas, situation with
the chemically reduced graphene oxide (CRG) and thermally reduced graphene oxide (TRG) is differ-
ent, the presence of defects arise in carbon lattice due to the reduction process certainly have an ad-
verse effect on the mechanical properties [120,317,322]. High surface defects and wrinkles in TRG
reinforced in poly (ethylene-2,6-naphthalate) (PEN) indicated a relatively small increase in tensile
properties compared to the graphite reinforced PEN.
The interaction of graphene and polymer at the interface of effective load transfer has been exten-
sively investigated. The tailoring of mechanical properties by a covalent and non-covalent bond con-
guration between the matrix and sheets reinforcement can provide exceptional features. The
responsible Van der Waals forces and hydrogen-bond interactions were reported for improved
mechanical properties [316,333]. A recent ATRP strategy has been shown to grow styrene, methyl
methacrylate, or butyl acrylate polymer brushes directly from the GO surfaces without damaging
the GO structure [102]. One study used a similar strategy and revealed that when pre modied GO
with PMMA chain synthesized via ATRP and mixed with PMMA matrix have better dispersion and
interfacial bonding. The results showed that the loading of 1% (w/w) GO grafted PMMA made tougher
lms than the pure PMMA lms and unmodied GOPMMA lms. The elastic modulus and tensile
strength values were slightly lower than that of the pure PMMA lms [314].
Research in graphene-based composites has been concentrated on improving the stiffness and the
mechanical strength using graphene as ller [317,334337]. Other mechanical properties, fracture
toughness, fatigue, and impact strength of the graphene reinforced composites were also studied
[284,338340]. Recent, investigation about graphene reinforced Nayon-12, has shown the signicant
improvement with 0.6 wt% addition of graphene ller in tensile strength and elongation at break by
35% and 200% respectively. While, the improvement in K
Ic
and impact failure energy were by 72%
and 175% respectively. It has also shown that the graphene ller suppressed the crack propagation
in epoxy polymer matrix. The improvement in fracture and fatigue resistance was similar to CNT
and nanoparticles reinforcement but only need one to two orders of magnitude lower weight fraction
of graphene nanoller to achieve the same degree of reinforcement [284]. The superior mechanical
properties of composite made of graphene platelets over carbon nanotubes was related to their high
specic surface area, enhanced nanoller matrix adhesion/interlocking arising from their wrinkled
(rough) surface and 2-D at geometry [340].
Fig. 6.5. (a) Representative stress-strain curves of the pristine PS and nanocomposite lms with different contents of graphene
sheets. (b) Youngs modulus and tensile strength changes with increasing graphene content. (Reproduced with permission from
[101].)
6.1.3. Electrical properties
The most fascinating property of graphene is its very high electrical conductivity. When used as ll-
ers with insulating polymer matrix, conductive graphene may greatly enhance the electrical conduc-
tivity of the composites. Various factors have been corroborated by experimental results that inuence
the electrical conductivity and the percolation threshold of the composite. These factors include the
aggregation of ller, the presence of functional groups on graphene sheets, concentration of lers, as-
pect ratio of the graphene sheets, inter-sheet junction, distribution in the matrix, wrinkles and folds,
processing methods, etc. The pristine graphene has the highest conductivity, however difculty in pro-
ducing a large amount by mechanical exfoliation limits its use and compels to rely on CRG and TRG.
Although graphene oxide is electrically insulating, the thermal reduction eliminates the oxygen
functional groups and partially restores the electrical conductivity, making reduced graphene oxide
suitable ller for composite. Reduced graphene oxide sheets in composite provides a conductive path
for the electron when the concentration of the conductive ller is above the percolation threshold. The
lowest electrical percolation threshold (0.1 vol%) of graphene has been reported for the hydrazine re-
duced PS-isocyanate treated GO mixture [69]. It is reported that thermally reduced graphene has high-
er electrical conductivity than CRG due to absence of oxygenated functional groups. Thus, polymer
composite with TRG might show better electrical conductivity than that with CRG. Various polymer
matrices such as polyurethane, epoxy [341], polyamide, polyaniline [342], PVDF, PVA [343], polycar-
bonate [344] for CRG, TRG and GO reinforcement have been studied in the past few years. These com-
posite materials can be used for electromagnetic shielding [345], photovoltaic devices, sensors and
conducting paint. As explained earlier, that pristine graphene offers great electrical and transport
properties, however the application is limited by its poor dispersion into individual sheet in matrix.
Therefore, functionalized sheets may provide better opportunities for improved dispersion in polymer
matrix, which can be helpful for improving the mechanical properties. The attachment of the foreign
molecules may change the charge transport properties. Thus, sometimes it is important to trade off
the properties.
Macosko and coworkers [346] studied the effect of exfoliation (thermal and chemical) processes
and different dispersion methods including solvent blending, in situ polymerizations, and melt com-
pounding on electrical property of graphene/thermoplastic polyurethane (TPU) composites. Increased
electrical conductivity was observed for both graphite and TRG lled composites. However, the perco-
lation threshold was lower for TRG (0.5 vol%) than that of graphite (2.7 vol%) due to the difference in
aspect ratio. Among the TRG composites, the conductivity of solvent blended and in situ polymerized
samples was higher than the melt blended for the same volume of TRG. The sheets reaggregation in
melt blending reduced conductive surfaces and attrition during the melt extrusion reduced the lateral
size of TRG. The effect of graphene sheets orientation and different processing methods (compression,
injection molding, and long term annealing) was also demonstrated by studying polycarbonate/graph-
ene composites [323]. Various useful properties of polycarbonate matrix make the composite an
important engineering polymeric material for various applications. For electrical percolation rein-
forcement of TRG in polycarbonate required only 0.66 vol%, the composite was prepared by melt
extrusion, and the TRG remained highly exfoliated throughout the matrix as compared to graphite
[323]. Alignment of the TRG sheets has noticeable effect on electrical conductivity. For instance, the
squeezed lms or injection molded polycarbonate/TRG samples have shown lower conductivity than
the annealed disks. A similar composite system (polycarbonate/graphene) was studied by emulsion
mixing and solution blending followed by compression molding [344], which exhibited lower electri-
cal percolation threshold of ~0.14 and ~0.38 vol%, respectively compared to injection molded com-
posites [323]. The low percolation threshold and high electrical conductivity were due to the
wrapping of single and few layer graphene sheets around the polycarbonate microsphere, which gen-
erated a high conductive path for electrons.
The effect of temperature on electrical conductivity of the graphene-based composite was studied
using PVDF nano composite reinforced with TRG produced by solution processing followed by com-
pression molding [320]. TRGPVDF showed a decrease in electrical resistance with temperature (neg-
ative temperature coefcient) as compared to the increased resistance (positive temperature
coefcient, PTC) of the expanded graphitePVDF composite. This behavior of the TRG-based composite
was attributed to the higher aspect ratio of graphene which leads to contact resistance predominating
over tunneling resistance. Whereas, tunable PTC of resistance was observed in graphene nanosheets/
polyethylene composite when composite was isothermally treated at 180 C for different time interval
due to low viscosity of the polymer matrix which helped in migration of graphene sheets and weaken
the overlapping conductive joints of graphene sheets [347].
6.1.4. Thermal conductivity
Thermal conductivity (j) of the material is governed by the lattice vibrations (phonon). The 2D
structure of graphene has shown highest thermal conductivity (~3000 W/mK) [6], making it excellent
candidate in various polymer matrices to enhance heat transport. The polymer composites of good
thermal conductivity have potential applications in electronic circuit boards, heat sink and light
weight high performance thermal management systems. In spite of the highest thermal conductivity
of the graphene sheets, the enhancement in thermal conductivity of nano composites was not like
electrical conductivity because the contrast in thermal conductivity (j
graphene
/j
polymer
) is of the order
of 4 in comparison to the contrast in electrical conductivity (r
graphene
/r
polymer
) which is the order of
1519. The second important factor is high interfacial thermal resistance between graphene sheet
and polymer matrix due to strong phonon scattering which affects heat transfer. Other factors such
as aspect ratio, orientation and dispersion of graphene sheets will also affect thermal property similar
to electrical and mechanical properties.
Improved thermal conductivity was demonstrated for various polymer matrices, reinforced with ex-
panded graphite and multilayer graphene sheets, such as, epoxy [348352], PVC [318], polypropylene
(PP) [353], and polyethylene (PE). For thermal conductivity of the polymer composites, most of the stud-
ies are focused on the epoxy matrix and graphite nano platelets (GNPs). Haddon and coworkers [348]
prepared graphite nano platelets fromnatural graphite by the acid intercalation followed with the exfo-
liationby rapidthermal shock. These GNPs were dispersedinepoxymatrixandshowedthermal conduc-
tivity up to 6.44 W/mK at 25 vol% of GNP loading, which is higher than the neat epoxy. The effect of
orientation of GNPs on thermal properties was noticed by Drzal and coworkers [353]. They measured
coefcient of thermal expansion (CTE) along the longitudinal and the transverse direction of the ow
of the melt during injection molding for GNPPP composite. They found that the loading of 3 vol% GNPs
reduced the CTE of PP by 2025% in both transverse and longitudinal directions. The thermal conductiv-
ity ~1.21.5 W/mKwas achieved at 25 vol%GNP, which is six times higher than that of PP. In an effort in
keeping highaspect ratio andgooddispersionof GNPs inmatrix during processing, Veca et al. [354] used
expandedgraphite reinforcement inepoxymatrixwhere the expandedgraphitewas exfoliatedinsheets
using alcohol and oxidative acidtreatment by simultaneous stir and vigorous sonication. This treatment
facilitatedthe well dispersionof the sheets inepoxymatrix witha thickness of less than10 nm. The ther-
mal conductivity properties of the composite were highly anisotropic with a large ratio between the in-
plane and cross-plane thermal conductivities. The 33 vol% loading of nanosheets showed thermal con-
ductivity of 80 W/mK (based on diffusivity value) in plane, whereas cross-plane thermal conductivities
were about one tenth to one fth of the in-plane value. It was observed that the conductivity increased
linearly with addition of nanosheets due to the reduced interfacial thermal resistance. However, the
composite lost its exibility above 33 vol% loading of graphene llers.
Toreduceinterfacial phononscattering, ahybridof carbonnanotubeandGNPs inpolymer matrixwas
proposed by Yu et al. [355]. They have combined SWCNT and GNPS ller in epoxy and achieved a syner-
gistic effect inthethermal conductivityenhancement of thecomposite. Theyproposedthat theenhance-
ment was originated from the bridging of planar nano platelets by the SWCNT, which decreased the
thermal interface resistance due to the extended area of the SWNTGNP junctions. The composite with
the optimizedloading of SWNTGNP hybrid ller in the range of 1020 wt%and the ratio of ller SWNT/
GNP around 1:3 has shown the highest thermal conductivity (1.75 W/mK). Recently, Yang et al. [349]
have also demonstrated the synergistic effect of graphene platelets and MWCNT in improving thermal
conductivity of the epoxy composite. The stacking of GNP was inhibited by the MWCNT and their long
tortuous feature bridge adjacent to GNP, resulting in highcontact area betweenhybridandpolymer ma-
trix. Thermal conductivity was increased by 147% by adding 1 wt% (MWCNT:GNP ratio of 1:9). As men-
tioned in earlier sections, the functionalization of graphene can enhance the interface bonding between
graphene ller and polymer matrix, which can also minimize phonon scattering. In one study, function-
alizing graphene with 4,4
/
diaminodiphenyl sulphone (DDS) to enhance bonding between sheets and
polymer matrix for improvedinterfacial heat transfer was also reported [351]. The thermal conductivity
of the functionalized graphene composite (0.49 W/mK) shows 30% enhancement over that of function-
alized MWCNT composite (0.38 W/mK) at 0.5 vol% loading.
6.1.5. Other properties
The reduced gas permeability and high thermal stability of the graphene reinforced polymer have
also been demonstrated. The permeability of the gases is the gas channeling through the polymer. Var-
ious studies showed that the dispersion of impenetrable graphite nanoplatelets, graphene and GO
sheets of the high aspect ratio and surface area, into polymer matrices provide a tortuous path for
the diffusing gas molecules, enhancing the gas barrier properties as compared to neat polymer
[356,357]. The recent study by Compton et al. [357] have shown that the incorporation of 0.02 vol%
of crumpled graphene sheets in polystyrene matrix drastically inhibit the O
2
molecules permeation.
The reduction of phenyl isocyanates functionalized GO in the presence of polystyrene have provided
a fully dispersed polymer graphene nano composite leading to the densication of polystyrene lm
just by the addition of a small amount (0.02 vol%) of sheets. The transmittance was also reduced for
280 lm thick composite lm by three times at 350 nm. Detailed studies by Macosko group on perme-
ability of different gases through the graphene and graphite oxide reinforced polymer composites
have concluded the signicant improvement in gas barrier properties compared to that of the graphite
reinforced composite [322,323,346]. For example, permeation of N
2
and helium was suppressed by
39% and 32% respectively by the addition of 1.6 vol% TRG in poly carbonate matrix [323]. The compar-
ison of different processing techniques reinforced with various form of carbon (graphite, TRG, GO, and
isocyanate treated GO) in thermoplastic polyurethane have shown a great difference in N
2
permeabil-
ity (Fig. 6.6) [346]. The incorporation of isocyanate treated GO showed a 90% reduction in N
2
perme-
ability at 1.6 vol% loading due to high aspect ratio of the exfoliated sheets. Among three commonly
used techniques for composite production, the solvent-based blending technique has shown more
effective distribution of sheets in polymer matrices. The oxygen permeability study by Drzal group
on graphite nanoplatelets reinforcement on widely used and important thermoplastic, polypropylene
indicated 20% improvement in gas barrier property at 3 vol% [356]. Whereas, higher oxygen perme-
ability was observed for other additives of different shapes and aspect ratios such as carbon black,
nano clay, and PAN-based carbon ber for similar amount of loading.
Outstanding thermal stability of graphene makes it attractive ller for fabrication of thermally sta-
ble composites. The thermal degradation temperature measured by thermogravimetry method
showed the improvement in thermal stability for graphene/GO composite with PVA [332,343], PMMA
[358] and PS [359]. One study showed the improvement in thermal stability by 100 C for
Fig. 6.6. N
2
permeability, P
Nitrogen
, of TPU composites normalized by permeability P0 of unlled TPU. (Reproduced with
permission from [346].) Permeability data for graphite composites are reproduced in the inset. Solid curves are predictions
based on Ref. [361].
PVA10 wt%RGO composite [343]. In addition of raising the thermal degradation temperature, graph-
ene llers reduce thermal decomposition kinetics due to strong interaction between sheet and poly-
mer, which impedes the chain mobility.
Similar to SWCNTs, graphene sheets have negative in plane coefcient of thermal expansion (CTE)
as compared to the host polymer matrix. Thus, it is reasonable to expect the improvement in CTE by
graphene and GO reinforcement in polymer. Comparative studies show that the SWCNT and graphene
have similar affect in decreasing CTE in epoxy matrix. The test results also demonstrate that the
increasing graphene fraction reduces CTE more signicantly. The 5 wt% GO/epoxy composite showed
31.7% reduction in CTE below the glass transition temperature [360].
6.1.6. Applications
The reinforcement of graphene and GO in polymer matrices has shown very exciting results in
improving electrical conductivity at a very low percolation threshold, increase in strength and elastic
modulus, high thermal conductivity and stability, and reduced permeation of gas molecules. All of
these results open a new avenue for developing high strength light weight structural polymer com-
posites for automobile, aerospace, and thermally conductive support in the electronic industry for
thermal management. Graphene-based polymer composites can also nd application in packaging
for food, medicine, electronics and beverages due to low permeability of gas molecules such as N
2
,
O
2
, moisture and CO
2
[322,323,346]. However, it is too early to commercialize the graphene-based
polymer composites because of challenges in mass production of the low cost high quality graphene
and the control dispersion in polymer matrix.
Few applications of graphene/polymer composites in energy storage [362367], electrically con-
ductive polymers [69,246], antistatic coatings and electromagnetic interference shielding [345] have
been demonstrated. Extensively studied graphene/polyaniline nano composites have shown high spe-
cic capacitance up to 1046 F/g and good cyclic stability, which can be used for exible supercapacitor
electrodes [367]. Whereas, other carbon additives i.e. SWCNT, MWCNT to PANI have shown capaci-
tance of 450500 F/g [368,369]. It is important to note that non-conductive polymer can be made elec-
trically conductive/semi conductive by percolation of graphene network. This has shown the
possibility of their use in electronic devices. Recently, a composite lm of graphene/PS was prepared
using solution blending, showed the semi conductive nature and exhibited the eld effective ambipo-
lar property [246]. These lms were electrically conducting with a conductivity of 124 S/m.
Other potential applications of graphene polymer composites have also been explored in making
transparent conductive electrode for dye-sensitized solar cells with conducting polymer [370], and
electrode for electrochromic devices [371]. The graphene and poly (3,4-ethyldioxythiophene) (PEDOT)
composite lms exhibited excellent transparency, exibility, conductivity and thermal stability may
be a promising component for the future touch screens, video displays, and plastic solar cells [372].
6.2. Graphenenanoparticles composites
The nano particles synthesis is the well established, and explored for many applications, as
extraordinary properties of graphene opened new frontiers for their composite with nano particles
(NPs) to achieve the synergistic effects of individual components. Recently, various metals, metal oxi-
des and semiconducting NPs have been incorporated to graphene 2-D structures aiming to realize
exceptional properties in composite form. It is worthy to mention that the NPs are directly decorated
on the graphene sheets, and no molecular linkers are needed to bridge the NPs and the graphene
which may prevent additional trap states along the sheets. Therefore, many types of second phase
can be deposited on graphene sheets in the form of nanoparticles to impart new functionality to
graphene aiming at catalytic, energy storage, photocatalytic, sensor, and optoelectronics applications.
6.2.1. Synthesis
Few important issues need to be addressed for bulk grapheneNPs composites synthesis. These is-
sues include: (1) separation of individual pure graphene sheets (2) non-uniform dispersion of NPs on
graphene sheets (3) the mechanism of NPs attachment to two-dimensional structures (4) the role of
intentional/unintentional functional groups on GO/RGO in hybrid structures formation (5) the
interaction between NPs and graphene, and its effect on intended property and (6) the effect of graph-
ene size and presence of defect.
Many different types of synthesis methods have been developed for preparing grapheneNPs
composites, includes three main strategies; pre-graphenization, post-graphenization and syn-
graphenization (often called one-pot strategy).
v Pre-graphenization: In this method pre-synthesized RGO is mixed with the nano particles for com-
posite manufacturing. The incorporation of second phase NPs and solubility of RGO in various sol-
vents are important considerations for the composite preparation. The hydrophobic nature of RGO
restricts the process to limited organic solvents, explained earlier in this article.
v Post-graphenization: This method consists of thorough mixing separately prepared NPs and/or salt
precursors with GO suspension followed by reduction. Initial studies of composite preparation
show mixing of GO aqueous suspension with water soluble metal precursors followed by the
reduction to form RGO/NPs composite. This synthesis technique has been used to deposit metal
NPs (e.g. Au, Pd, Pt, Ag), metal oxide NPs (Fe
2
O
3
, Fe
3
O
4
, Al
2
O
3
, SnO
2
, NiO, MnO
2
, TiO
2
, ZnO, Cu
2
O
and Co
3
O
4
) and semiconducting NPs (CdSe, CdS, ZnS) on GO. The procedure consisted of mixing
respective metal salts (HAuCl
4
, K
2
PtCl
4
, K
2
PdCl
4
, and AgNO
3
) to GO suspension followed by the
reduction using hydrazine monohydrate or sodium borohydride [85]. Attachment of NPs prevents
the aggregation and restacking of RGO in the reduction process. The incorporation of NPs could be
through physical absorption, electrostatic interaction or covalent bonding with RGO. The possibil-
ities of detachment of NPs, incorporated by physical absorption or electrostatic attraction, can be
surmounted using functionalized NPs that can form covalent bonding.
v Syn-graphenization strategies: This is often called the one-pot approach. The second components of
the composite act as a stabilizer for improving composite properties.
Based on these strategies, numerous composites have demonstrated an integration of NPs on the
surfaces of graphene to achieve unique properties from individual components and from their inter-
action. Various composites based on functionalized graphene with metals, semiconductors and metal
oxides are summarized in Table 6.1.
Various synthesis strategies have been proposed for NPs/RGO composites. In situ growing graph-
ene/NPs have been adopted from the methods to produce CNT composites. The major advantage of
the technique is direct contact between graphene sheets and NPs. The homogeneous distribution of
NPs on 2D sheet occurs due to nucleation of NPs in situ. The functional groups and defects (due to syn-
thesis) on GO surface can assist the nucleation and size control of NPs. The functional group on GO,
including carboxylic, hydroxyl, and epoxy groups can be utilized as nucleating sites on GO to control
the size, morphology and crystallinity of grown NPs [383]. Furthermore, lattice defects (missing
atoms) in 2-D crystal are thermodynamically unstable high energy sites those favor the nucleation
and trap nano particles.
Althoughthe functional groups on GOand RGOcan provide preferred reactive site for nucleation and
anchoring sites for grown NPs [385] GO and RGO have different nucleation sites that generate different
NP morphology. Wang et al. [383] demonstrated a different growth mechanismof Ni(OH)
2
nano crystal
onGOandRGOsheets. The functional groups onGOprovidedstronginteractions withthe depositedspe-
cies, providing pinning forces to restrict diffusional growth of small particles. In contrast, RGO has less
functional groups than GO, which allows easy diffusion and re-crystallization to formlarge single crys-
tals as shown in Fig. 6.7. The similar synthesis strategy was extended to Co
3
O
4
and Mn
3
O
4
graphene hy-
brids to fabricate anode material for lithium batteries, since graphene can act as a high conductive
support, and its chemical stability can improve the electrochemical performance of the electrode [386].
The stable suspension of GO/RGO and reduced aggregation during composite formation is further
improved by solvothermal synthesis. Solvothermal can be performed through one-pot reaction to syn-
thesize NPs decorated graphene composites without any reducing agent (toxic hydrazine)
[392,397,401]. High temperature and pressure during the solvothermal reaction reduces graphene
oxide leading to composite formation. Fig. 6.8 (a,b) shows solvothermal scheme to produce RGO/
CdS in dimethyl sulfoxide (DMSO) [397]. This approach overcomes low yield production of single layer
graphene and prevents the aggregation of graphene layers. The electrical conductivity of the
Table 6.1
A summary of NP decorated RGO composite and their proposed application.
Nano
particles
Graphenization Synthesis Application References
CdSe Post- GO + CdSe + TOPO ligands Transparent lm, photo
switching
[373]
Au Post- LBL method, Au NPs formation by reduction
of Au ions in a gold salt solution on the RGO
lms
[374]
Pt Pre- N doped RGO + DMF + NaOH + ethylene
glycol + H
2
PtCl
6
+ 6H
2
O (stirring at 160 C)
Electrocatalytic activity
(methanol fuel cell)
[375]
Fe
3
O
4
Post- GO + Fe
3
O
4
+ doxorubicin hydrochloride
(DXR)
Magnetic hybrid graphene
(drug delivery)
[376]
Fe
3
O
4
Pre- High temperature reaction of ferric
triacetylacetonate with GO in 1-methyl-2-
pyrrolidone
Magnetized RGO [377]
Si, SnO
2
,
TiO
2
,
Co
3
O
4
Post- APS modied NPs + GO > encapsulating GO/
NPs
Lithium storage electrode
(capacitor)
[378]
SnO
2
Post- GO + HCl + SnCl
2
+ 60 C for 6 h Capacity behavior [379]
Pt, Au, Pd Post- Ethylene glycol + metal precursor (K
2
PtCl
4
,
K
2
PdCl
4
, HAuCl
4
+ H
2
O) 100 C heat in oil
bath
Metal nano composite
prevents restacking graphene
[380]
Pt/Au, Au Pre- Naon + glucose oxidase + chloroplatinic
acid (H
2
PtCl
6
, 6H
2
O) phosphate buffer
(K
2
HPO
4
+ KH
2
PO
4
) + RGO
Biosensor (ampeometric
biosensor)
[381]
Au GO + H
2
SO
4
+ HNO
3
+ KClO
3
reacted with
ODA thionyl chloride
Showed potential for
utilization in plasmonics and
optoelectronic devices
[382]
Ni(OH)
2
Post- Ni(CH
3
COO)
2
+ DMF + GO > crystal growth
on graphene Ni(OH)
2
[383]
Pd Pre- H
2
electrochemical plasma
RGO + Na
2
PdCl
4
+ LiClO
4
Gas sensing [290]
Ag Syn- Heating 75 C GO on 3-
aminopropyltriethoxysilane (APTES) + Ag
NPs
[384]
Fe
3
O
4
Post- GO + Fe
3
O
4
functionalizing with TEOS,
APTES, EDC, NHS and magnetic separation
Magnetic hybrid graphene
(heterogenous catalysts and
drug delivery)
[284]
TiO
2
Post- Direct growing, 2 step method
(TiO
2
+ GO) + antanase hydrothermal
treatment
Photocatalytic activity (solar
cell and lithium ion battery)
[385]
Mn
3
O
4
Post- Mn
3
O
4
on GO, 2 step method (Ni(OH)
2
+ GO,
TiO
2
+ GO) + KMnO
4
= Mn(CH
3
COO)
2
+ DMF/
H
2
O]
Lithium ion battery [386]
SnO
2
Pre RGO + SnO
2
(obtained from hydrolysis of Sn
Cl
4
+ NaOH)
Lithium energy storage [387]
TiO
2
Syn GO + TiCl
3
+ H
2
O
2
in SDS solution > self-
assembly TiO
2
Investigation Li ion insertion
properties
[388]
TiO
2
Post- GO + TiCl
3
+ Na
2
SO
4
+ H
2
O
2
(self-assembly) Photocatalytic activity, p/n
heterojunction
[389]
CdS Post- In situ growth Photoeletrochemical cells [390]
Graphene
QDs
Hydrothermal treat 200300 C 2 h in
furnace with N
2
Blue luminescence (PL)
(optoelectronics and
biological labeling)
[273]
TiO
2
Post- GO + Ti(OBu)
4
+ DEA + NH
4
OH + H
2
O
2
(sol
gel process)
Photoconductor for ink print
methods
[391]
CdSe Pre- Cd(SA)
2
/HDA/TOPO (in situ growing) Optoelectronic device [392]
TiO
2
Post- TiO
2
colloidal solution + GO (UV light
reaction)
Dye sensitized solar cell [283]
TSCuPc Post- TSCuPc + GO (hydrate heat 1 h at 90 C with
stirring)
Optoelectronics devices [107]
(continued on next page)
Table 6.1 (continued)
Nano
particles
Graphenization Synthesis Application References
ZnO nano
wire
Post- ZnO nano wire grown on RGO/PDMS
substrate using hydrothermal method
Transparent and exible
optoelectronics
[393]
TiO
2
/Ag Post- TiO
2
+ UV> + GO (became RGO)> + Ag ion
(photocatalytic methods)
Chem/biological sensor [394]
TiO
2
Post- TiO
2
+ GO sheets (photocatalytic reduction)
100 mW/cm
2
mercury lamp at 275, 350,
660 nm
Photoinactivation of bacteria
in solar light irradiation
[395]
ZnO Pre- RGO + ultrasonic spray pyrolysis ZnO (LBL
assembly)
Supercapacitor [396]
CdS Syn- DMSO Reduction of GO an deposing CdS
occur simultaneously (solvothermal)
Optoelectronic device [397]
Co
3
O
4
Post- GO + Co
3
O
4
Di water + H
2
O
2
centrifugation,
HCl wash and vacuum oven 60 C for 3 days
Catalytic effect for Al
perchlorate decomposition
[398]
RuO
2
Post- GO + RuCl
3
+ NaOH (reduced at 150 C) Electrochemical capacitor
and supercapacitor (energy
storage)
[399]
CdTe Post- CdTe + GO + Molecular beacon + abtamer Biomolecular sensor [400]
CdS, ZnS Syn- Cd(CH
3
COO)
2
2H
2
O + GO
Zn(CH
3
COO)
2
2H
2
O + GO (solvothernal)
Photovoltaics [401]
TiO
2
Post- TiO
2
colloidal solution + GO (UV light
reduction)
photoactive devices [402]
Silica Post- TMOS + GO (solgel) Transparent conductors [403]
Au Pre- Au NPs deposited on top of RGO (micro-
pattening method)
Memory devices [404]
LBL: layer by layer assembly, APS: aminopropyltrimethoxysilane, TEOS: tetraethyl orthosilicate, APTES: 3-aminopropyl tri-
ethoxysilane, EDC: 1-ethyl-3-(3-dimethyaminopropyl) carbodiimide, NHS: N-hydroxysuccinnimide, SDS: sodium dodecyl
sulfate, TMOS: tetramethyl orthosilicate.
Fig. 6.7. Schematic illustration of two-step Ni(OH)
2
nanocrystal growth on (A) graphene sheets (GS) and (B) graphite oxide
(GO). Dark gray balls, Carbon atoms; blue balls, H atoms; red balls, O atoms; green plates, Ni(OH)
2
. After the rst step of the
growth process (Ni precursor coating), the same coating of Ni(OH)
2
0.75H
2
O was obtained both on GS and GO. After the second
step (hydrothermal transformation), however, the coating on GS diffused and recrystallized into large single-crystalline
hexagonal Ni(OH)
2
nanoplates (C), while the coating on GO remained as densely packed nanoparticles pinned by the functional
groups and defects on the GO surface (D). (Reproduced with permission from [383].)
composite produced from this method was comparable to or slightly better than those produced from
the hydrazine reduction. In comparison to NP attached to RGO through molecules, the in situ grown
device showed faster and dramatically enhanced photo response because the NPs (e.g. CdSe) domi-
nantly reside on the RGO via their non-polar facets [392].
The functional groups on GO and RGO have provided anchoring sites for NPs, leading to various
applications. However, this approach is limited by several factors including the lack of control of
the functional groups on GO and RGO surface, and the poor dispersity of GO in organic solvents and
RGO in water. Future research is needed to control the functionalization of GO and RGO to achieve
controlled deposition of NPs. Other method such as, solgel, UV assisted reduction and solution mix-
ing has also been employed for grapheneNPs composites.
The Solgel method was initially employed to fabricate graphene/silica composite thin lms for
transparent conductors [403], consisted of hydrolysis of tetramethyl orthosilicate in presence of GO
suspension in water. This lm was subsequently reduced in presence of hydrazine vapors for RGO/
SiO
2
conductive composite lm. Recently, a modied solgel method was adopted for TiO
2
/GO com-
posite using blending of GO sheets with a titanium hydroxide-based ionic salt, which was further re-
duced photocatalytically [391].
UV-assisted photocatalytic reduction of GO was also observed and employed for composite forma-
tion. Kamat and coworkers, have shown photocatalytic reduction of GO under ultra violet light (UV) in
presence of TiO
2
NPs [402,405]. This strategy avoids the chemical reduction and maintains well dis-
persed TiO
2
-RGO in suspension. Under UV radiation, TiO
2
NPs generate long life-time electronhole
pairs. The generated holes are scavenged, leaving electrons on TiO
2
[406] surface and reduce the oxi-
dized groups on GO surface (Fig. 6.8c). The UV assisted reduction is fast and straight forward but only
applicable to those NPs system which are sensitive to external light irradiation such as TiO
2
and ZnO.
Another method consists of adding pre-synthesized NPs to GO suspension followed by chemical
and/or thermal reduction for hybrid composite synthesis. The ex situ synthesis allows precise control
of the size and surface properties of NPs as there is no interference from the GO/RGO and their reduc-
ing chemicals, as observed in the in situ case. However, synthesis process involves a chemical/thermal
reduction to obtain NPs/RGO composite which may change the NPs surface properties and damage
graphene lattice. Therefore, further investigation may require revealing the impact of the reduction
processes on the composite properties.
6.2.2. Applications
6.2.2.1. Optoelectronic devices. To extend the application of graphene-based electronics to the eld of
optoelectronics, it has been proposed to incorporate with excited states of semiconducting NPs (or
Fig. 6.8. (a) Scheme of the solvothermal one-step synthesis of graphene/CdS in DMSO. (b) Bottle (I),GO suspension in DMSO;
bottle (II), completion of reaction as grapheneCdS settles down; bottle (III), after washing with acetone and ethanol; bottle (IV),
re-suspension in ethanol. (Reproduced with permission from [397]). (c) Schematic of TiO
2
graphene composite and its response
under UV-excitons. (Reproduced with permission from [402].)
quantum dots), so that the optoelectronic properties of the composite materials can be tuned over a
wider range of the spectrum.
Formation of the photogenerated excitons in semiconductor nanoparticles is the primary event for
the photocurrent generation. To enhance the photocurrent, retardation of the recombination of the
electronhole species is essential. Due to high electronic conductivity of graphene, it can act as ef-
cient electron-transport matrices that retard the recombination reactions. The photocurrent genera-
tion in graphene/semiconducting NP QDs composite shows potential for large area optoelectronic
devices. Several semiconducting nanoparticles such as CdS [397], CdSe [373,392], ZnO [396], TiO
2
[283,378,385,388,389,391,395,407,408] TSCuPc [107] and Co
3
O
4
[398] have been anchored on graph-
ene for hybrid solar cell and optoelectronic device applications. For example, RGO/CdSe NPs composite
showed a dramatically enhanced photo response with fast time response under visible light (Fig. 6.9)
[373,392]. Such behavior can be interpreted by the efcient and separate transfer of the photo-
induced carriers from the CdSe NPs to the RGO. The photosensitivity, a ratio of the current under
the irradiation to that of dark, of the CdSe composites showed improvement of 1700 % [392]. The pho-
tosensitivity of the composites was also improved by three folds using composite with CdSe. The
photoconductivity of the composite lm can be up to 10 orders of magnitude higher than that of
intrinsic CdSe QD lms [373]. Another study detected a picoseconds ultrafast electron transfer from
the excited CdS to graphene by time-resolved uorescence spectroscopy, suggesting that CdS/graph-
ene can also be a potential candidate for harvesting optoelectronic applications [397].
In addition, the number of photo generated free carrier and the photo response of the composite
lm can be tuned by changing wave length and intensity of light source [389]. This suggests that
RGO/semiconducting NPs can be a potential candidate for tunable semiconductors. Until now, most
of the optoelectronic applications of graphene/NPs composites are focused from UV to visible light
range. If the ranges are extended to the wider regime, graphene composite devices could have poten-
tial for planar-integrable active optical sources, modulators, channel monitors and switches at tele-
communication wavelengths.
6.2.2.2. Graphene composite for energy storage.
6.2.2.2.1. Lithium ion batteries. Increasing energy demands have motivated researchers to look for the
alternative energy resources. Among various alternatives, a considerable attention has been given to the
lithium ion batteries due to its rechargeable characteristics, higher specic energy and longer cycle life.
The unique properties of graphene including superior electrical conductivity, high surface to vol-
ume ratio, ultrathin exible nature and chemical stability make it ideal candidate to build the compos-
ites with metal and metal oxide nanoparticle for energy storage applications. In such composites,
Fig. 6.9. (A) Typical IV characteristic of the RGO/CdSe NP nanocomposite without (curve a) and with irradiation (curve b);
inset is the corresponding SEM image of the sample after being drop cast onto a gold interdigital electrode. (B) Current response
vs. time under chopped irradiation (under a bias voltage of 8 V). (Reproduced with permission from [392].)
graphene provides support for nanoparticles and prevent the volume expansion-contraction of nano-
particles during charge and discharge process.
Various electrode materials based on transition metal oxides such as SnO
2
, Co
3
O
4
, Fe
3
O
4
, TiO
2
,
Mn
3
O
4
are proposed for lithium ion batteries (LIBs) to achieve higher specic capacities than currently
being used graphite. These transition metal oxides have very high theoretical capacities but extremely
low electrical conductivity that restricts their direct application in LIBs. For instance, Mn
3
O
4
has elec-
trical conductivity about 10
7
10
8
S/cm that limits its specic capacity lower than 400 mA h/g.
Whereas, a superior specic capacity of SnO
2
(an anode material with theoretical specic capacitance
of 780 mA h/g) in LIBs is affected by its phase transformation and pulverization due to Li ion insertion
and extraction during the chargedischarge cycles [387]. Furthermore, electrochemical stability of ac-
tive materials at various current densities and decrease in cyclic performance are other issues with
LIBs. Therefore, various conductive additives such as CNTs [409411] and carbon particles [412] have
been added to increase specic capacity. Currently used graphitize carbon anode material show low
capacity (372 mA h/g) because of limited Li ion storage sites within sp
2
carbon hexahedrons. One pos-
sibility to increase the Li intercalation in the charge/discharge process is using the layered structure of
graphene nanosheets. Yoo et al. [413], reported the enhanced specic capacity of these carbon-based
electrodes through the interaction of graphene nanosheets with C60 and CNT, which facilitates the
nano space size for lithium ion (r ~ 0.06 nm) intercalation. Higher reversible capacity (794
1054 mA h/g) and cyclic stability was also demonstrated in disordered graphene nanosheets, as the
presence of edge and vacancies defects in graphene sheets provides additional reversible storage sites
for Li ions (Fig. 6.10) [414].
Recent studies show the addition of the graphene-based material to transition metal oxide en-
hances the specic capacity of the electrodes at high discharge rare and improve the electrochemical
stability for longer cycles. The improvement was attributed to the excellent electronic conductivity,
high surface area, thermal and chemical stability and mechanical exibility of monolayer graphene
sheets. The exible graphene sheets accommodate a large volume expansion of metal oxide during
the chargedischarge process and prevent the pulverization of the electrodes leading to higher elec-
trical conductivity of the electrode. Moreover, high surface area of graphene facilitates Li ions interca-
lation. Researchers have made a signicant effort towards the development of high cyclic performance
of the LIBs using nano metal oxide and graphene composite, summarized in Table 6.2. These metal
oxide nano particles are grown on graphene oxide using solution chemistry followed by hydrothermal,
thermal or chemical reduction to intimate contact between RGO and NPs.
Wang et al. [386], have demonstrated a simple two-step solution based method for Mn
3
O
4
-
grpahene hybrids using slow hydrolysis of their salts (Manganese acetate) in DMF and hydrothermal
Fig. 6.10. Reversible (charge) capacity verse cycle numbers at a current density of 0.05 A/g, for natural graphite (i), pristine GO
(ii), hydrazine reduced GO (iii) 300 C pyrolytic GO (iv), 600 C pyrolytic GO (v), and electron-beam-reduced GO (vi).
treatment for reduction of GO in to RGO. The slow hydrolysis has shown the uniform distribution of
the nano particles on RGO sheets, resulting enhanced capacity at various current density (Fig. 6.11).
To avoid the aggregation of nanoparticles during the chargedischarge cycle, a new strategy con-
sisting encapsulation of metal oxide particles by graphene sheets was developed (Fig. 6.12) [378]
through the co-assembly of negatively charged graphene oxide with positively charged oxide nano-
particles using electrostatic attraction. The resultant composite has shown very high reversible capac-
ity (1100 mA h/g in rst 10 cycles) for graphene-encapsulated Co
3
O
4
and 1000 mA h/g after 130
cycles.
The functionalization of hydrophobic graphene sheets before mixing with the hydrophilic oxide
nanoparticles is an another excellent approach to form a uniform metal oxide coating [388]. The
use of anionic surfactant (i.e., sodium dodecyle sulfate) helps in dispersing individual graphene sheets
and in situ crystallization of metal oxide particles. TiO
2
/RGO composites were prepared for LIBs elec-
trodes using surfactant assisted growth of nanoparticles of TiO
2
and showed the more than double
specic capacity than control rutile TiO
2
at a high discharge rate of 30 C [388]. The ternary self-
assembly approach has been used to prepare well controlled and ordered metal oxide (SnO
2
, SiO
2
,
NiO, MnO
2
)/graphene nanocomposites includes self-assembly of metal oxides, surfactants, and graph-
ene for LIB electrodes. The high concentration of RGO (3060 wt%) with anionic surfactant has been
used to build layered metal oxidegraphene composite lm electrolyte (Fig. 6.13) [417].
The controlled growth of TiO
2
on graphene oxide sheets was achieved by limiting the rate of hydro-
lysis during synthesis without surfactants [385]. The TiO
2
-RGO composite showed superior photocat-
alytic activity than a variety of other TiO
2
materials. Furthermore, study is not limited to the inorganic
oxide particlesgraphene composite. Recently, nitrogen doped graphene was also tried for the LIBs an-
ode fabrication [53].
6.2.2.2.2. Supercapacitors. Supercapacitors or ultra capacitors are passive and static electrical energy
storage devices for short load cycle applications. Supercapacitors with very high power density, fast
charge/discharge ability without degradation and burst release characteristic makes them ideal can-
didates for applications in mobile electronic gadgets and hybrid electric automobiles.
Energy stored in supercapacitor is through the ion adsorption at the electrode interface which
make electrical double layer (electrical double layer capacitors, EDLC) or due to electron transfer be-
tween the electrolyte and the electrode through fast Faradic redox reactions (psuedocapacitors). Sev-
eral supercapacitor materials have been studied to enhance specic capacitance and power density.
Table 6.2
Graphene based lithium ion battery materials and properties.
Material Energy density
(mA h/g)
Current density
(mA/g)
Cycles References
Graphene encapsulated-Co
3
O
4
10001100 74 ~130 [378]
Graphene anchored Co
3
O
4
935 50 ~30 [415]
GrapheneMn
3
O
4
730780 400 ~50 [386]
Free Mn
3
O
4
115300 40 ~10 [386]
Pure Co
3
O
4
900 [416]
SnO
2
graphene 625 10 ~10 [417]
Pure SnO
2
782 [418]
Graphene-wrapped Fe
3
O
4
1026 35 ~30 [419]
580 700 ~100
Anatase TiO
2
-FGS 160 ~100 (at 1C charge/
discharge rates)
[388]
Rutile TiO
2
-FSG 170
GrapheneSi 2200 ~50 [420]
1500 ~200
Graphene nanosheets 290 50 ~20 [413]
(GNS) GNS + C60 600 50 20
GNS + CNT 480 50 20
Disordered graphene 7941054 [414]
GrapheneSnO
2
(nanoporous
electrode)
810 50 ~30 [387]
Pure graphite 372
Among them carbon based materials such as activated carbons, carbon bers and CNTs have been
extensively investigated as an electrode material for EDL supercapacitors owing to their good electri-
cal conductivity, chemical and mechanical stability, long cycle life, and highly modiable nanostruc-
tures [421424]. Whereas, materials such as,
Fig. 6.11. Electrochemical characterizations of a half-cell composed of Mn
3
O
4
/RGO and Li. The specic capacities are based on
the mass of Mn
3
O
4
in the Mn
3
O
4
/RGO hybrid. (a) Charge (red) and discharge (blue) curves of Mn
3
O
4
/RGO for the rst cycle at a
current density of 40 mA/g. (b) Representative charge (red) and discharge (blue) curves of Mn
3
O
4
/RGO at various current
densities. (c) Capacity retention of Mn
3
O
4
/RGO at various current densities. (d) Capacity retention of free Mn
3
O
4
nanoparticles
without graphene at a current density of 40 mA/g. (Reproduced with permission from [386].)
Fig. 6.12. (A) SEM and, (B) TEM images of graphene-encapsulated silica spheres. (Reproduced with permission from [378].)
RuO
2
and MnO
2
and polymer are promising for psuedocapacitors. Various graphene-based super
capacitor materials are summarized in Table 6.3.
Supercapacitors store charge electrostatically by the adsorption of ions onto electrodes that have
high accessible specic surface area. Therefore, a high specic capacitance active electrode plays a vi-
tal role in efcient energy storage. Various forms of porous carbon, for instance CNT [433436], mes-
oporous carbon [437], activate carbon [438] and carbide derived carbon [439] have been studied for
electrodes in this respect. A new class of material e.g. graphene and RGO, have also been predicted
as a potential candidate for supercapacitor electrodes due to very high specic surface area
(2675 m
2
/g), chemical stability, excellent electrical, thermal conductivity and capacitance and low
cost [331,425,427,440]. Interestingly, graphene has demonstrated the intrinsic capacitance near
21 lF/cm
2
, that set new upper limit for capacitance [441]. Ruoff and coworkers [425], pioneered
the application of chemically reduced graphene in supercapacitor. They have shown CRGs potential
as an electrode for super capacitor, even though the used surface area was 707 m
2
/g and graphene
sheets were not fully accessible by the electrolyte. The supercapacitor had specic capacitances of
135 F/g and 99 F/g in aqueous KOH and organic electrolytes, respectively. Improved capacitance
(191 F/g, in KOH) was obtained after using microwave power to expand GO layers and reduce the
Fig. 6.13. Schematic illustrations of the ternary self-assembly approach to ordered metal oxidegraphene nanocomposites. (a)
Graphene or graphene stacks, which are used as the substrate instead of graphite. Adsorption of surfactant hemimicelles on the
surfaces of the graphene or graphene stacks causes its dispersion in surfactant micelles in an aqueous solution. (b) The self-
assembly of anionic sulfonate surfactant on the graphene surface with oppositely charged metal cation (e.g., Sn2+) species and
the transition into the lamella mesophase toward the formation of SnO
2
graphene nanocomposites, where hydrophobic
graphenes are sandwiched in the hydrophobic domains of the anionic surfactant. (c) Metal oxidegraphene layered
nanocomposites composed of alternating layers of metal oxide nanocrystals and graphene/graphene stacks after crystallization
of metal oxide and removal of the surfactant. (d) Self-assembled hexagonal nanostructure of metal oxide precursor (e.g.,
silicate) with nonionic surfactants (e.g., Pluronic P123) on graphene stacks. (Reproduced with permission from [417].)
GO to RGO (surface area ~463 m
2
/g) [442]. Wang et al. [427] have achieved specic capacitance value
~205 F/g for hydrazine reduce GO of effective surface area ~320 m
2
/g. It is worth noting that the sur-
face area of graphene sheets plays a signicant role which directly affects the performance of the
supercapacitors.
A main drawback of using graphene and RGO is the agglomeration and restacking due to Van der
Waals attraction between the neighboring sheets. The aggregation reduces the effective surface area
resulting loss of capacitance. Therefore, a few researchers have made effort to keep graphene sheets
separated by addition of metal oxide nanoparticles [399]. Metal oxide RuO
2
, MnO
2
and polyaniline
(PANI), nano composite with graphene have also been explored for superior capacitance (Table 6.3).
The approach utilizing nanoparticles to improve the electrochemical performance is an indication of
a positive synergistic effect of graphene sheets and nanoparticles. For example, in RuO
2
/graphene
composite, graphene sheets were well separated by RuO
2
nanoparticles that were attached through
the oxygen containing functional groups on graphene surfaces. The composite exhibited a high spe-
cic capacitance of 570 F/g for 38.3% Ru loading with excellent electrochemical stability (97.9% reten-
tion after 1000 cycles) and high energy density (20.1 W h/kg) at high power density (10 kW/kg).
Similarly, MnO
2
/GO composite electrode had a capacitance of 216 F/g that is much higher than that
of individual GO (10.9 F/g) and bulk MnO
2
(6.8 F/g) [429]. Wu, et al. [432], demonstrated a MnO
2
/
graphene high voltage asymmetric capacitor based on graphene as a negative electrode and MnO
2
/
graphene composite a positive electrode, which exhibited a superior energy density of 30 kW/kg
and power density (5 kW/kg at 7 W h/kg). Although the metal oxidegraphene nano composite have
Table 6.3
Graphene based supercapacitor materials and properties.
Material Specic
Capacitance
(F/g)
Energy
density
Power
density
Electrolyte References
Chemically reduced GO 135 Aqueous KOH [425]
99 Organic electrolyte
Graphenehydrous RuO
2
(38.3 wt%)
570 20.1 W h/kg
at 100 mA/g
1 M H
2
SO
4
[399]
10 kW/kg at
4.3 W h/kg
Graphene (2675 m
2
/g) 550
Graphene (microwave assisted
reduction of GO)
191 At 150 mA/
g discharge
current
5M KOH electrolyte [442]
Thermal reduction in propylene
carbonate
120 Organic electrolyte [426]
Graphene (hydrazine reduced GO) 205 28 W h/kg KOH [427]
10 kW h/g
GraphenePANI (50:50 wt%)
(microwave-solvothermal)
408 1 M H
2
SO
4
[428]
GraphenePANI (in situ anodic
electro-polymerization of PANI
lm on graphene paper)
233 [363]
GraphenePANI 1046 6 M KOH [363]
GrapheneMnO
2
216 1 M Na
2
SO
4
[429]
Polymer modied graphene
sheet + MWCNT
120 [430]
Curved Graphene Sheets 100250 at
current
density 1 A/g
85.6 W h/kg
at 1 A/g
1-Ethyl-3-methylimidazolium
tetrauoroborate
[431]
Thermally reduced graphene 75 F/g 31.9 W h/kg N-butyl-N-methylpyrrolidinium
bis(triuoromethanesulfonyl)imide
(PYR14TFSI)
[421]
117 F/g H
2
SO
4
MnO
2
nanowiregraphene 31 F/g 30.4 W h/kg Neutral aqueous Na
2
SO
4
[432]
shown a great prominence for the supercapacitors and high energy density capacitor, the high energy
density supercapacitors with high charge/discharge rates are still up to research stage. Recent study of
Jang and coworkers [431] reveals the graphene-based supercapacitor that exhibits specic energy
density of 85.6 W h/kg at room temperature and 136 W h/kg at 80 C at very high current density
of 1 A/g. These values are comparable to Ni metal hydride (40100 W h/kg). They have reported that
the mesoporous structure of the curved graphene sheet are responsible, the curved nature of graphene
sheets prevent face to face restacking and maintain large pore size (225 nm) and capacitance
(Fig. 6.14). Further quick chargedischarge ability in seconds and minimal loss of capacity or energy
density make it prominent candidate better than existing batteries.
Recently, graphenepolymer composites have also received much attention owing to their exibil-
ity, and superior capacitance than existing carbon-polymer based capacitor. Among various conduc-
tive polymers, PANI has been considered as a most promising conductive electrode material and
studied considerably with CNT and carbon system [367,369,443446]. A graphene nanosheetsPANI
composite was synthesized by in situ polymerization [367]. The specic capacitance of 1046 F/g
was obtained at a scan rate of 1 mV/s. Conductive graphene nanosheets provide more active sites
for nucleation of PANI and is homogeneously coated by PANI nano particles on both sides, resulting
in energy density of 39 kW h/g at a power density of 70 kW/kg. GraphenePANI composite paper
was also prepared by in situ anodic electropolymerization of polyaniline lm on graphene paper
(Fig. 6.15) [363]. The exible as prepared composite paper combined the high conductivity and ex-
ibility properties of graphene sheet with large capacitance polymer and showed the gravimetric
capacitance of 233 F/g.
6.2.2.3. Other applications. Fuel cells are considered as one of the most promising power sources for the
mobile and stationary applications due to their high energy conversion efciency, low operating tem-
perature and ease of handling. Pt and Pt based materials are widely used for the fuel cell, which ren-
ders them ineffective and prevents fuel oxidation. Recently, graphene based materials have been
explored for fuel cell applications [447449]. The proton exchange membrane (PEM) fuel cells proto-
type using graphene was developed by Serger et al. [448]. They constructed using a Toray paper mod-
ied with RGO/Pt composites as a cathode and Pt-dispersed on carbon black as an anode. The
performance of the fuel cell was compared to unsupported Pt cathode PEM (Fig. 6.16).
The RGO/Pt-based fuel cell showed a maximum power of 161 mW/cm
2
compared to 96 mW/cm
2
for an unsupported Pt-based fuel cell. The role of graphene support not only maximized the availabil-
ity of electrocatalyst surface area for electron transfer but also provided better mass transport of reac-
tants to the electrocatalyst.
Fig. 6.14. Scanning electron microscopy image of curved graphene sheets (scale bar 10 lm). (Reproduced with permission from
[431].)
For biological applications of GO/RGO, RGO-based single-bacterium biodevice, label-free DNA sen-
sor, bacterial DNA/protein and polyelectrolyte chemical transistor have been reported [99]. Liu et al.
observed that the GO sheets are biocompatible without obvious toxicity and employed GO for drug
delivery [97]. One of the promising targeting methods is the use of magnetic particles loaded with
drugs. Thus, magnetic NPs with graphene composites have been used in various areas of drug carrier
and magnetic resonance imaging (MRI) [284,376,377,450]. The magnetization curve of GOFe
3
O
4
composite was measured at room temperature (Fig. 6.17) showed a magnetic hysteresis loop of S
line curve with nearly zero value of the magnetic remanence. This suggested that GOFe
3
O
4
exhibited
a superparamagnetic behavior.
Myung et al. reported the assembly of Au NPs fabricated on top of a reduced GO junction [404]. At
the crossing point the forward bias from10 to 10 V (or reverse bias from 10 to 10 V) sweep curves
showed a positive (or negative) slope indicating an n-type (or p-type) FET behavior (Fig. 6.18a). It indi-
cates that in the forward sweep, charges move along in n-type channels (right of Fig. 6.18b). While, in
reverse sweep, charge transfer shows p-type characteristics left of Fig. 6.18b. These properties
Fig. 6.15. Digital camera images of (left) two freestanding G-papers (30 mm, 10 mm) and (right) a exible G-paper.
Fig. 6.16. Galvanostatic fuel cell polarization (IV) curves (ac) and power characteristics (a
/
c
/
) of a fuel cell at 60 C and 1 atm
of back pressure. The cathode composed of (a and a
/
) Pt, (b and b
/
) 1:1 GO-Pt, and 1:1 GO-Pt (hydrazine, 300 C treated).
Electrocatalyst concentration maintained at 0.2 mg/cm
2
Pt. (Reproduced with permission from [448].)
suggested that the metal NPs based graphene device can be operated as a conventional conductive
switching memory by adjusting the charge density on the metal NPs.
Despite the rapid increase of research on chemically functionalized graphene-based NPs composite,
there is lack of theoretical understanding of charge transport studies. Therefore, theory based trans-
port studies with energy band are strongly encouraged in pristine graphene [451,452].
7. Toxicity of graphene/graphene oxide/reduced graphene oxide
Recent advancement in nanoscience opens a wide range of applications of nanoparticles towards
industrial level as well as in medicine. Nanoparticles exhibit extraordinary physiochemical properties
and reect their unique electrical, thermal, and mechanical properties which further bring along a con-
cern about their toxic behavior when exposed to the environment and living system. In the near, the
future potential occupational and public exposure to the nanoparticles will be dramatically increased
due to the versatile applications of nanomaterials [453]. In the recent years government and scientic
Fig. 6.17. Magnetization curve of GOFe
3
O
4
hybrid. (Reproduced with permission from [376].)
Fig. 6.18. Type-switching memory devices and recongurable logic circuits. (a) Typical hysteresis curve of type-switching
memory device based on GO and NPs. It exhibited both n-type and p-type characteristics near zero gate bias voltage. (b)
Operation principle of type-switching memory device. (Reproduced with permission from [404].)
communities put forward more attention towards the bio-safety aspect of the nanomaterials. The main
agenda in the eld of nanotoxicology is to understand the exposure and assessment of nanoparticles,
environmental and biological fate, transport, persistence, transformation, recyclability and overall sta-
bility of the nanoparticles [453]. For example, though carbon nanotubes (CNTs) were an exceptional
scientic nding in the eld of electronics; its wide use allows potential exposure to the environment
and living systems. Several reports have revealed that the CNTs could induce genotoxicity via induction
of reactive oxygen species (ROS) [454,455]. Similarly, graphene and graphene oxide are nowvery much
attractive due to their potential applications such as electrochemical devices, energy storage, and catal-
ysis, adsorption of enzyme, cell imaging, drug delivery, and biosensors. However, information related to
the long term fate, health, and environmental risk assessment of this newly discovered graphene is
widely lacking [456].
RGOs good conductive property has a potential for developing various bio-medical applications
including biosensor, transplant devices, invasive instruments, and implants [457]. RGO and RGO-
Tween 20 paper like composites have been studied for their toxicological aspects. In vitro experi-
ments with mouse broblast cell shows no toxicity of RGO paper [458]. Though surface of the
RGO-Tween 20 composite is electrically insulating, RGO-Tween 20 composite also reported to be
non-toxic towards Vero cells, bovine embryonic cells and CrandellRees feline kidney cells [457].
In contrast to this report, GO-nanosheets reported to be toxic to the bacterial cell [459]. GO-nano-
sheets showed 60% and 70% cell viability decrease in Escherichia coli and Staphylococcus aureus,
respectively. Toxicity of graphene nanosheets towards the E. coli has also been reported [460]. Met-
abolic activity of the E. coli decreased to 13% when incubated with 85 lg/ml GO nanosheets. More-
over, bacterial cell viability loss was almost 98.5% in the same concentration. A transmission
electron microscope study revealed disruption of the bacterial cell membrane and a loss of mem-
brane integrity. Therefore, it may be concluded that the toxicity of graphene oxide nanosheets
mainly attributed to the mechanical damage of the cell membrane of the bacteria due to the sharp
edges of the nanosheets. Moreover, hydrazine reduced GO nanosheets were reported to be more
toxic to the bacterial cell, may be due to the better charge transfer efciency in addition to their
sharp edges [459].
In the in vitro mammalian cell line experiment, the cytotoxic effect of GO was found to be dose and
time dependent, even at a concentration of less than 20 lg/ml. Above 50 lg/ml, GO severely affects
the cell survival rate and induces apoptosis in human broblast cell line [456]. Alteration of cellular
morphology by GO treated broblast cell is shown in Fig. 7.1.
Similar cytotoxic effects were also observed in other cell lines such as MGC803, MCF-7, MDA-MB-
435, and HepG2. Experimental data also demonstrates that the GO enters into the cytoplasm of the
cell and was found to be present in the sub cellular compartments such as lysosomes, mitochondrion,
endoplasm, and even in the nucleus. It has been hypothesized that GO attaches to the cell membrane
and induces down regulation of the adhesion associated gene which in turns affect the cell adhesion
and causing cell to oat in medium. Moreover, GO enters into the cell and can interfere with cellular
metabolism and nally results in cell apoptosis and death [456]. In a recent report, the toxicological
effect of CNTs and graphene nanomaterial towards neuronal PC12 cells are compared [454]. Relative
toxicity of graphene nanostructure is less as compared to CNTs. The 100 lg/ml of the graphene signif-
icantly increases the ROS generation and lactate dehydrogenase release, which are markers of cell
death via necrosis. The reports further document that the shape and size of graphene play a critical
role in evaluating the toxicity caused by graphene. Concentrations and size of the GO used to evaluate
in vitro cytotoxicityy are summarized in Table 7.1.
Recently, the size effect of the GO towards cytotoxicity has been reported [461]. The cytotoxicity of
smaller size GO (160 90 nm) was found to have higher values compared to larger size GO nanosheets
(430 300 nm and 780 410 nm). Smaller size GO also induced apoptosis to the A549 cell at a con-
centration of 200 lg/ml. Though apoptosis was not observed in the presence of larger GO nanosheets
(780 410 nm), a slight increase in necrosis was noticed. Medium size GO nanosheets neither showed
apoptosis nor necrosis towards A549 cells. A similar effect was observed on the cell viability and the
cell mortality was observed in the following order; 160 90 nm size nanosheets >780 410 nm nano-
sheets >430 300 nm nanosheets. The nanosheets of size 430 300 nm showed a signicant decrease
in cell viability only at 200 lg/ml concentration, whereas 160 90 nm and 780 410 nm size nano-
Fig. 7.1. Morphology of human broblast cell line in GO treated and control cell; A-Control, B-100 lg/ml for 1 day; C-20 lg/ml
for 3 days; D-5 lg/ml 5 days. (Reproduced with permission from [456].)
Table 7.1
Size, concentration, and cytotoxicity of GO nanosheet.
Size range Concentration
(lg/ml)
Intra-cellular
localization
Cell/cell line Toxic concentration
(lg/ml)
References
12 lm 5100 Lysosomes,
mitochondrion,
endoplasm, and
nucleus
Human broblast cell,
MGC803, MCF-7,
MDA-MB-435, and
HepG2 cell lines
50 [456]
35 nm 0.1100 PC12 cells 100 [454]
70250 nm 10200 Hardly localized
inside the cell
A549 50 [461]
inside the cell
A549 200 [461]
inside the cell
A549 50 [461]
100700 nm 2085 Endosome A549 85 [460]
100700 nm 2085 E. coli 85 [460]
sheets showed a decrease at a concentration of 50 lg/ml. The reduction in cell viability has been cor-
related to oxidative stress which is generated by GO nanosheets. It has also been found that the GO
nanosheets generate reactive oxygen species in cell free F12 K medium, which is further supported
by the oxidative stress, induced cell viability reduction. The extent of reactive oxygen species gener-
ation is 50% higher in 780 410 nm size nanosheets as compared to 160 90 nm and 430 300 nm
size nanosheets. However, cell proliferation in the GO lm was found to be similar as control and
no cellular internalization of graphene nanosheets was observed. Therefore it can be concluded that
the oxidative stress induced to the cells by GO nanosheets is due to external generation of reactive
oxygen species.
The in vivo study in mice model does not show any toxicity at a dose 60.25 mg per mouse. How-
ever, 0.4 mg per mouse was found to be lethal to the mouse, and all four mice died within 17 days
of GO injection. Histopathology of the lung tissues showed a blocking of the major airways by the
GO conglomeration. Moreover, a loss of 10% body weight was observed within the 1st week of the
GO injection. Long term stay of the GO in kidney makes it a very poor agent for in vivo application,
although GO has been investigated as a cellular imaging and drug delivery agent. It is a challenge to
reduce the toxicity effect of the GO and successfully use GO for medical applications. Therefore,
graphene has been tried to conjugate with biocompatible polymer such as polyethylene glycol
(PEG) and chitosan, for safe bio-medical application. The graphene functionalized with PEG shows
a better solubility and stability in physiological solution and has been studied for in vitro drug deliv-
ery, imaging, and in vivo photothermal therapy for tumor. In vitro experiments with PEG function-
alized GO do not show any cytotoxicity towards HCT-116 cell line [97]. No toxic side effect was
reported in the case of PEG functionalized GO in in vivo mice model at a dose of 20 mg/kg of the
body weight, however an excellent passive targeting of the tumor was achieved. Moreover, haema-
toxylin and eosin stained organ slices did not reveal any organ damage. The tumor disappeared in
the mice received PEG functionalized GO after 1 day of photothermal therapy and no tumor growth
was noticed within 40 days time [462]. However, there is always a chance of quenching the uores-
cence (Cy7) which may leads to in inaccurate conclusion regarding the bio-distribution. The same
group has conducted a similar kind of study with
125
I labeled PEGGO for in vivo pharmacokinetics,
bio-distribution and toxicological study. Stability of the
125
I labeled PEGGO was conrmed by incu-
bating the
125
I labeled PEGGO in 0.9% NaCl solution, mouse plasma and serum at 37 C.
125
I labeled
PEGGO was injected intravenously and radioactive levels in the blood were estimated over times.
PEGGO followed a two component blood circulation model with a half life of 0.39 0.097 h for the
rst phase and 6.97 0.62 h for the second phase. PEGGO was found to be accumulated mainly in
the liver, kidneys, and spleen, however, accumulation in bone marrow was also observed at the early
in the experiments. Radioactivity level measurement and histology analysis of the organs revealed
that with time, accumulated PEGGO cleared out from the organs like the liver, kidneys and spleen.
PEGGO was excreted from the body though renal and fecal excretion which also reectd the kidney
and intestine uptake of PEGGO. Body weight loss or toxic side effects were not observed within the
3 months after the introduction of PEGGO. Moreover, blood biochemistry, hematological and histo-
logical analysis did not reveal any potential toxic effects [463]. Besides the PEGgraphene study,
graphenechitosan composites have also been studied for tissue engineering application; they are
reported to be biocompatible [333]. Recently, few other polymers were tried to reduce graphene
toxicity towards living cells and to make it more compatible for bio-medical use. The 3,4,9,10-
perylene tetracarboxylic acid (PTCA) is one of them, PTCA functionalized graphene sheets did not
show any signicant toxicity towards HeLa cells. PTCAgraphene and aptamer AS1411 sensor have
been successfully shown to differentiate cancer and normal cells [464]. Graphenepolyethylenimine
(PEI) composite also found to be less toxic towards HeLa cells as compared to graphene alone. More-
over, graphenePEI nanocomposite has been demonstrated as an efcient gene transfection vehicle
[465].
Controversial reports exist on cytotoxicity of the graphene/GO/RGO which restricts their potential
bio-medical applications. This may be associated with the different preparation, size of the sheets and
the functionalization. Therefore, thorough toxicology studies of functionalized and bare graphene/GO/
RGO at different doses using different animal model is necessary before any potential bio-medical
applications.
8. Future prospects
It has become evident that the exceptional properties of graphene (including electrical, thermal,
mechanical, optical, and long electron mean free paths) made it compelling for various engineering
applications. Much effort has been devoted to exploring the fundamental physics and chemistry of
graphene. Novel properties such as room temperature quantum Hall effect, highest charge transport
and thermal conductivity originated from graphenes 2-dimensional structures have not been ob-
served earlier from most conventional three-dimensional materials. A large amount of research pub-
lications in the past 5 years signies the importance of graphene that might surpass silicon research in
the development of microelectronics. While silicon based research is at its mature stage to overcome
the technological barrier, graphene is being extensively investigated as it holds the future for micro to
nano scale electronics. The inherent semi-metal characteristic of graphene has been modied to real-
ize the applications in transistors. Graphene nanoribbons and bilayer graphene are the results of such
modication that leads to a suitable band gap and allows the applications in FET. However, graphene
as a new material still faces many challenges ranging from synthesis and characterization to the nal
device fabrication. The exceptional properties were observed in the defect free pristine graphene pre-
pared by graphite exfoliation using scotch tape method which is not appropriate for any large scale
device manufacturing. The alternative methods have progressed to CVD and epitaxially grown single,
bilayer and few-layer graphene. Recent reports demonstrated the scalability using CVD method to wa-
fer scale on different substrates and facile transfer of graphene layer for subsequent device fabrication.
These breakthroughs offer novel and exciting opportunities for semiconductor industries. The chem-
ical exfoliation of graphite into GO followed by thermal and chemical reduction, has offered a cost-
effective production route of reduced graphene oxide on a large scale. However, the chemical and
thermal modication lowers the electrical and mechanical properties, along with its chemical reactiv-
ity leading to lack of control in functionalization by other groups. The controlled oxidation/reduction
and functionalization are very important in tuning the material properties such as band gap, electrical
conductivity, and mechanical properties. Therefore, controlled modication of graphite, GO, and RGO
is crucial in expanding the applications of graphene-based materials. In addition, the large surface of
low density GO and RGO in mass production may possess handling difculty, which can lead to a
health risk due to inhaling and handling toxic reducing chemicals. The health risk associated with
graphene and their derivatives needs to be evaluated through the investigation of the toxicity and bio-
compatibility of these novel carbon structures and its derivatives.
The possible applications of graphene-based material include transparent exible electrodes,
graphene/polymer composites for mechanical parts, energy storage, sensors and organic electronics.
Graphene/polymer composites have showed the lowest percolation threshold for electrical conductiv-
ity and improved mechanical, thermal, and gas barrier properties. However, the core issues such as the
homogeneous distribution of individual graphene platelets, their orientation, connectivity, and inter-
face bonding with matrix still require more investigation. The charge mobility of RGO is considerably
higher than that of the amorphous silicon and existing semi-conducting conjugated polymers, enlight-
ening the probable path for the application in electronics. The main hurdles with any device fabrica-
tion using RGO including defects at atomic level, the folding/wrinkling of RGO and the over lapping of
RGO at macro-scale require continuous research endeavors.
The visibility of monolayer graphene under an optical microscope requires the suitable substrate to
create contrast between different layers due to interference. Current detection of graphene using an
optical microscope depends on the substrate thickness and incident light wavelength. More research
is needed to develop a simple detection method of pristine graphene that is independent of support
material. Aberration corrected high resolution TEM made it possible to reveal defect structures and
graphene quantum dot at atomic resolutions, providing opportunities to visually examine the doping
and defects at atomic levels.
Although the advanced deposition technique of single layer and bilayer made it possible to fabri-
cate large area devices, creating band gap in a controlled and practical manner is still challenging for
the application in logic devices. Several methods aiming at tuning the substrates properties and nano-
ribbon dimension have been proposed to introduce tunable band gap essential for nanoelectronics.
Particularly, this energy band gap can be achieved through quantum connement, bilayer graphene,
and chemical functionalization. The former, quasi-one-dimensional graphene nanoribbon has been
considered with either edge localization or Coulomb blockade effects. Graphene nanoribbon with
appropriate dimension (i.e. 10 nm) is expected to provide right band gap for efcient FET devices.
Cutting graphene into nanoribbon has shown great promise for FET logic applications, but associ-
ated with the electron scattering at the rough edges and disorder fromthe back substrate. On the other
hand, FETs based on graphene bilayer still require large on/off ratio for logic applications. The new op-
tions such as tunnel FETs and bilayer pseudospin FETs have been suggested to tackle the challenge of
the graphene devices problems based on the conventional FET principle. These concepts are supported
by simulation studies but need to be experimented. The latter, oxides form of graphene (GO), has trig-
gered signicant research interest due to large scale integration. However, the electronic band struc-
ture is not clearly understood due to the nanoscale inhomogeneity. Recent atomic scale systematical
investigation and geometrical microscopic studies provided the evidence of tunable band gap through
varying oxidation level and reduction process. Therefore band gap opened graphene based through
GNR and GO have been encouraged to become future practical nano electronic devices comparable
to complementary metal oxide semiconductor circuits.
Acknowledgements
This work is supported by the National Science Foundation for nanotechnology research. We
acknowledge the nancial support obtained from NSF: ECCS 0748091, ECCS 0801924, and NSF:
DMR 0746499 and CBET 0930170. Authors would like to acknowledge editors for their valuable com-
ments and suggestions on the articles.
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Graphene based materials: Past, present and future

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