CHAPTER 1

1.1 INTRODUCTION

Graphene, a two-dimensional, single-layer sheet of sp2 hybridized carbon

atoms is the foundation of all carbon-based systems: the graphite we find
in our pencils is simply a stack of graphene layers; carbon nano-tubes are
made of rolled-up sheets of graphene; and buckminsterfullerene molecules
are nanometer size spheres of wrapped-up graphene.

Graphene has many extraordinary properties. It is about 100 times stronger

than steel by weight,[3] conducts heat and electricity with great efficiency
and is nearly transparent. Researchers have identified the bipolar transistor
effect, ballistic transport of charges and large quantum oscillations in the
material.

Its two-dimensional nature has made graphene—a one-atom-thick crystal

with sp2-carbon honeycomb structure— one of the most attractive
materials for next generation technologies in many fields. It is the basic
structural element of all the other allotropes of carbon, namely graphite,
charcoal, Carbon nano-tubes (CNT) and fullerenes. Graphene has attracted
world-wide attention and research interest, owing to its exceptional
physical properties, such as high electronic conductivity, good thermal
stability, and excellent mechanical strength. It is remarkably strong for its
very low weight (100 times stronger than steel), conducts heat and
electricity with great efficiency and is nearly transparent.

While scientists had theorized about graphene for decades, it was first
produced and isolated by Andre Guim and Konstantin Novoselov in 2004
at University of Manchester.

1
Graphene is very simple as a concept, as it is simply a two dimensional
hexagonal lattice of carbon atoms. However, as simple as the material is,
the properties that emerge as a consequence of this simple structure are
phenomenal. Researchers have been able to identify the bipolar transistor
effect, ballistic transport of charges and large quantum oscillations.
Because it is virtually two-dimensional, it interacts oddly with light and
with other materials.

1.2 STRUCTURE

Fig:-1-1

Graphene is a crystalline allotrope of carbon with 2-dimensional

properties. Its carbon atoms are densely packed in a regular atomic-scale
chicken wire (hexagonal) pattern.

Each atom has four bonds, one σ bond with each of its three neighbors and
one π-bond that is oriented out of plane. The atoms are about 1.42 Å apart.

2
Graphene's hexagonal lattice can be regarded as two interleaving triangular
lattices. This perspective was successfully used to calculate the band
structure for a single graphite layer using a tight-binding approximation.

Graphene's stability is due to its tightly packed carbon atoms and a sp2
orbital hybridization – a combination of orbitals s, px and py that constitute
the σ-bond. The final pz electron makes up the π-bond. The π-bonds
hybridize together to form the π-band and π∗-bands. These bands are
responsible for most of graphene's notable electronic properties, via the
half-filled band that permits free-moving electrons.

Graphene can self-repair holes in its sheets, when exposed to molecules

containing carbon, such as hydrocarbons. Bombarded with pure carbon
atoms, the atoms perfectly align into hexagons, completely filling the
holes.

The atomic structure of isolated, single-layer graphene was studied by

transmission electron microscopy (TEM) on sheets of graphene suspended
between bars of a metallic grid. Electron diffraction patterns showed the
expected honeycomb lattice. Suspended graphene also showed "rippling"
of the flat sheet, with amplitude of about one nanometer. These ripples may
be intrinsic to the material as a result of the instability of two-dimensional
crystals, or may originate from the ubiquitous dirt seen in all TEM images
of graphene. Atomic resolution real-space images of isolated, single-layer
graphene on SiO2 substrates are available via scanning tunneling
microscopy. Photoresist residue, which must be removed to obtain atomic-
resolution images, may be the "adsorbates" observed in TEM images, and
may explain the observed rippling. Rippling on SiO2 is caused by
conformation of graphene to the underlying SiO2, and is not intrinsic.

1.3 PROPERTIES

3
 Fig:-1-2

Graphene has attracted world-wide attention and research interest, owing

to its exceptional physical properties, such as high electronic conductivity,
good thermal stability, and excellent mechanical strength.

1.3.1 CHEMICAL

Graphene is the only form of carbon (or solid material) in which every
atom is available for chemical reaction from two sides (due to the 2D
structure). Atoms at the edges of a graphene sheet have special chemical
reactivity. Graphene has the highest ratio of edge atoms of any allotrope.
Defects within a sheet increase its chemical reactivity. The onset
temperature of reaction between the basal plane of single-layer graphene
and oxygen gas is below 260 °C (530 K). Graphene burns at very low
temperature (e.g., 350 °C (620 K)). Graphene is commonly modified with
oxygen- and nitrogen-containing functional groups and analyzed by
infrared spectroscopy and X-ray photoelectron spectroscopy. However,
determination of structures of graphene with oxygen- and nitrogen-
functional groups requires the structures to be well controlled.

4
In 2013, Stanford University physicists reported that single-layer graphene
is a hundred times more chemically reactive than thicker sheets.

1.3.2 ELECTRONIC

Fig:-1-3

Graphene is a zero-gap semiconductor, because its conduction and valence

bands meet at the Dirac points. Graphene displays remarkable electron
mobility at room temperature, with reported values in excess of 15000
cm2⋅V−1⋅s−1.[36] Hole and electron mobilities were expected to be nearly
identical. The mobility is nearly independent of temperature between 10 K
and 100 K, which implies that the dominant scattering mechanism is defect
scattering. Scattering by graphene's acoustic phonons intrinsically limits
room temperature mobility to 200000 cm2⋅V−1⋅s−1 at a carrier density of
1012 cm−2, 10×106 times greater than copper.

5
The corresponding resistivity of graphene sheets would be 10−6 Ω⋅cm.
This is less than the resistivity of silver, the lowest otherwise known at
room temperature.[84] However, on SiO2 substrates, scattering of
electrons by optical phonons of the substrate is a larger effect than
scattering by graphene’s own phonons. This limits mobility to 40000
cm2⋅V−1⋅s−1.

Charge transport has major concerns due to adsorption of contaminants

such as water and oxygen molecules. This leads to non-repetitive and large
hysteresis I-V characteristics. Researchers must carry out electrical
measurements in vacuum. The protection of graphene surface by a coating
with materials such as SiN, PMMA, h-BN, etc., have been discussed by
researchers. In January 2015, the first stable graphene device operation in
air over several weeks was reported, for graphene whose surface was
protected by aluminum oxide. In 2015 lithium-coated graphene exhibited
superconductivity, a first for graphene.

Graphene doped with various gaseous species (both acceptors and donors)
can be returned to an undoped state by gentle heating in vacuum. Even for
dopant concentrations in excess of 1012 cm−2 carrier mobility exhibits no
observable change. Graphene doped with potassium in ultra-high vacuum
at low temperature can reduce mobility 20-fold. The mobility reduction is
reversible on heating the graphene to remove the potassium.

Due to graphene's two dimensions, charge fractionalization (where the

apparent charge of individual pseudoparticles in low-dimensional systems
is less than a single quantum) is thought to occur. It may therefore be a
suitable material for constructing quantum computers using anonic
circuits.

6
1.3.3 OPTICAL

Graphene's unique optical properties produce an unexpectedly high opacity

for an atomic monolayer in vacuum, absorbing πα ≈ 2.3% of red light,
where α is the fine-structure constant. This is a consequence of the "unusual
low-energy electronic structure of monolayer graphene that features
electron and hole conical bands meeting each other at the Dirac point...
[which] is qualitatively different from more common quadratic massive
bands." Based on the Slonczewski–Weiss–McClure (SWMcC) band model
of graphite, the interatomic distance, hopping value and frequency cancel
when optical conductance is calculated using Fresnel equations in the thin-
film limit.

Although confirmed experimentally, the measurement is not precise

enough to improve on other techniques for determining the fine-structure
constant.

Graphene's band gap can be tuned from 0 to 0.25 eV (about 5 micrometre

wavelength) by applying voltage to a dual-gate bilayer graphene field-
effect transistor (FET) at room temperature. The optical response of
graphene nano-ribbons is tunable into the terahertz regime by an applied
magnetic field. Graphene/graphene oxide systems exhibit electrochromic
behavior, allowing tuning of both linear and ultrafast optical properties.

A graphene-based Bragg grating (one-dimensional photonic crystal) has

been fabricated and demonstrated its capability for excitation of surface
electromagnetic waves in the periodic structure by using 633 nm He–Ne
laser as the light source.

1.3.4 THERMAL CONDUCTIVITY

Thermal transport in graphene is an active area of research, which has

attracted attention because of the potential for thermal management

7
applications. Early measurements of the thermal conductivity of suspended
graphene reported an exceptionally large thermal conductivity of
approximately 5300 W⋅m−1⋅K−1, compared with the thermal conductivity
of pyrolytic graphite of approximately 2000 W⋅m−1⋅K−1 at room
temperature. However, later studies have questioned whether this ultrahigh
value had been overestimated, and have instead measured a wide range of
thermal conductivities between 1500 – 2500 W⋅m−1⋅K−1 for suspended
single layer graphene. The large range in the reported thermal conductivity
can be caused by large measurement uncertainties as well as variations in
the graphene quality and processing conditions. In addition, it is known
that when single-layer graphene is supported on an amorphous material,
the thermal conductivity is reduced to about 500 – 600 W⋅m−1⋅K−1 at
room temperature as a result of scattering of graphene lattice waves by the
substrate, and can be even lower for few layer graphene encased in
amorphous oxide. Likewise, polymeric residue can contribute to a similar
decrease in the thermal conductivity of suspended graphene to
approximately 500 – 600 W⋅m−1⋅K−1for bilayer graphene. Thermal
transport in graphene is a thriving area of research, thanks to graphene's
extraordinary heat conductivity properties and its potential for use in
thermal management applications.

The measured thermal conductivity of graphene is in the range 3000 - 5000

W/mK at room temperature, an exceptional figure compared with the
thermal conductivity of pyrolytic graphite of approximately 2000
W⋅m−1⋅K−1 at room temperature. There are, however, other researches that
estimate that this number is exaggerated, and that the in-plane thermal
conductivity of graphene at room temperature is about 2000–4000
W⋅m−1⋅K−1 for freely suspended samples. This number is still among the
highest of any known material.
Graphene is considered an excellent heat conductor, and several studies
have found it to have unlimited potential for heat conduction based on the
size of the sample, contradicting the law of thermal conduction (Fourier’s
law) in the micrometer scale. In both computer simulations and
experiments, the researchers found that the larger the segment of graphene,
the more heat it could transfer. Theoretically, graphene could absorb an
unlimited amount of heat.

The thermal conductivity increases logarithmically, and researchers

believe that this might be due to the stable bonding pattern as well as being
a 2D material. As graphene is considerably more resistant to tearing than
steel and is also lightweight and flexible, its conductivity could have some
attractive real-world applications.

8
1.3.5 MECHANICAL

Thermal transport in graphene is an active area of research, which has

attracted attention because of the potential for thermal management
applications. Early measurements of the thermal conductivity of suspended
graphene reported an exceptionally large thermal conductivity of
approximately 5300 W⋅m−1⋅K−1, compared with the thermal conductivity
of pyrolytic graphite of approximately 2000 W⋅m−1⋅K−1 at room
temperature. However, later studies have questioned whether this ultrahigh
value had been overestimated, and have instead measured a wide range of
thermal conductivities between 1500 – 2500 W⋅m−1⋅K−1 for suspended
single layer graphene.[133][134][135][136] The large range in the reported
thermal conductivity can be caused by large measurement uncertainties as
well as variations in the graphene quality and processing conditions. In
addition, it is known that when single-layer graphene is supported on an
amorphous material, the thermal conductivity is reduced to about 500 –
600 W⋅m−1⋅K−1 at room temperature as a result of scattering of graphene
lattice waves by the substrate, and can be even lower for few layer
graphene encased in amorphous oxide.[139] Likewise, polymeric residue
can contribute to a similar decrease in the thermal conductivity of
suspended graphene to approximately 500 – 600 W⋅m−1⋅K−1for bilayer
graphene.

1.3.6 BIOLOGICAL

In 2015 researchers used graphene to create sensitive biosensors by using

epitaxial graphene on silicon carbide. The sensors bind to the 8-
hydroxydeoxyguanosine (8-OHdG) and is capable of selective binding
with antibodies. The presence of 8-OHdG in blood, urine and saliva is

9
commonly associated with DNA damage. Elevated levels of 8-OHdG have
been linked to increased risk of developing several cancers.

The Cambridge Graphene Centre and the University of Trieste in Italy

conducted a collaborative research on use of Graphene as electrodes to
interact with brain neurons. The research was recently published in a
journal of ACS Nano.

The research revealed that uncoated Graphene can be used as neuro-

interface electrode without altering or damaging the neural functions such
as signal loss or formation of scar tissue. Graphene electrodes in body stay
significantly more stable than modern day electrodes (of tungsten or
silicon) because of its unique properties such as flexibility, bio-
compatibility, and conductivity. It could possibly help in restoring sensory
function or motor disorders in paralysis or Parkinson patients.

1.4 FORMS
1.4.1 MONOLAYER SHEETS

Fig:- 1-4

10
In 2013 a group of Polish scientists have presented a production unit that
allows to manufacture continuous monolayer sheets. The process is based
on graphene growth on a liquid metal matrix. The product of this process
was called HSMG. It can also be produced by exfoliation.

1.4.2 BILAYER

Fig:-1-5

Bilayer graphene displays the anomalous quantum Hall effect, a tunable

band gap and potential for excitonic condensation –making it a promising
candidate for optoelectronic and nanoelectronic applications. Bilayer
graphene typically can be found either in twisted configurations where the
two layers are rotated relative to each other or graphitic Bernal stacked
configurations where half the atoms in one layer lie atop half the atoms in
the other. Stacking order and orientation govern the optical and electronic
properties of bilayer graphene.

11
One way to synthesize bilayer graphene is via chemical vapor deposition,
which can produce large bilayer regions that almost exclusively conform
to a Bernal stack geometry.

1.4.3 NANORIBBONS

Fig:-1-6

Graphene nanoribbons ("nanostripes" in the "zig-zag" orientation), at low

temperatures, show spin-polarized metallic edge currents, which also
suggests applications in the new field of spintronics. (In the "armchair"
orientation, the edges behave like semiconductors.)

12
 1.4.4 QUANTUM DOTS

Fig:-1-7

Graphene quantum dots (GQDs) have been mainly fabricated by the

microwave assisted hydrothermal method (MAH), the Soft-Template
method, the hydrothermal method, the ultrasonic exfoliation method the
electron beam lithography method, the chemical synthesis method, the
electrochemical preparation method, the graphene oxide (GO) reduction
method, and the C60 catalytic transformation method, etc.

1.5 OXIDE

Using paper-making techniques on dispersed, oxidized and chemically

processed graphite in water, the monolayer flakes form a single sheet and
create strong bonds. These sheets, called graphene oxide paper have a
measured tensile modulus of 32 GPa. The chemical property of graphite
oxide is related to the functional groups attached to graphene sheets. These
can change the polymerization pathway and similar chemical processes.
Graphene oxide flakes in polymers display enhanced photo-conducting
properties. Graphene is normally hydrophobic and impermeable to all
gases and liquids (vacuum-tight). However, when formed into graphene
oxide-based capillary membrane, both liquid water and water vapor flow
through as quickly as if the membrane was not present.

13
 1.5.1 REINFORCED

Fig:-1-8

Graphene reinforced with embedded carbon nanotube reinforcing bars

("rebar") is easier to manipulate, while improving the electrical and
mechanical qualities of both materials.[194][195]

Functionalized single- or multiwalled carbon nanotubes are spin-coated on

copper foils and then heated and cooled, using the nanotubes themselves
as the carbon source. Under heating, the functional carbon groups
decompose into graphene, while the nanotubes partially split and form in-
plane covalent bonds with the graphene, adding strength. π–π stacking
domains add more strength. The nanotubes can overlap, making the
material a better conductor than standard CVD-grown graphene. The
nanotubes effectively bridge the grain boundaries found in conventional

14
graphene. The technique eliminates the traces of substrate on which later-
separated sheets were deposited using epitaxy.

Stacks of a few layers, have been proposed as a cost-effective and

physically flexible replacement for indium tin oxide (ITO) used in displays
and photovoltaic cells.

1.5.2 AEROGEL

Fig:- 1-9

An aerogel made of graphene layers separated by carbon nanotubes was

measured at 0.16 milligrams per cubic centimeter. A solution of graphene
and carbon nanotubes in a mold is freeze dried to dehydrate the solution,
leaving the aerogel. The material has superior elasticity and absorption. It
can recover completely after more than 90% compression, and absorb up
to 900 times its weight in oil, at a rate of 68.8 grams per second. A
graphene aerogel that is seven times lighter than air, and 12% lighter than
the previous record holder . A cubic centimeter of the graphene aerogel
weighs just 0.16 milligrams or, if you’re having a problem conceptualizing

15
that, a cubic meter weighs just 160 grams (5.6 ounces). The graphene
aerogel is so light that an cube inch of the stuff can be balanced on a blade
of grass, the stamen of a flower, or the fluffy seed head of a dandelion

16
 CHAPTER 2

PROCDUCTION AND SYNTHESIS

A rapidly increasing list of production techniques have been developed to

enable graphene's use in commercial applications.

Isolated 2D crystals cannot be grown via chemical synthesis beyond small

sizes even in principle, because the rapid growth of phonon density with
increasing lateral size forces 2D crystallites to bend into the third
dimension.

In all cases, graphite must bond to a substrate to retain its 2d shape.

2.1. EXFOIIATION

As of 2014 exfoliation produced graphene with the lowest number of

defects and highest electron mobility.

2.1.1. Adhesive tape

Andre Geim and Konstantin Novoselov initially used adhesive tape to split
graphite into graphene. Achieving single layers typically requires multiple
exfoliation steps, each producing a slice with fewer layers, until only one
remains. After exfoliation the flakes are deposited on a silicon wafer.
Crystallites larger than 1 mm and visible to the naked eye can be obtained.

2.1.2. Wedge-based

In this method, a sharp single-crystal diamond wedge penetrates onto the

graphite source to exfoliate layers. This method uses highly ordered
pyrolytic graphite (HOPG) as the starting material. The experiments were
supported by molecular dynamic simulations.

17
 2.1.3. Graphite oxide reduction

P. Boehm reported producing monolayer flakes of reduced graphene oxide

in 1962. Rapid heating of graphite oxide and exfoliation yields highly
dispersed carbon powder with a few percent of graphene flakes. Reduction
of graphite oxide monolayer films, e.g. by hydrazine with annealing in
argon/hydrogen also yielded graphene films. Later the oxidation protocol
was enhanced to yield graphene oxide with an almost intact carbon
framework that allows efficient removal of functional groups, neither of
which was originally possible. The measured charge carrier mobility
exceeded 1,000 centimetres (393.70 in)/Vs. Spectroscopic analysis of
reduced graphene oxide has been conducted.

2.1.4. Shearing

In 2014 defect-free, unoxidized graphene-containing liquids were made

from graphite using mixers that produce local shear rates greater than
10×104. The method was claimed to be applicable to other 2D materials,
including boron nitride, Molybdenum disulfide and other layered crystals.

2.2. Chemical vapor deposition

2.2.1. Epitaxy

Epitaxy refers to the deposition of a crystalline overlayer on a crystalline

substrate, where there is registry between the two. In some cases epitaxial
graphene layers are coupled to surfaces weakly enough (by Van der Waals
forces) to retain the two dimensional electronic band structure of isolated
graphene.[22][23] An example of this weak coupling is epitaxial graphene
on SiC.

18
 2.2.2 Silicon carbide

Heating silicon carbide (SiC) to high temperatures (>1100 °C) under low
pressures (~10−6 torr) reduces it to graphene.[25] This process produces
epitaxial graphene with dimensions dependent upon the size of the wafer.
The face of the SiC used for graphene formation, silicon- or carbon-
terminated, highly influences the thickness, mobility and carrier density.

Graphene's electronic band-structure (so-called Dirac cone structure) was

first visualized in this material. Weak anti-localization is observed in this
material, but not in exfoliated graphene produced by the drawing method.
Large, temperature-independent mobilities approach those in exfoliated
graphene placed on silicon oxide, but lower than mobilities in suspended
graphene produced by the drawing method. Even without transfer,
graphene on SiC exhibits massless Dirac fermions. The graphene–substrate
interaction can be further passivated.

The weak van der Waals force that coheres multilayer stacks does not
always affect the individual layers' electronic properties. That is, while the
electronic properties of certain multilayered epitaxial graphenes are
identical to that of a single layer,[38] other properties are affected,[26][27]
as they are in bulk graphite. This effect is well understood theoretically and
is related to the symmetry of the interlayer interactions.

Epitaxial graphene on SiC can be patterned using standard

microelectronics methods. A band gap can be created and tuned by laser
irradiation.

2.2.2 substrates Metal

The atomic structure of metal substrates can seed the growth of graphene.

19
 2.2.1.1 Nickel

High-quality sheets of few-layer graphene exceeding 1 cm2 (0.2 sq in) in

area have been synthesized via CVD on thin nickel films using multiple
techniques. First the film is exposed to Argon gas at 900–1000 degrees
Celsius. Methane is then mixed into the gas, and the methane's
disassociated carbon is absorbed into the film. The solution is then cooled
and the carbon diffuses out of the nickel to form graphene films

2.2.1.1. Copper

Copper foil, at room temperature and very low pressure and in the presence
of small amounts of methane produces high quality graphene. The growth
automatically stops after a single layer forms. Arbitrarily large films can
be created. The single layer growth is due to the low concentration of
carbon in methane. The process is surface-based rather than relying on
absorption into the metal and then diffusion of carbon into graphene layers
on the surface.

2.3. Nanotube slicing

Graphene can be created by cutting open carbon nanotubes. In one such

method multi-walled carbon nanotubes are cut open in solution by action
of potassium permanganate and sulfuric acid. In another method graphene
nanoribbons were produced by plasma etching of nanotubes partly
embedded in a polymer film.

2.4. Carbon dioxide reduction

A highly exothermic reaction combusts magnesium in an oxidation–

reduction reaction with carbon dioxide, producing a variety of carbon

20
nanoparticles including graphene and fullerenes. The carbon dioxide
reactant may be either solid (dry-ice) or gaseous. The products of this
reaction are carbon and magnesium oxide. US patent 8377408 was issued
for this process.

2.5. Spin coating

In 2014, carbon nanotube-reinforced graphene was made via spin coating

and annealing functionalized carbon nanotubes. The resulting material was
stronger, flexible and more conductive than conventional graphene.

2.6. Supersonic spray

Supersonic acceleration of droplets through a Laval nozzle was used to

deposit small droplets of reduced graphene-oxide in suspension on a
substrate. The droplets disperse evenly, evaporate rapidly and display
reduced flake aggregations. In addition, the topological defects (Stone-
Wales defect and C2 vacancies) originally in the flakes disappeared. The
result was a higher quality graphene layer. The energy of the impact
stretches the graphene and rearranges its carbon atoms into flawless
hexagonal graphene with no need for post-treatment.The high amount of
energy also allows the graphene droplets to heal any defects in the
graphene layer that occur during this process.

2.7. Laser

In 2014 a laser-based single-step, scalable approach to graphene

production was announced. The technique produced and patterned porous
three-dimensional graphene film networks from commercial polymer
films. The system used a CO2 infrared laser. The sp3-carbon atoms were
photothermally converted to sp2-carbon atoms by pulsed laser irradiation.
The result exhibits high electrical conductivity. The material can produce

21
interdigitated electrodes for in-plane microsupercapacitors with specific
capacitances of >4 mF cm−2 and power densities of ~9 mW cm−2. Laser-
induced production appeared to allow roll-to-roll manufacturing processes
and provides a route to electronic and energy storage devices.

22
 CHAPTER 3

APPLICATIONS

Potential graphene applications include lightweight, thin, flexible, yet durable display
screens, electric circuits, and solar cells, as well as various medical, chemical and
industrial processes enhanced or enabled by the use of new graphene materials.

In 2008, graphene produced by exfoliation was one of the most expensive materials on
Earth, with a sample the area of a cross section of a human hair costing more than
$1,000 as of April 2008 (about $100,000,000/cm2).Since then, exfoliation procedures
have been scaled up, and now companies sell graphene in large quantities. The price of
epitaxial graphene on Silicon carbide is dominated by the substrate price, which was
approximately $100/cm2 as of 2009. Hong and his team in South Korea pioneered the
synthesis of large-scale graphene films using chemical vapour deposition (CVD) on
thin nickel layers, which triggered research on practical applications,[4] with wafer
sizes up to 30 inches (760 mm) reported.

In 2013, the European Union made a €1 billion grant to be used for research into
potential graphene applications. In 2013 the Graphene Flagship consortium formed,
including Chalmers University of Technology and seven other European universities
and research centers, along with Nokia.

3.1. Medicine
3.1.1. Tissue engineering

Graphene has been investigated for tissue engineering. It has been used as a reinforcing
agent to improve the mechanical properties of biodegradable polymeric
nanocomposites for engineering bone tissue applications. Dispersion of low weight %
of graphene (~0.02 wt.%) increased in compressive and flexural mechanical properties
of polymeric nanocomposites. The addition of graphene nanoparticles in the polymer
matrix lead to improvements in the crosslinking density of the nanocomposite and
better load transfer from the polymer matrix to the underlying nanomaterial thereby
increasing the mechanical properties.

23
 3.1.2 Contrast agents/bioimaging

Functionalized and surfactant dispersed graphene solutions have been designed as

blood pool MRI contrast agents. Additionally, iodine and manganese incorporating
graphene nanoparticles have served as multimodal MRI-CT contrast agents. Graphene
micro- and nano-particles have served as contrast agents for photoacoustic and
thermoacoustic tomography. Graphene has also been reported to be efficiently taken up
cancerous cells thereby enabling the design of drug delivery agents for cancer therapy.
Graphene nanoparticles of various morphologies such as graphene nanoribbons,
graphene nanoplatelets and graphene nanoonions are non-toxic at low concentrations
and do not alter stem cell differentiation suggesting that they may be safe to use for
biomedical applications.

3.1.3 Devices

Graphene's modifiable chemistry, large surface area, atomic thickness and molecularly
gatable structure make antibody-functionalized graphene sheets excellent candidates
for mammalian and microbial detection and diagnosis devices. Graphene is so thin
water has near-perfect wetting transparency which is an important property particularly
in developing bio-sensor applications This means that a sensors coated in graphene
have as much contact with an aqueous system as an uncoated sensor, while it remains
protected mechanically from its environment.

Energy of the electrons with wavenumber k in graphene, calculated in the Tight

Binding-approximation. The unoccupied (occupied) states, colored in blue–red
(yellow–green), touch each other without energy gap exactly at the above-mentioned
six k-vectors.

Integration of graphene (thickness of 0.34 nm) layers as nanoelectrodes into a

nanopore[17] can potentially solve a bottleneck for nanopore-based single-molecule
DNA sequencing.

On November 20, 2013 the Bill & Melinda Gates Foundation awarded $100,000 'to
develop new elastic composite materials for condoms containing nanomaterials like
graphene'.

24
In 2014, graphene-based, transparent (across infrared to ultraviolet frequencies),
flexible, implantable medical sensor microarrays were announced that allow the
viewing of brain tissue hidden by implants. Optical transparency was >90%.
Applications demonstrated include optogenetic activation of focal cortical areas, in
vivo imaging of cortical vasculature via fluorescence microscopy and 3D optical
coherence tomography.

3.1.4 Drug delivery

Researchers in Monash University discovered that the sheet of graphene oxide can be
transformed into liquid crystal droplets spontaneously – like a polymer - simply by
placing the material in a solution and manipulating the pH. The graphene droplets
change their structure at the presence of an external magnetic field. This finding opens
the door for potential use of carrying drug in the graphene droplets and drug release
upon reaching the targeted tissue when the droplets change shape under the magnetic
field. Another possible application is in disease detection if graphene is found to change
shape at the presence of certain disease markers such as toxins.[21][22]

A graphene ‘flying carpet’ was demonstrated to deliver two anti-cancer drugs

sequentially to the lung tumor cells (A549 cell) in a mouse model. Doxorubicin (DOX)
is embedded onto the graphene sheet, while the molecules of tumor necrosis factor-
related apoptosis-inducing ligand (TRAIL) are linked to the nanostructure via short
peptide chains. Injected intravenously, the graphene strips with the drug playload
preferentially concentrate to the cancer cells due to common blood vessel leakage
around the tumor. Receptors on the cancer cell membrane bind TRAIL and cell surface
enzymes clip the peptide thus release the drug onto the cell surface. Without the bulky
TRAIL, the graphene strips with the embedded DOX are swallowed into the cells. The
intracellular acidic environment promotes DOX’s release from graphene. TRAIL on
the cell surface triggers the apoptosis while DOX attacks the nucleus. These two drugs
work synergistically and were found to be more effective than either drug alone.

3.1.5 Biomicrorobotics

Researchers demonstrated a nanoscale biomicrorobot (or cytobot) made by cladding a

living endospore cell with graphene quantum dots. The device acted as a humidity
sensor.

25
 3.1.6 Testing

In 2014 a graphene based blood glucose testing product was announced.

3.2 Electronics

For integrated circuits, graphene has a high carrier mobility, as well as low noise,
allowing it to be used as the channel in a field-effect transistor. Single sheets of
graphene are hard to produce and even harder to make on an appropriate substrate.

In 2008, the smallest transistor so far, one atom thick, 10 atoms wide was made of
graphene.[29] IBM announced in December 2008 that they had fabricated and
characterized graphene transistors operating at GHz frequencies.[30] In May 2009, an
n-type transistor was announced meaning that both n and p-type graphene transistors
had been created.[31][32] A functional graphene integrated circuit was demonstrated –
a complementary inverter consisting of one p- and one n-type graphene transistor.
However, this inverter suffered from a very low voltage gain.

According to a January 2010 report, graphene was epitaxially grown on SiC in a

quantity and with quality suitable for mass production of integrated circuits. At high
temperatures, the quantum Hall effect could be measured in these samples. IBM built
'processors' using 100 GHz transistors on 2-inch (51 mm) graphene sheets.

In June 2011, IBM researchers announced that they had succeeded in creating the first
graphene-based integrated circuit, a broadband radio mixer. The circuit handled
frequencies up to 10 GHz. Its performance was unaffected by temperatures up to 127
°C.

In June 2013 an 8 transistor 1.28 GHz ring oscillator circuit was described.

3.2.1 Transistors

Graphene exhibits a pronounced response to perpendicular external electric fields,

potentially forming field-effect transistors (FET). A 2004 paper documented FETs with
an on-off ratio of ~30 at room temperature.[citation needed] A 2006 paper announced
an all-graphene planar FET with side gates.[38] Their devices showed changes of 2%

26
at cryogenic temperatures. The first top-gated FET (on–off ratio of <2) was
demonstrated in 2007. Graphene nanoribbons may prove generally capable of replacing
silicon as a semiconductor.

US patent 7015142 for graphene-based electronics was issued in 2006. In 2008,

researchers at MIT Lincoln Lab produced hundreds of transistors on a single chip and
in 2009, very high frequency transistors were produced at Hughes Research
Laboratories.

A 2008 paper demonstrated a switching effect based on a reversible chemical

modification of the graphene layer that gives an on–off ratio of greater than six orders
of magnitude. These reversible switches could potentially be employed in nonvolatile
memories.

In 2009, researchers demonstrated four different types of logic gates, each composed
of a single graphene transistor.

Practical uses for these circuits are limited by the very small voltage gain they exhibit.
Typically, the amplitude of the output signal is about 40 times less than that of the input
signal. Moreover, none of these circuits operated at frequencies higher than 25 kHz.

In the same year, tight-binding numerical simulations demonstrated that the band-gap
induced in graphene bilayer field effect transistors is not sufficiently large for high-
performance transistors for digital applications, but can be sufficient for ultra-low
voltage applications, when exploiting a tunnel-FET architecture.

In February 2010, researchers announced transistors with an on/off rate of 100

gigahertz, far exceeding the rates of previous attempts, and exceeding the speed of
silicon transistors with an equal gate length. The 240 nm devices were made with
conventional silicon-manufacturing equipment.

In 2013, researchers demonstrated graphene's high mobility in a detector that allows

broad band frequency selectivity ranging from the THz to IR region (0.76–33 THz)[51]
A separate group created a terahertz-speed transistor with bistable characteristics,
which means that the device can spontaneously switch between two electronic states.
The device consists of two layers of graphene separated by an insulating layer of boron
nitride a few atomic layers thick. Electrons move through this barrier by quantum

27
tunneling. These new transistors exhibit “negative differential conductance,” whereby
the same electric current flows at two different applied voltages.

Graphene does not have an energy band-gap, which presents a hurdle for its
applications in digital logic gates. The efforts to induce a band-gap in graphene via
quantum confinement or surface functionalization have not resulted in a breakthrough.
The negative differential resistance experimentally observed in graphene field-effect
transistors of "conventional" design allows for construction of viable non-Boolean
computational architectures with the gap-less graphene. The negative differential
resistance — observed under certain biasing schemes — is an intrinsic property of
graphene resulting from its symmetric band structure. The results present a conceptual
change in graphene research and indicate an alternative route for graphene's
applications in information processing.

In 2013 researchers reported the creation of transistors printed on flexible plastic that
operate at 25 gigahertz, sufficient for communications circuits and that can be
fabricated at scale. The researchers first fabricate the non-graphene-containing
structures—the electrodes and gates—on plastic sheets. Separately, they grow large
graphene sheets on metal, then peel it off and transfer it to the plastic. Finally, they top
the sheet with a waterproof layer. The devices work after being soaked in water, and
are flexible enough to be folded.

3.2.2 Trilayer graphene

An electric field can change trilayer graphene's crystal structure, transforming its
behavior from metal-like into semiconductor-like. A sharp metal scanning tunneling
microscopy tip was able to move the domain border between the upper and lower
graphene configurations. One side of the material behaves as a metal, while the other
side behaves as a semiconductor. Trilayer graphene can be stacked in either Bernal or
rhombohedral configurations, which can exist in a single flake. The two domains are
separated by a precise boundary at which the middle layer is strained to accommodate
the transition from one stacking pattern to the other.

Silicon transistors function as either p-type or n-type semiconductors, whereas

graphene could operate as both. This lowers costs and is more versatile. The technique

28
provides the basis for a field-effect transistor. Scalable manufacturing techniques have
yet to be developed.

In trilayer graphene, the two stacking configurations exhibit very different electronic
properties. The region between them consists of a localized strain soliton where the
carbon atoms of one graphene layer shift by the carbon–carbon bond distance. The free-
energy difference between the two stacking configurations scales quadratically with
electric field, favoring rhombohedral stacking as the electric field increases.

This ability to control the stacking order opens the way to new devices that combine
structural and electrical properties. Graphene-based transistors could be much thinner
than modern silicon devices, allowing faster and smaller configurations.[citation
needed]

3.2.3 Transparent conducting electrodes

Graphene's high electrical conductivity and high optical transparency make it a

candidate for transparent conducting electrodes, required for such applications as
touchscreens, liquid crystal displays, organic photovoltaic cells, and organic light-
emitting diodes. In particular, graphene's mechanical strength and flexibility are
advantageous compared to indium tin oxide, which is brittle. Graphene films may be
deposited from solution over large areas.

Large-area, continuous, transparent and highly conducting few-layered graphene films

were produced by chemical vapor deposition and used as anodes for application in
photovoltaic devices. A power conversion efficiency (PCE) up to 1.71% was
demonstrated, which is 55.2% of the PCE of a control device based on indium tin oxide.

Organic light-emitting diodes (OLEDs) with graphene anodes have been

demonstrated.[60] The electronic and optical performance of graphene-based devices
are similar to devices made with indium tin oxide.

A carbon-based device called a light-emitting electrochemical cell (LEC) was

demonstrated with chemically-derived graphene as the cathode and the conductive
polymer PEDOT as the anode.[61] Unlike its predecessors, this device contains only
carbon-based electrodes, with no metal.

29
In 2014 a prototype graphene-based flexible display was demonstrated.

3.2.4 Frequency multiplier

In 2009, researchers built experimental graphene frequency multipliers that take an

incoming signal of a certain frequency and output a signal at a multiple of that
frequency.

3.2.5 Optoelectronics

Graphene strongly interacts with photons, with the potential for direct band-gap
creation. This is promising for optoelectronic and nanophotonic devices. Light
interaction arises due to the Van Hove singularity. Graphene displays different time
scales in response to photon interaction, ranging from femtoseconds (ultra-fast) to
picoseconds. Potential uses include transparent films, touch screens and light emitters
or as a plasmonic device that confines light and alters wavelengths.

3.2.6 Quantum dots

Graphene quantum dots (GQDs) keep all dimensions less than 10 nm. Their size and
edge crystallography govern their electrical, magnetic, optical and chemical properties.
GQDs can be produced via graphite nanotomy[67] or via bottom-up, solution-based
routes (Diels-Alder, cyclotrimerization and/or cyclodehydrogenation reactions).[68]
GQDs with controlled structure can be incorporated into applications in electronics,
optoelectronics and electromagnetics. Quantum confinement can be created by
changing the width of graphene nanoribbons (GNRs) at selected points along the
ribbon. It is studied as a catalyst for fuel cells.

3.3 Storage
3.3.1 Supercapacitor

Due to graphene's high surface area to mass ratio, one potential application is in the
conductive plates of supercapacitors.

In February 2013 researchers announced a novel technique to produce graphene

supercapacitors based on the DVD burner reduction approach.

30
In 2014 a supercapacitor was announced that was claimed to achieve energy density
comparable to current lithium-ion batteries.

3.3.2 Batteries

Silicon-graphene anode lithium ion batteries were demonstrated in 2012.

Stable Lithium ion cycling was demonstrated in bi- and few layer graphene films grown
on nickel substrates, while single layer graphene films have been demonstrated as a
protective layer against corrosion in battery components such as the battery case. This
creates possibilities for flexible electrodes for microscale Li-ion batteries where the
anode acts as the active material as well as the current collector.

Researchers built a lithium-ion battery made of graphene and silicon, which was
claimed to last over a week on a single charge and only took 15 minutes to charge.

31