CHAPTER 2

GRAPHENE
2.1 INTRODUCTION
Carbon is one of the most distinctive elements in the periodic table.
Carbon bonds allow an almost infinite number of carbon derivatives with
other elements, forming the basis of all known organic materials.
Furthermore, carbon atoms can also form very stable bonds with
themselves.
"Graphene" is a combination of graphite and the suffix ene, named by
Hanns Peter Boehm, who described single layer carbon foils in 1962.
Graphene is an allotrope of carbon in the form of a two dimensional,
atomic scale, Honeycomb lattice in which one atom forms each vertex. It is
the basic structural element of other allotropes, including graphite,
charcoal, carbon nanotubes and fullerenes. It can also be considered as an
indefinitely large aromatic molecule, the ultimate case of the family of flat
polycyclic aromatic hydrocarbons.
Graphene has many extraordinary properties. It is about 100 times stronger
than the strongest steel with a hypothetical thickness of 3.35 which is
equal to thickness of the graphene sheet. It conducts heat and electricity
efficiently and is nearly transparent. Researchers have identified the bipolar
transistor effect, ballistic transport of charges and large quantum
oscillations in material.
GRAPHENE DISCOVERY:
Scientists have theorized about graphene for decades. It has likely been
unknowingly produced in small quantities for centuries, through the use of
pencils and other similar applications of graphite. It was originally
observed in electron microscopes in 1962, but not studied further.
8

The material was later rediscovered, isolated and characterized in 2004 by

Andre Geim and Konstantin Novoselov at the University of Manchester.
Research was informed by existing theoretical descriptions of its
composition, structure and properties. High quality graphene proved to be
surprisingly easy to isolate, making more research possible. This work
resulted in the two winning the Nobel Prize in Physics in 2010 "for ground
breaking experiments regarding the two dimensional material graphene."

Figure 2.1 Classification of Carbon allotropes

Figure 2.2 Graphene building block

9

Graphene is the two dimensional building block for carbon based

nanomaterials of all other dimensionalities. It can be wrapped up into 0-D
fullerenes, rolled into 1-D carbon nanotubes or stacked into 3-D graphite as
shown in figure.
2.2 RESEARCH INTEREST
Research interest in graphene (as well as other allotropes of carbon)
has increased, as demonstrated by the publications and patents published as
a function of time. As interest in graphene research increased every year.

Figure 2.3 Graphene publications and patenting by year, compiled from

Web of Science
2.3 PROPERTIES OF GRAPHENE
Graphene has a theoretical specific surface area of 2630 m2/g. This is
much larger than that reported to date for carbon black (typically smaller
than 900 m2/g) or for carbon nanotubes, from 100 to 1000 m2/g and is
similar to activated carbon.
10

2.3.1 Structural properties

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 bond
with each of its three neighbors and one bond that is oriented out of
plane. The atoms are about 1.42 apart. 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 bond. The final pz electron makes up the
bond. The bonds hybridize together to form band and bands. These
bands are responsible for most of graphene's notable electronic properties,
via the half-filled band that permits free moving electrons.

Figure2.4
a) Schematic of graphene crystallite with armchair & zigzag edges.
b) Schematic of electron s- and p-orbitals of one carbon atom in graphene.
c) Band diagram of graphene at k = 0.
2.3.2 Chemical properties
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.

11

The onset temperature of reaction between basal plane of single layer

graphene and oxygen gas is below 260C (530K). It burns at very low
temperature (e.g., 350C (620 K)).
Graphene is commonly modified with oxygen and nitrogen containing
functional groups and analyzed by IR 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. In 2013, Stanford University physicists
reported that single layer graphene is 100 times more chemically reactive
than thicker sheets.

2.3.3 Electronic properties

Graphene is a zero-gap semiconductor, because its conduction and
valence bands meet at the Dirac points. The Dirac points are six locations
in momentum space, on the edge of the Brillouin zone, divided into two
nonequivalent sets of three points. The two sets are labeled K and K'.
Four electronic properties separate it from other condensed matter systems.
However, if the in-plane direction is no longer infinite, but confined, its
electronic structure would change. They are referred to as Graphene
nanoribbons. If it is "zigzag", the band gap would still be zero. If it is
"armchair", the band gap would be non-zero.

2.3.4 Optical properties

Graphene's produce an unexpectedly high opacity for an atomic
monolayer in vacuum, absorbing 2.3% of red light, where 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.

12

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

wavelength) by applying voltage to a dual-gate bilayer GFET at room
temperature.

2.3.5 Stability
Ab-initio

calculations

show

that

graphene

sheet

is

thermodynamically unstable if its size is less than about 20 nm ("graphene

is the least stable structure until about 6000 atoms") and becomes the most
stable fullerene (as within graphite) only for molecules larger than 24,000
atoms.

2.3.6 Thermal conductivity

Early measurements of the thermal conductivity of suspended
graphene reported an exceptionally large thermal conductivity of
approximately 5300 Wm1K1, compared with the thermal conductivity of
pyrolytic graphite of approximately 2000 Wm1K1 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 15002500 Wm1K1 for single layer graphene.

2.3.7 Mechanical properties

The carboncarbon bond length in graphene is about 0.142
nanometers. Graphene sheets stack to form graphite with an inter-planar
spacing of 0.335 nm. Graphene is the strongest material ever tested, with an
intrinsic Tensile strength of 130GPa and a Young's modulus (stiffness) of 1
TPa (150000000 psi). The Nobel announcement illustrated this by saying
that a 1m2 graphene hammock would support a 4 kg cat but would weigh
only as much as one of the cat's whiskers, at 0.77 mg (about 0.001% of the
weight of 1 m2 of paper).
13

Graphene sheets were suspended over SiO2 cavities where an atomic

force microscope (AFM) tip was used to apply a stress to the sheet to test
its mechanical properties. Its spring constant was in range 15 N/m and the
stiffness was 0.5 TPa, which differs from that of bulk graphite. These
intrinsic properties could lead to applications such as NEMS as pressure
sensors and resonators.

2.4 FABRICATION OF GRAPHENE

2.4.1 Exfoliation
Basically there are two different approaches to preparing graphene.
On the one hand graphene can be detached from an already existing
graphite crystal, the so-called exfoliation methods, on the other hand the
graphene layer can be grown directly on a substrate surface.
The first reported preparation of graphene was by Novoselov and Geim in
2004 by exfoliation using a simple adhesive tape.
The Scotch Tape Method
In this micromechanical exfoliation method, graphene is detached
from a graphite crystal using adhesive tape. After peeling it off the
graphite, multiple-layer graphene remains on the tape. By repeated peeling
the multiple-layer graphene is cleaved into various flakes of few-layer
graphene. Afterwards the tape is attached to the substrate and the glue
solved, e.g. by acetone, in order to detach the tape. Finally one last peeling
with an unused tape is performed. The obtained flakes differ considerably
in size and thickness, where the sizes range from nanometers to several tens
of micrometers for single-layer graphene, depending on the preparation of
the used wafer.

14

Single- layer graphene has an absorption rate of 2%, nevertheless it is

possible to see it under alight microscope on SiO2/Si, due to interference
effects. However, it is difficult to obtain larger amounts of graphene by this
method, not even taking into account the lack of controllability. The
complexity of this method is basically low, nevertheless the graphene
flakes need to be found on the substrate surface, which is labour intensive.

Graphite Oxide Exfoliation

The principle of liquid-phase exfoliation can also be used to exfoliate
graphite oxide. Due to several functional groups like epoxide or hyroxyl,
graphene oxide is hydrophilic and can be solved in water by sonication or
stirring. Thereby the layers become negatively charged and thus a
recombination is inhibited by the electrical repulsion.

Figure 2.5
(a) Solution of graphene in liquid phase. The flasks contain solutions after
centrifugation at different frequencies.
(b) Scheme of the exfoliation of graphite oxide. The graphite gets oxidized
and solved in water. Afterwards it gets reduced to graphene.

After centrifugation the graphene oxide has to be reduced to regular

graphene by thermal or chemical methods. It is hardly possible to dispose
of all the oxygen. In fact, an atomic C/O ratio of about 10 still remains.
15

The performance of this method is very similar to liquid-phase exfoliation

of pristine graphene. Only the complexity is higher, since graphite oxide
has to be produced first, which requires the use of several chemicals. Also
the obtained graphene oxide has to be reduced afterwards, using thermal
treatments or chemicals again. The reduced graphene oxide is of very bad
quality compared to pristine graphene, nevertheless graphene oxide could
be the desired product. Graphene oxide modified with Ca and Mg ions is
capable of forming very tensile graphene oxide paper, as the ions are cross
linkers between the functional groups of the graphene flakes.

2.4.2 Dispersion of Graphite

Graphene can be prepared in liquid-phase. This allows up-scaling the
production, in order to obtain a much higher amount of graphene. The
easiest method would be to disperse the graphite in an organic solvent with
nearly the same surface energy as graphite. Thereby, the energy barrier is
reduced, which has to be overcome in order to detach a graphene layer
from the crystal. The solution is then sonicated in an ultrasound bath for
several hundred hours or a voltage is applied. After the dispersion, the
solution has to be centrifuged in order to dispose of the thicker flakes. The
quality of the obtained graphene flakes is very high. Its size however is still
very small, neither is the controllability given. On the other hand,
complexity is very low, and it allows preparing large amounts of graphene.

2.4.3 Substrate Preparation

There are different methods for substrate preparation in order to use
the dispersed graphene in a non-liquid-phase. By vacuum filtration the
solution is sucked through a membrane using a vacuum pump. As a result
the graphene flakes end up as filtration cake of graphene paper.

16

The deposition of graphene on a surface can be done by simple dropcasting where a drop of the solution is placed on top of the substrate. After
the solvents have evaporated, the graphene flakes remain on the surface. In
order to achieve a more homogeneous coating the sample can be rotated
using the spin coating method in order to disperse the solution with the help
of the centrifugal force. With spray-coating, the solution is sprayed onto the
sample, which allows the preparation of larger areas.

2.4.4 Growth on Surfaces

A totally different approach to obtaining graphene is to grow it
directly on a surface. Consequently the size of the obtained layers are not
dependent on initial graphite crystal. The growth can occur in two different
ways. Either carbon already exists in substrate or it has to be added by
chemical vapour deposition (CVD).

Epitaxial Growth
Graphene can be prepared by simply heating and cooling down a SiC
crystal. Generally speaking single- or bi-layer graphene forms on the Si
face of the crystal, whereas few-layer graphene grows on the C face. The
results are highly dependent on parameters used, like temperature, heating
rate, or pressure. In fact, if temperatures and pressure are too high, growth
of nanotubes instead of graphene. The graphitization of SiC was discovered
in 1955, but it was regarded as unwelcome side effect instead of a method
of preparing graphene. The Ni surface has a lattice structure very similar to
the one of graphene, with a miss match of the lattice constant at about 1.3%
.Thus by use of the nickel diffusion method a thin Ni layer is evaporated
onto a SiC crystal. Upon heating the carbon diffuses through the Ni layer
and forms a graphene or graphite layer on the surface, depending on the
heating rate.
17

Thus the produced graphene is easier to detach from the surface than
the graphene produced by the growth on a simple SiC crystal without Ni.

.
Figure 2.6
SEM image of graphene on copper foil. At several locations on the surface
graphene islands form and grow together.
The growth of graphene starts at several locations on the crystal
simultaneously and these graphene islands grow together, as shown in
Figure. Therefore the graphene is not perfectly homogeneous, due to
defects or grain boundaries. Its quality therefore is not as good as that of
exfoliated graphene. However, size of the homogeneous graphene layer is
limited by the size of crystal used. The possibility to produce large amounts
of graphene by epitaxial growth is not as good as by liquid-phase
exfoliation, though the controllability to gain reproducible results is given.
Also the complexity of these methods is comparatively low.

2.4.5 Chemical Vapour Deposition

Chemical vapour deposition is a well-known process in which a
substrate is exposed to gaseous compounds.

18

These compounds decompose on the surface in order to grow a thin film,

whereas the by-products evaporate.

Figure 2.7
(a) Scheme of preparation of graphene by CVD and transfer via polymer
support. The carbon solves into the Ni during the CVD and forms graphene
on the surface after cooling. With a polymer support the graphene can be
stamped onto another substrate, after etching of the Ni layer.
Patterning of the Ni layer allows a control of the shape of the graphene.
(b) Roll-to-roll process of graphene films grown on copper foils and
transferred on a target substrate.

There are a lot of different ways to achieve this, e.g. by heating the sample
with a filament or with plasma. Graphene can be grown by exposing of a
Ni film to a gas mixture of H2, CH4 and Ar at about 1000C. The methane
decomposes on the surface, so that the hydrogen evaporates. The carbon
diffuses into the Ni.
After cooling down in an Ar atmosphere, a graphene layer grows on the
surface, a process similar to the Ni diffusion method. Hence, the average
number of layers depends on the Ni thickness and can be controlled in this
way. Furthermore, the shape of the graphene can also be controlled by
patterning of the Ni layer.
19

These graphene layers can be transferred via polymer support, which

will be attached onto the top of the graphene. After etching the Ni, the
graphene can be stamped onto the required substrate and the polymer
support gets peeled off or etched away. Using this method several layers of
graphene can be stamped onto each other in order to decrease the
resistance. Due to rotation relatively to the other layers, the turbostratic
graphite does not have the Bernal stacking and consequently the single
graphene layers hardly change their electronic properties, since they
interact marginally with the other layers.

2.5 ENERGY BAND STRUCTURE OF GRAPHENE

The band-structure of graphene differs from the band-structures of
semiconductors in that the energy dispersion around the band edges is
linear instead of quadratic. The mobility of charge carriers is limited by
defects in the supporting material or defects in graphene. Electronic
transport that is limited by scattering is called ballistic transport. Ballistic
transport is possible in very pure and defect free graphene. Naturally,
obtaining clean and defect free graphene is difficult and is often not
achieved.
The linearity of band dispersion in graphene means that the velocity of
electrons is independent of energy or momentum. Furthermore, the velocity
of electrons in graphene is at maximum the Fermi velocity, which is 1/300
of the speed of light.
Dirac point at low energies, which leads to zero effective mass of electrons
and holes. Dirac point is the point where the energy bands; viz., the
conduction and valance bands, merge at the six corners of the Brillouin
Zone in Graphene.

20

PHYSICAL DEVICE MODEL

The fundamental physics governing graphene device behavior and
current state of the art. Graphene, a semi-metal allotrope of carbon, is a 2dimensional planar material. In this work, we examine the behavior of
mono-layer and few-layer graphene materials. The physical properties of
the material are largely dictated by the band structure, shown in Figure 2.1.
The band structure describes the allowable energy values that an electron
may have within the material: below the conduction band, but above the
valence band.
At the K point, we observe that the conduction and valence bands touch,
which gives the material its semi-metal properties. At this point, the
electrons are effectively massless. Unfortunately, equations describes full
band structure are not compact, so that nearest neighbor tight-binding
approximation is applied to describes band structure close to K point,
where mobility is highest.

where a is atom-to-atom length in carbon, 1.42 , and k is wave vector.

The approximation is locally accurate, as tight-binding formulation reduces
complexity of relationships by assuming that only atoms nearest
neighbor affects the atom itself.
This formulation allows us to plot the dependence of energy on the 2D
wave-vector (Figure 2.10). The plot indicates that at the 6 K-points, the
conduction band and valence band contact. We can further simplify the
relationship between energy and the wave-vector by looking closer at the
Dirac points. At these points, the dispersion relation can be approximated
as the tip of a cone.
21

Ab-initio band structure of graphene

Fig 2.8 Ab-initio band structure of graphene (energy normalized to EF)

Fermi energy (EF) and the valence band for values less than EF.

where is the reduced Plancks constant and is the Fermi velocity, with
the wave vector k decomposed into the x and y directions. This expression
has been experimentally demonstrated up to 6 eV.
This dispersion relation is used to calculate the density of states g(E),
which describes the occupied Bloch states per energy differential. The
density of states (DoS) can be calculated, based on the Dirac cone model,
as follows

Where the DoS is 0 at the Fermi-Dirac Energy EF.

22

The Fermi-Dirac distribution is given by

where is Boltzmanns constant and is temperature in Kelvins. The

Fermi-Dirac distribution is given by

where Emax can be set to infinity to account for all energy levels.
The Electron concentration in intrinsic graphene is calculated and graph is
plotted by use of MATLAB tool at chapter 5.
Single layer: Tight-binding approach
Graphene is made out of carbon atoms arranged in hexagonal
structure, as shown in Figure. The structure can be seen as a triangular
lattice with a basis of two atoms per unit cell. The lattice vectors can be
written as,

Where a1, a2 are the lattice unit vectors a 1.42 - carbon-carbon distance.
The reciprocal-lattice vectors are given by,

Of particular importance for the physics of graphene are the two points K
and K at the corners of the graphene Brillouin zone.
Their positions in momentum space are given by,

23

The three nearest-neighbour vectors in real space are given by,

The tight-binding Hamiltonian for electrons in graphene considering that

electrons can hop to both nearest- and next-nearest-neighbour atoms has
the form (we use units such that =1).

Fig. 2.9 Honeycomb lattice and its Brillouin zone. Left: lattice structure of
graphene, made out of two interpenetrating triangular lattices.
Right: Dirac cones are located at the K and K points.

Fig 2.10 Nearest neighbor tight-binding formulation for graphene bandstructure (Energy normalized to EF) at 6K points.
24

Comparison of Semiconductor and Graphene energy band diagram

Fig 2.11
In an insulator or semiconductor, an electron bound to an atom can break
free only if it gets enough energy from heat or photon to jump the band
gap. But in graphene the gap is infinitesimal. This is the main reason why
graphenes electron can move easily and very fast.
In graphene, mobility remains high even at high n (> 10 12 cm-2) in both
electrically and chemically-doped devices, which translates into ballistic
transport on submicron scale.At low temperatures, all metallic systems with
high

resistivity

should

exhibit

large

quantum

interference

magentoresistance, leading to metal-insulator transition. This behavior has

been absolutely universal but it was found missing in graphene. Away from
the dirac point graphene becomes a good metal.
Relatively low on-off ratios do not seem to be fundamental problem for
high frequency applications and transistors operating at THz is possible
with graphene-based electronics.

25

Crystal structure and Electrical transport

The most notable feature of graphene is probably its 2D structure.
Compared to its 1D counterpart, carbon nanotubes, this enables some key
advantages for device application.
The advantage of 2D over 3D is that there is no body or bulk charge in a
purely 2D system. This is mainly advantageous compared to silicon-oninsulator (SOI) or deeply scaled transistors, where bulk charge can degrade
device performance. In silicon-MOS technology, these adverse effects are
addressed by complicated device structures such as Tri-Gate FETs, while
graphene inherently circumvents these.
At room temperature, suspended samples have mobility values that can
exceed 100,000 cm/V sec, making graphene the fastest semiconductor at
room temperature.
Although high mobility is a desirable feature, in short channel FETs the
carrier speeds are mainly dictated by the saturation velocity or source
injection velocity. Here, the advantage of graphene over traditional
semiconductors is less obvious and requires further investigation.
Another advantage of graphene is the Ohmic contact resistance with
metals.
In carbon nanotubes, contact resistance is quantized and limited by the
number of modes available within the Fermi energy and generally limited
to 6 k. The continuous band structure in graphene does not pose such
restrictions and contact resistance can be as small as 50 m. Maximum
attainable current densities are also remarkable, higher than 1 mA/m,
almost six orders of magnitude higher than copper.

26