EPL 335: LOW DIMENSIONAL PHYSICS

Term Paper
on
GRAPHENE

Submitted by:
Aishwarya Kumar
2008PH10605
 1. Introduction
Graphene is the name given to a flat monolayer of carbon atoms tightly packed
into a two-dimensional (2D) honeycomb lattice, and is a basic building block for
graphitic materials of all other dimensionalities. It can be wrapped up into 0D
fullerenes, rolled into 1D nanotubes or stacked into 3D graphite. The carbon-
carbon bond length in graphene is about 0.142 nm. Graphene sheets stack to
form graphite with an interplanar spacing of 0.335 nm, which means that a stack
of 3 million sheets would be only one millimeter thick. Graphene is the basic
structural element of some carbon allotropes including graphite, charcoal, carbon
nanotubes, and fullerenes. It can also be considered as an indefinitely large
aromatic molecule, the limiting case of the family of flat polycyclic aromatic
hydrocarbons. Theoretically, graphene (or ‘2D graphite’) has been studied for
sixty years, and is widely used for describing properties of various carbon-based
materials.

Fig 1. Graphene can be wrapped up into 0D fullerenes, rolled into 1D nanotubes or stacked into
3D graphite.
The charge carriers in graphene have a unique nature. Its charge carriers mimic
relativistic particles and are more easily and naturally described starting with the
Dirac equation rather than the Schrödinger equation. Although there is nothing
particularly relativistic about electrons moving around carbon atoms, their
interaction with the periodic potential of graphene’s honeycomb lattice gives rise
to new quasiparticles that at low energies E are accurately described by the (2+1)-
dimensional Dirac equation with an eff ective speed of light vF ≈ 106 m/s. Th ese
quasiparticles, called massless Dirac fermions, can be seen as electrons that have
lost their rest mass m0 or as neutrinos that acquired the electron charge e. The
relativistic like description of electron waves on honeycomb lattices has been
known theoretically for many years, never failing to attract attention, and the
experimental discovery of graphene now provides a way to probe quantum
electrodynamics (QED) phenomena by measuring graphene’s electronic
properties.
2. Properties

Electron diffraction patterns have shown the expected hexagonal lattice of

graphene. Suspended graphene also showed "rippling" of the flat sheet,
with amplitude of about one nanometer. These ripples may be intrinsic to
graphene as a result of the instability of two-dimensional crystals, or may
be extrinsic, originating from the ubiquitous dirt seen in all TEM images of
graphene.

Graphene differs from most conventional three-dimensional materials.

Intrinsic graphene is a semi-metal or zero-gap semiconductor.
Understanding the electronic structure of graphene is the starting point for
finding the band structure of graphite. It was realized early on that the E-k
relation is linear for low energies near the six corners of the two-
dimensional hexagonal Brillouin zone, leading to zero effective mass for
electrons and holes.

Experimental results from transport measurements show that graphene

has a remarkably high electron mobility at room temperature, with
reported values in excess of 15,000 cm2V−1s−1. Additionally, the symmetry
of the experimentally measured conductance indicates that the mobilities
for holes and electrons should be nearly the same. 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 the
acoustic phonons of graphene places intrinsic limits on the room
temperature mobility to 200,000 cm2V−1s−1 at a carrier density of 1012 cm−2.
The corresponding resistivity of the graphene sheet would be 10−6 Ω·cm.
This is less than the resistivity of silver, the lowest resistivity substance
known at room temperature. However, for graphene on silicon dioxide
substrates, scattering of electrons by optical phonons of the substrate is a
larger effect at room temperature than scattering by graphene’s own
phonons. This limits the mobility to 40,000 cm2V−1s−1.

Despite the zero carrier density near the Dirac points, graphene exhibits a
minimum conductivity on the order of 4e2 / h. The origin of this minimum
conductivity is still unclear. However, rippling of the graphene sheet or
ionized impurities in the SiO2 substrate may lead to local puddles of
carriers that allow conduction. Several theories suggest that the minimum
conductivity should be 4e2 / πh; however, most measurements are of order
4e2 / h or greater and depend on impurity concentration.

Recent experiments have probed the influence of chemical dopants on the

carrier mobility in graphene. Doped graphene with various gaseous species
(some acceptors, some donors), and found the initial undoped state of a
graphene structure can be recovered by gently heating the graphene in
vacuum. Even for chemical dopant concentrations in excess of 1012 cm−2
there is no observable change in the carrier mobility.

Due to its two-dimensional property, charge fractionalization (where the

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

Graphene's unique electronic properties produce an unexpectedly high

opacity for an atomic monolayer, with a startlingly simple value: it absorbs
πα ≈ 2.3% of white light, where α is the fine-structure constant. Recently it
has been demonstrated that the bandgap of graphene can be tuned from 0
to 0.25 eV (about 5 micrometer wavelength) by applying voltage to a dual-
gate bilayer graphene field-effect transistor (FET) at room temperature. It is
further confirmed that such unique absorption could become saturated
when the input optical intensity is above a threshold value. This nonlinear
optical behavior is termed saturable absorption and the threshold value is
called the saturation fluence. Graphene can be saturated readily under
strong excitation over the visible to near-infrared region, due to the
universal optical absorption and zero band gap.

Graphene is thought to be an ideal material for spintronics due to small

spin-orbit interaction and near absence of nuclear magnetic moments in
carbon. Electrical spin-current injection and detection in graphene was
recently demonstrated up to room temperature.
By dispersing oxidized and chemically processed graphite in water, and
using paper-making techniques, the monolayer flakes form a single sheet
and bond very powerfully. These sheets, called graphene oxide paper have
a measured tensile modulus of 32 GPa.The peculiar chemical property of
graphite oxide is related to the functional groups attached to graphene
sheets. They even can significantly change the pathway of polymerization
and similar chemical processes. Graphene Oxide flakes in polymers also
shown enhanced photo-conducting properties.

The near-room temperature thermal conductivity of graphene was recently

measured to be between (4.84±0.44) ×103 to (5.30±0.48) ×103 Wm−1K−1.
These measurements, made by a non-contact optical technique, are in
excess of those measured for carbon nanotubes or diamond. It can be
shown by using the Wiedemann-Franz law, that the thermal conduction is
phonon-dominated. However, for a gated graphene strip, an applied gate
bias causing a Fermi energy shift much larger than kBT can cause the
electronic contribution to increase and dominate over the phonon
contribution at low temperatures. The ballistic thermal conductance of
graphene is isotropic. Despite its 2-D nature, graphene has 3 acoustic
phonon modes. The two in-plane modes (LA, TA) have a linear dispersion
relation, whereas the out of plane mode (ZA) has a quadratic dispersion
relation. Due to this, the T2 dependent thermal conductivity contribution of
the linear modes is dominated at low temperatures by the T1.5 contribution
of the out of plane mode.

Graphene appears to be one of the strongest materials ever tested.

Measurements have shown that graphene has a breaking strength 200
times greater than steel, a bulk strength of 130GPa.Using an atomic force
microscope (AFM), the spring constant of suspended graphene sheets has
been measured. Graphene sheets, held together by van der Waals forces,
were suspended over silicon dioxide cavities where an AFM tip was probed
to test its mechanical properties. Its spring constant was in the range 1-5
N/m and the Young's modulus was 0.5 TPa, which differs from that of the
bulk graphite. These high values make graphene very strong and rigid.
These intrinsic properties could lead to using graphene for NEMS
applications such as pressure sensors and resonators.
3. Production of Graphene

3.1 Drawing
In 2004, the Russian researchers obtained graphene by mechanical
exfoliation of graphite. They used cohesive tape to repeatedly split
graphite crystals into increasingly thinner pieces. The tape with attached
optically transparent flakes was dissolved in acetone and, after a few
further steps, the flakes including monolayers were sedimented on a
silicon wafer. Individual atomic planes were then hunted in an optical
microscope. A year later, the researchers simplified the technique and
started using dry deposition, avoiding the stage when graphene floated in
a liquid. Relatively large crystallites (first, only a few micrometres in size
but, eventually, larger than 1 mm and visible by a naked eye) were
obtained by the technique. It is often referred to as a scotch tape or
drawing method. The latter name appeared because the dry deposition
resembles drawing with a piece of graphite. The key for the success
probably was the use of high throughput visual recognition of graphene
on a proper chosen substrate, which provides a small but noticeable
optical contrast.

3.2 Epitaxial Growth

Yet another method of obtaining graphene is to heat silicon carbide to

high temperatures (>1100 °C) to reduce it to graphene. This process
produces a sample size that is dependent upon the size of the SiC
substrate used. The face of the silicon carbide used for graphene creation,
the silicon-terminated or carbon-terminated, highly influences the
thickness, mobility and carrier density of the graphene.

Many important graphene properties have been identified in graphene

produced by this method. For example, the electronic band-structure (so-
called Dirac cone structure) has been first visualized in this material. Weak
anti-localization is observed in this material and not in exfoliated graphene
produced by the pencil trace method. Extremely large, temperature
 independent mobilities have been observed in SiC epitaxial graphene.
They approach those in exfoliated graphene placed on silicon oxide but
still much lower than mobilities in suspended graphene produced by the
drawing method. It was recently shown that even without being
transferred graphene on SiC exhibits the properties of massless Dirac
fermions such as the anomalous quantum Hall effect.

The weak van der Waals force that provides the cohesion of multilayer
graphene stacks does not always affect the electronic properties of the
individual graphene layers in the stack. That is, while the electronic
properties of certain multilayered epitaxial graphenes are identical to that
of a single graphene layer, in other cases the properties are affected as they
are for graphene layers in bulk graphite. This effect is theoretically well
understood and is related to the symmetry of the interlayer interactions.

Epitaxial graphene on silicon carbide can be patterned using standard

microelectronics methods.

Graphene can also be epitaxially grown on metals. This method uses the
atomic structure of a metal substrate to seed the growth of the graphene
(epitaxial growth). Graphene grown on ruthenium doesn't typically yield a
sample with a uniform thickness of graphene layers, and bonding between
the bottom graphene layer and the substrate may affect the properties of
the carbon layers. Graphene grown on iridium on the other hand is very
weakly bonded, uniform in thickness, and can be made highly ordered. Like
on many other substrates, graphene on iridium is slightly rippled. Due to
the long-range order of these ripples generation of minigaps in the
electronic band-structure (Dirac cone) becomes visible. High-quality sheets
of few layer graphene exceeding 1 cm2 (0.2 sq in) in area have been
synthesized via chemical vapor deposition on thin nickel films. These sheets
have been successfully transferred to various substrates, demonstrating
viability for numerous electronic applications. An improvement of this
technique has been found in copper foil where the growth automatically
stops after a single graphene layer, and arbitrarily large graphene films can
be created.
4. Applications

4.1 Gas Detection

Graphene makes an excellent sensor due to its 2D structure. The fact that its
entire volume is exposed to its surrounding makes it very efficient to detect
adsorbed molecules. Molecule detection is indirect: as a gas molecule
adsorbs to the surface of graphene, the location of absorption experiences a
local change in electrical resistance. While this effect occurs in other
materials, graphene is superior due to its high electrical conductivity (even
when few carriers are present) and low noise which makes this change in
resistance detectable.

The operational principle of graphene gas detectors is based on changes in

their electrical conductivity, due to gas molecules adsorbed on graphene's
surface and acting as donors or acceptors, similar to other solid-state
sensors. However, the following characteristics of graphene make it possible
to increase the sensitivity to its ultimate limit and detect individual dopants.
First, graphene is a strictly two-dimensional material and, as such, has its
whole volume exposed to surface adsorbates, which maximizes their effect.
Second, graphene is highly conductive, exhibiting metallic conductivity and,
hence, low Johnson noise even in the limit of no charge carriers, where a
few extra electrons can cause notable relative changes in carrier
concentration, n. Third, graphene has few crystal, which ensures a low level
of excess (1/f) noise caused by their thermal switching. Fourth, graphene
allows four-probe measurements on a single-crystal device with electrical
contacts that are ohmic and have low resistance. All of these features
contribute to make a unique combination that maximizes the signal-to-noise
ratio to a level sufficient for detecting changes in a local concentration by
less than one electron charge, e, at room temperature.

Graphene-based gas sensors allow the ultimate sensitivity such that the
adsorption of individual gas molecules could be detected. Large arrays of
such sensors would increase the catchment area , allowing higher sensitivity
for short-time exposures and the detection of active (toxic) gases in as
minute concentrations as practically desirable. The epitaxial growth of few-
layer graphene offers a realistic promise of mass production of such devices.
Our experiments also show that graphene is sufficiently electronically quiet
to be used in single-electron detectors operational at room temperature
and in ultrasensitive sensors of magnetic field or mechanical strain, in which
the resolution is often limited by 1/f noise.

4.2 Graphene Nanoribbons

Graphene nanoribbons (GNRs) are essentially single layers of graphene that

are cut in a particular pattern to give it certain electrical properties.
Depending on how the un-bonded edges are configured, they can either be
in a zigzag or armchair configuration. Calculations based on tight binding
predict that zigzag GNRs are always metallic while armchairs can be either
metallic or semiconducting, depending on their width. However, recent
density functional theory calculations show that armchair nanoribbons are
semiconducting with an energy gap scaling with the inverse of the GNR
width. Indeed, experimental results show that the energy gaps do increase
with decreasing GNR width. Zigzag nanoribbons are also semiconducting
and present spin polarized edges. Their 2D structure, high electrical and
thermal conductivity, and low noise also make GNRs a possible alternative
to copper for integrated circuit interconnects. Some research is also being
done to create quantum dots by changing the width of GNRs at select
points along the ribbon, creating quantum confinement.

4.3 Graphene Transistors

Due to its high electronic quality, graphene has also attracted the interest
of technologists who see it as a way of constructing ballistic transistors.
Graphene exhibits a pronounced response to perpendicular external
electric fields, allowing one to build FETs (field-effect transistors In 2006,
Georgia Tech researchers announced that they had successfully built an all-
graphene planar FET with side gates. Their devices showed changes of 2%
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 in modern technology.
Facing the fact that current graphene transistors show a very poor on-off
ratio, researchers are trying to find ways for improvement. In 2008 a new
switching effect in graphene field-effect devices was demonstrated. This
switching effect is based on a reversible chemical modification of the
graphene layer and gives an on-off ratio of greater than six orders of
magnitude. These reversible switches could potentially be applied to
nonvolatile memories.

In 2009 researchers at the Politecnico di Milano demonstrated four

different types of logic gates, each composed of a single graphene
transistor. In the same year, the Massachusetts Institute of Technology
researchers built an experimental graphene chip known as a frequency
multiplier. It is capable of taking an incoming electrical signal of a certain
frequency and producing an output signal that is a multiple of that
frequency. Although these graphene chips open up a range of new
applications, their practical use is limited by a very small voltage gain
(typically, the amplitude of the output signal is about 40 times less than
that of the input signal). Moreover, none of these circuits was
demonstrated to operate at frequencies higher than 25 kHz.

In February 2010, researchers at IBM reported that they have been able to
create graphene transistors with an on and off rate of 100 gigahertz, far
exceeding the rates of previous attempts, and exceeding the speed of
silicon. The 240 nm graphene transistors made at IBM were made using
extant silicon-manufacturing equipment, meaning that for the first time
graphene transistors are a conceivable—though still fanciful—replacement
for silicon.
5. Conclusion

Graphene is a rapidly rising star on the horizon of materials science and

condensed-matter physics. This strictly two-dimensional material exhibits
exceptionally high crystal and electronic quality, and, despite its short
history, has already revealed a cornucopia of new physics and potential
applications, which are briefly discussed here. Whereas one can be
certain of the realness of applications only when commercial products
appear, graphene no longer requires any further proof of its importance
in terms of fundamental physics. Owing to its unusual electronic
spectrum, graphene has led to the emergence of a new paradigm of
‘relativistic’ condensed-matter physics, where quantum relativistic
phenomena, some of which are unobservable in high-energy physics, can
now be mimicked and tested in table-top experiments. More generally,
graphene represents a conceptually new class of materials that are only
one atom thick, and, on this basis, offers new inroads into low-
dimensional physics that has never ceased to surprise and continues to
provide a fertile ground for applications.
6. References

1. Progress Article Nature Materials 6, 183 - 191 (2007)

doi:10.1038/nmat1849 : The rise of graphene, A. K. Geim & K. S.
Novoselov

2. 100 GHz Transistors from Wafer Scale Epitaxial Graphene Y.-M. Lin*, C.
Dimitrakopoulos, K. A. Jenkins, D. B. Farmer, H.-Y. Chiu, A. Grill, and Ph.
Avouris

3. Detection of individual gas molecules adsorbed on graphene F.

Schedin, A. K. Geim, S. V. Morozov, E. W. Hill, P. Blake, M. I. Katsnelson
& K. S. Novoselov

4. Z-shaped graphene nanoribbon quantum dot device , Z. F. Wang1, Q.

W. Shi, Qunxiang Li, Xiaoping Wang, J. G. Hou, Huaixiu Zheng, Yao Yao,
and Jie Chen

5. www.wikipedia.org

6. www.grapheneworld.org