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A thin flake of ordinary carbon, just one atom thick, lies behind this years Nobel
Prize in Physics. Andre Geim and Konstantin Novoselov have shown that carbon in
such a flat form has exceptional properties that originate from the remarkable world
of quantum physics.
A d G i K t ti N l Andre Geim
Born: 1958, Sochi, Russia
University of Manchester
Konstantin Novoselov
Born: 1974, Nizhny Tagil, Russia
University of Manchester
Prize motivation: "for groundbreaking
experiments regarding the two-dimensional
material graphene"
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1 Department of Physics, University of Manchester, Manchester M13 9PL, UK.
2 Institute for Microelectronics, Technology, 142432 Chernogolovka, Russia.
* To whom correspondence should be addressed. E-mail: geim@man.ac.uk
We describe monocrystalline graphitic films which are a few atoms thick but are nonetheless stable We describe monocrystalline graphitic films, which are a few atoms thick but are nonetheless stable
under ambient conditions, metallic, and of remarkably high quality. The films are found to be a two-
dimensional semimetal with a tiny overlap between valence and conductance bands, and they exhibit a
strong ambipolar electric field effect such that electrons and holes in concentrations up to 10
13
per square
centimeter and with room-temperature mobilities of ~10,000 square centimeters per volt-second can be
induced by applying gate voltage.
What is Graphene?
The term graphene was first used in 1987, referring to a single
layer of graphite within a larger compound (Mouras, 1987)
(A) Allotropes of carbon
http://earthobservatory.nasa.gov/Features/CarbonCycle/carbon_cycle4.php
Carbon is the
most important
element in the
ecosystem (12
th
most abundant
element).
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Carbon can form structures from zero to three-dimensions
Diamond
Dimensionality is one of the most defining material parameters. The
various structural forms of carbon (polymorphism) give carbon a
unique variety of properties and applications.
(B) Graphene
G h i i l l f Graphene is a single layer of
carbon packed in a hexagonal
(honeycomb) lattice, with a
carbon-carbon distance of 0.142
nm. It is the first truly two-
dimensional crystalline
material.
Graphene is a basic building block for graphitic materials of all other
dimensionalities
Graphene
Bilayer graphitic films
Graphite Graphite
Graphene is stronger and stiffer than diamond, yet can be
stretched by a quarter of its length, like rubber. Its surface area
is the largest known for its weight. - Andre Geim
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(C) Bonding in graphene
Electronic configuration: 1s
2
2s
2
2p
2
Orbital Hybridization
Orbital Energy
In graphene, sp
2
hybridized orbitals
are responsible for bonding in the x-
y plane, while the remaining 2p
orbital exists perpendicular to the
plane, contributing 1 conduction
electron per C atom.
(D) Crystal lattice of graphene
Direct lattice
R i l l tti Reciprocal lattice
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Why is Graphene Interesting and Significant?
Graphene is the first truly 2-dimensional material that is stable at room
temperature. It is believed that graphene will bring revolutionary
changes in microelectronics, material science and theoretical physics.
Imagine a piece of paper but a million times thinner. This is how thick
graphene is.
Imagine a material stronger than diamond. This is how strong graphene is
(in the plane).
Imagine a material more conducting than copper. This is how conductive
graphene is
A quote from Andre Geim:
graphene is.
Imagine a machine that can test the same physics that scientists test in, say,
CERN, but small enough to stand on top of your table. Graphene allows
this to happen.
Having such a material in hand, one can easily think of many useful things
that can eventually come out. As concerns new physics, no one doubts
about it already
Landau (1937) and Peierls (1935) argued that strictly 2D crystals were
thermodynamically unstable and could not exist. Their theory pointed
out that a divergent contribution of thermal fluctuations in low-
dimensional crystal lattices should lead to such displacements of atoms
that they become comparable to interatomic distances at any finite
t t
(A) The difficulties of obtaining 2-dimensional crystals
temperature.
The argument was later extended by Mermin (1968) and is strongly
supported by many experimental observations.
The melting temperature of thin films rapidly decreases with
decreasing thickness, and the films become unstable (segregate or
decompose) at a thickness of, typically, dozens of atomic layers.
Before Geims team observed the single atomic layer graphene, it was
believed that true 2D materials could never exist, because it was
thought that any atomic monolayer would have to roll or fold in order to
achieve its lowest potential energy. `
p ) , yp y, y
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- Using electron microscopy it has been observed that within graphene
monolayers small ripples exist. These imperfections are believed to
prevent graphene from rolling and also help to suppress thermal
vibrations.
Why is monolayer graphene stable?
- The strong interatomic bonds ensure that
thermal fluctuations cannot lead to the
generation of dislocations or other crystal
defects even at room temperature.
(B) The electronic configuration of graphene
The unique electrical properties of graphene
come from its electronic configuration, which is
rather different from usual three-dimensional
materials.
Its Fermi surface is characterized by six double
cones In intrinsic (undoped) graphene the
c
Conduction band (empty)
Fermi level
Since the density of states of the material is zero at
the Fermi level, the electrical conductivity of intrinsic
graphene is quite low.
The Fermi level can however be changed by an
cones. In intrinsic (undoped) graphene the
Fermi level is situated at the connection points
of these cones.
k
x
Valence band (full)
Fermi level
electric field so that the material becomes either n-
doped (with electrons) or p-doped (with holes)
depending on the polarity of the applied field.
The electrical conductivity for doped graphene is
potentially quite high.
Valence band
Conduction band
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m
k
m
p
2 2
2 2 2

= = c
m dk
d
2
2
2

=
c
For electrons
The electron behaves like a particle with an
effective mass of:
1
2
2
2

|
|
.
|

\
|
=
dk
d
m
c

=
2
2
dk
d c
c
At the Fermi level, the electron
b h ff ti
. \
dk
This can also be shown from the
acceleration of an electron:
( ) ( )
) (
1 1 1 1
2
2
2
2
2
2 2
ma
dk
d
F
dk
d
dt
dp
dk
d
dt
k d
dk
d
dk
d
dt
dk
dk
d
dk
d
dk
d
dt
d
dt
dv
a
ext
g
c c c e e e

= = = |
.
|

\
|
= |
.
|

\
|
= |
.
|

\
|
= =
1
2
2

|
|
|

|
=
d
m
c

Therefore
= 0
behaves as a zero-effective mass
particle (massless Dirac fermions ).
2 |
|
.

\
=
dk
m
Therefore
Graphenes electrical conductivity is unparalleled at room temperature,
higher than silver (the least resistive metallic material).
Bi-layer graphene has a tunable band gap. Using an electrical field, bi-
layer graphene can be changed from a conductor to a semiconductor.
= 0
Quantum mechanical tunneling in graphene
Normal electrons:
mass = m
cannot reach the speed of light
kinetic energy =(1/2)mv
2
.
Massless elementary particles
( h t t i )
Classical particles: cannot propagate
through potential barriers
Quantum particles: can propagate
(photon, neutrino):
mass =0, speed = c
Electrons in graphene
mass = 0
speed c
g
~ 10
6
m/s (constant)
kinetic energy = c
g
p
- Mimicking relativistic behavior, but
at a much lower speed c ~ c/300
Quantum particles: can propagate
(tunnelling) but probability decays
exponentially with barrier height and
width
Ultrarelativistic quantum particles: can
propagate with the probability of order
of unity (Klein paradox)
at a much lower speed c
g
~ c/300
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(C) Optical properties of graphene
Graphene is practically transparent. In the visible region it
absorbs only 2.3% of the light. This number is given by ,
where, =e
2
/(4tc
0
hc)=1/137, is the fine structure constant that
sets the strength of the electromagnetic force.
-
(D) Thermal properties of graphene
The thermal conductivity of graphene is very high (much higher
than that of silver).
Thermal conductivity measurement on graphene
Temperature is
measured by
micro-Raman
spectroscopy
Diamond 900 2320
Aluminum 250
Silver 429
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Graphene is the strongest known material. The extraordinary strength
comes from the strong covalent carbon-carbon bond as well as the
absence of defects in the 2-dimensional crystal.
(D) Elastic properties of graphene
Elastic property measurement on graphene
Youngs modulus
- Graphene is much stronger than steel, very stretchable and can be
g
used as a flexible conductor.
- The intrinsic strength of graphene can be considered as an 'upper
bound' for the strength of materials that could serve as a goal for
engineers who design materials.
- The measured mechanical properties of graphene can also serve as a
benchmark to validate various theories and computer models.
How is Graphene Prepared?
The most commonly used method for
obtaining single layer graphene is
peeling from high quality graphite.
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Highly Ordered Pyrolytic Graphite
Graphene layers in graphite are held
3.4
Single-layer graphene has delocalized electrons on each side. These
electrons act as a barrier that prevents graphene from binding each other
too tightly In the meantime these electrons can help graphenes binding
together by weak van der Waals forces.
Therefore, it is easy to peel layers off the
bulk sample.
too tightly. In the meantime, these electrons can help graphene s binding
to other surfaces.
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(A) Making graphene samples by mechanical exfoliation
By repeated peeling of flakes of highly oriented pyrolytic graphite,
single and multiple layered graphene samples are obtained.
HOPG flakes
Peel HOPG
Transfer graphene
Pieces to the substrate
Identify graphene samples
under optical microscope
Peeling graphite with tapes has been done for a long time, but the peeled
pieces have a wide range of thicknesses. An efficient technique to screen
the samples for graphene was critical.
The breakthrough in getting single layer graphene was the
observation that graphene becomes visible in an optical microscope
with the color correlating to the number of layers (Novoselov et al.
2004). The sample was placed on top of a Si wafer with a carefully
chosen thickness of SiO
2
, and the visibility comes from a feeble
interference-like contrast with respect to an empty wafer.
The thickness of the SiO
2
coating is critical, a 5% difference in the
thickness can make single-layer graphene completely invisible.
Other (inefficient but can be more accurate) techniques that can be used to
indentify single-layer graphene are AFM, SEM, TEM, Raman, and QHE.
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AFMimage of graphene
TEM image of graphene
SEMimage of graphene. Two edge geometies
A step-by-step
guide for preparing
graphene samples
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(B) Making suspended graphene samples
What Are the Special Properties of Graphene?
The remarkable properties of graphene are due to several facts:
G h i l f t 2D t l Th f d i i d
Graphene has shown some extremely interesting properties that have
not yet observed in any other materials.
- Graphene is a nearly perfect 2D crystal. The error-free ordering is due
to the strong bonding of the carbon atoms. At the same time, the bonds
are flexible (can be stretched to 120%). The lattice also enables
electrons to travel long distances.
- The Fermi surface of graphene is situated at the connection points
between conduction band and valence band. The Fermi level can be
tuned by the application of an electric field.
- The electrons in graphene behave like massless particles, traveling at a
constant speed. This opens up the possibility of studying certain
phenomena more easily on a smaller scale, i.e. without the use of a large
particle accelerator
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(A) Tunable electrical conductivity
Density of states
Graphene displays ambipolar electric
field effect such that charge carriers
can be tuned continuously between
l d h l electrons and holes.
The charge carrier mobilities weakly
depend on temperature. Even at 300 K
the mobilities are still limited by
impurity scattering.
Klaus von Klitzing
Nobel Prize 1985
(B) Quantum hall effect (QHE) in graphene
nect
IB
w E V
y H
= =
B
L
A
w
t
,
1
2
h
e
i
V
I
A
L
H H
H
= = =

o
The Quantum Hall Conductivity
i = 1, 2, 3,
The QHE is an example of a quantum phenomenon occurring on a
macroscopic scale. The QHE is exclusive to two-dimensional (2D)
metals and has elucidated many important aspects of quantum physics
and deepened our understanding of interacting systems.
As many other quantum phenomena, the observation of QHE usually
requires very low temperatures T ~ 1 K.
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In graphene, QHE can be observed at room temperature. This is due to
the highly unusual nature of charge carriers in graphene, which behave
as massless relativistic particles (Dirac fermions) and move with little
scattering under ambient conditions .
graphene
A
L
I
V
xy
H
=
B
x
y
z
L
A
What Are the Potential Applications of Graphene?
Graphene is a very attractive material for a wide range of applications
due to its unusual properties: mechanically very strong, transparent,
flexible, electrical conductivity tunable over a large range either by
chemical doping or electric field.
(A) Electronic applications
- Super-Small Transistors : 1-nanometer graphene transistor is possible
(one atom thick and 10 atoms across. The absolute physical limit of
Moores Law). Graphene has the potential of replacing silicon as a
semiconductor and becomes the base material for integrated circuits,
ultra capacitors, and future electronic devices.
- High frequency electronic devices: The charge carrier mobilities of
graphene are very high.
- Graphene based quantum computation: Low spin-orbit coupling in
graphene may make it a ideal q-bit.
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(B) Material applications
- New composite materials: Composite materials based on graphene
will have great strength and low weight, which can be used for
gasoline tanks, plastic containers, sports equipment, aircraft and
automobile parts, wind turbines, and medical implants.
- Screens and coatings: Graphene is a transparent conductor, it can be
d t t d ti l t d f t h li ht used as transparent conducting electrodes for touch screens, light
panels, solar cells, and organic light emitting devices.
- Energy storage: Graphene is capable of absorbing a large amount of
hydrogen due to the large surface area, and it is possible to make
energy storage devices based on graphene. Graphene powder can
also be used in electric batteries, replacing graphite. The large
surface-to-volume ratio and high conductivity can lead to
improvements in the efficiency of batteries improvements in the efficiency of batteries.
(C) Sensing applications
- Gas sensors: Graphene can be an excellent material for solid-state
gas detection. Its 2D structure, ability to store high amounts of
hydrogen, and change in local electrical resistance makes molecule
detection much easier.
(D) Fundamental physics applications
- Electrical resistance calibration: The quantum Hall effect in graphene
could also possibly contribute to an even more accurate resistance
standard in metrology.
I ti t h i l h i t di i l - Investigate physical phenomena in two-dimensional space
- Provide experimental support for theoretical models of 2D systems.
- Investigate properties of high energy particles on desktop.
What Are the Challenges for Graphene Applications?
- High-quality, large area graphene sheets suitable for industrial g q y, g g p
applications still remain to be demonstrated.
- Accurate control of individual features in graphene devices is still
difficult. Such control will be necessary to provide sufficient
reproducibility in their performance.
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