Growth in Field Emission

Properties of Graphene
Nanocomposites

Made by:
Prince Arora (2K12/EP/048)
Amish Popli (2K12/EP/009)
Ali Danish (2K12/EP/008)

ACKNOWLEDGEMENT
I take this opportunity to express my
profound gratitude and deep regards to my
mentor Prof. S.C. Sharma for his
exemplary guidance, monitoring and
constant encouragement throughout the
course of this project. The blessing, help
and guidance given by him time to time
shall carry me a long way in the journey of
life on which I am about to embark.

ABSTRACT
The proposed project is to solve a theoretical model for the field
emission properties of graphene composite thin films. In this
Project Report we study the basic synthesis, properties and
structure of graphene. We extensively study the field emission
properties of graphene which will be extremely helpful in our
future goals related to the project. We have referred many
research papers relating to our subject and made a note of our
findings in this report.

INDEX
S.No.
1

Topic

Basic Properties of graphene

Advantages and uses

Synthesis Of Graphene

Graphene Composites

Field Emission Property

Field emission property of

graphene composites

Conclusion

Bibliography

Introduction about graphene

Page No.

Introduction to graphene

Molecular structure of graphene

High resolution transmission electron

microscope images(TEM) of graphene

Brief History of Graphite Carbon takes its name from the latin
word carbo meaning charcoal. This element is unique in that its
unique electronic structure allows for hybridization to build up sp3,
sp2, and sp networks and, hence, to form more known stable
allotropes than any other element. The most common allotropic
form of carbon is graphite which is an abundant natural mineral
and together with diamond has been known since antiquity.
Graphite consists of sp2 hybridized carbon atomic layers which
are stacked together by weak van der Waals forces. The single
layers of carbon atoms tightly packed into a two-dimensional (2D)
honeycomb crystal lattice is called graphene. This name was

introduced by Boehm, Setton, and Stumpp in 1994 . Graphite

exhibits a remarkable anisotropic behavior with respect to thermal
and electrical conductivity. It is highly conductive in the direction
parallel to the graphene layers because of the in-plane metallic
character, whereas it exhibits poor conductivity in the direction
perpendicular to the layers because of the weak van der Waals
interactions between them. The carbon atoms in the graphene
layer form three bonds with neighboring carbon atoms by
overlapping of sp2 orbitals while the remaining pz orbitals overlap
to form a band of filled orbitals the valence band and a band
of empty * orbitals the conduction band which are
responsible for the high in-plane conductivity. The interplanar
spacing of graphite amounts to 0.34 nm and is not big enough to
host organic molecules/ions or other inorganic species. However
several intercalation strategies have been applied to enlarge the
interlayer galleries of graphite from 0.34 nm to higher values,
which can reach more than 1 nm in some cases, depending on
the size of the guest species. Since the first intercalation of
potassium in graphite, a plethora of chemical species have been
tested to construct what are known as graphite intercalation
compounds (GICs). The inserted species are stabilized between
the graphene layers through ionic or polar interactions without
influencing the graphene structure. Such compounds can be
formed not only with lithium, potassium, sodium, and other alkali
metals, but also with anions such as nitrate, bisulfate, or
halogens. In other cases the insertion of guest molecules may
occur through covalent bonding via chemical grafting reactions
within the interlayer space of graphite; this results in structural
modifications of the graphene planes because the hybridization of
the reacting carbon atoms changes from sp2 to sp3.

A characteristic example is the insertion of strong acids and

oxidizing reagents that creates oxygen functional groups on the
surfaces and at the edges of the graphene layers giving rise to
graphite oxide. Schafheutl first (1840) and Brodie, 19 years later
(1859) were the pioneers in the production of graphite oxide. The
former prepared graphite oxide with a mixture of sulfuric and nitric
acid, while the latter treated natural graphite with potassium
chlorate and fuming nitric acid. Staudenmaier proposed a
variation of the Brodie method where graphite is oxidized by
addition of concentrated sulfuric and nitric acid with potassium
chlorate. A century later (1958) Hummers and Offeman reported
the oxidation of graphite and the production of graphite oxide on
immersing natural graphite in a mixture of H2SO4, NaNO3, and
KMnO4 as a result of the reaction of the anions intercalated
between the graphitic layers with carbon atoms, which breaks the
aromatic character. The strong oxidative action of these species
leads to the formation of anionic groups on graphitic layers,
mostly hydroxylates, carboxylates, and epoxy groups. The out of
planar CO covalent bonds increase the distance between the
graphene layers from 0.35 nm in graphite to about 0.68 nm in
graphite oxide. This increased spacing and the anionic or polar
character of the oxygen groups formed impart to graphene oxide
(GO) a strongly hydrophilic behavior, which allows water
molecules to penetrate between the graphene layers and thereby
increase the interlayer distance even further. Thus graphite oxide
becomes highly dispersible in water. The formation of sp3 carbon
atoms during oxidation disrupts the delocalized system and
consequently electrical conductivity in graphite oxide deteriorates
reaching between 103 and 107 cm depending on the amount of
oxygen.

Graphene is a two-dimensional single-atom thick membrane of

carbon atoms arranged in a honeycomb crystal. It is a perfect
example of a two-dimensional electron system for a physicist, an
elegant form of a two-dimensional organic macromolecule
consisting of benzene rings for a chemist and a material with
immense possibilities for an engineer due to its excellent
electrical, magnetic, thermal, optical and mechanical properties.
Bilayer graphene is also an important material as shown and has
very unique electronic structure and transport properties. Another
direction is of nanopatterned graphene structures, most notably
grapheme nanoribbons consisting of one-dimensional stripes of
the honeycomb arrangement, which lead to bandgap opening,

edge functionalization, etc. Depending on the edge shape, two

important nanoribbons are armchair grapheme nanoribbons and
zigzag graphene nanoribbons shown in Fig. 1.1. Finally, when
multiple graphene layers are stacked, one obtains graphitic
materials, and multiple nanoribbons stacking leads to multilayer
graphene nanoribbons. Historically, the word graphene comes
from the Greek word graphein, which means to write one of the
earliest uses of this material. In the 1800s, the name graphite was
given to the bulk material used in pencils by the German chemist
Wagner. For some time, graphite was mistakenly thought to be a
form of lead. The confusion of lead pencils comes from that
misunderstanding. Nonetheless, grapheme and graphite have
been of immense use to mankind both in physical sciences and in
technology as well as in the art form. The inspiring arrangement
of carbon atoms
leads to the artistic and architectural lattice shell structures most
notable perhaps is Bucky ball by Buckminster Fuller.
The most important historical application of graphite was in the
molds to make cannon balls. It was truly a strategic material. In
fact, the British crown imposed embargo on graphite during the
Napoleonic wars. Other historical uses of graphite include
crucibles due to its refractory nature, lubrication because
graphene planes can slide against each other with ease,
electrodes and motor/generator brushes due to high conductivity,
and materials processing e.g. steel and alloy making. The
intercalation compounds of graphite were first reported in the
1840s and have been extensively studied since the 1930s. In
recent history, the use of graphite as a neutron moderator to
thermalize high energy neutrons in nuclear reactors has been of
great significance. The fundamental breakthroughs towards the
physical understanding of graphene and graphite were routed in
the 1940s and 1950s. Modern derivatives also include carbon
nanofibres (with diameters less than 10 nm) prepared and studied
extensively in the 1970s and 1980s. Graphene can also be
conceptually thought of as a mother material for Bucky ball

molecules and carbon nanotubes. Their discoverers in the 1980s

(by R. F. Curl Jr, H.W. Kroto, R. E. Smalley, J. R. Heath and coworkers) and 1990s (by S. Iijima), respectively, formed the basis
of not only new fundamental research areas, but also exciting
new set of applications.
Since graphene is just an atomic plane of graphite, it was known
to humans in the form of graphite deposits around the globe at
least for few centuries and was effectively discovered since the
invention of X-ray crystallography. It was important to isolate this
atomic plane and, much more important, to show that this is a
unique material worth further studying. Initial theoretical effort to
study its 2D electronic structure was made by P. R.Wallace in
1947 followed by its extension to the electronic structure of 3D
graphite by D. F. Johnston, J. W. McClure and
M. Yamazaki. J. W. McClure also emphasized that the
quasiparticles were Dirac-like, which was re-iterated by
G.Semenoff.
Graphene

Bilayer Graphene

Fundamental Characteristics
Before monolayer graphene was isolated in 2004, it was
theoretically believed that two dimensional compounds could not
exist due to thermal instability when separated. However, once
graphene was isolated, it was clear that it was actually possible,
and it took scientists some time to find out exactly how. After
suspended graphene sheets were studied by transmission
electron microscopy, scientists believed that they found the
reason to be due to slight rippling in the graphene, modifying the
structure of the material. However, later research suggests that it
is actually due to the fact that the carbon to carbon bonds in
graphene are so small and strong that they prevent thermal
fluctuations from destabilizing it.

Electronic Properties
One of the most useful properties of graphene is that it is a zerooverlap semimetal (with both holes and electrons as charge
carriers) with very high electrical conductivity. Carbon atoms have
a total of 6 electrons; 2 in the inner shell and 4 in the outer shell.
The 4 outer shell electrons in an individual carbon atom are
available for chemical bonding, but in graphene, each atom is
connected to 3 other carbon atoms on the two dimensional plane,
leaving 1 electron freely available in the third dimension for
electronic conduction. These highly-mobile electrons are called pi
() electrons and are located above and below the graphene
sheet. These pi orbitals overlap and help to enhance the carbon
to carbon bonds in graphene. Fundamentally, the electronic
properties of graphene are dictated by the bonding and antibonding (the valance and conduction bands) of these pi orbitals.
Combined research over the last 50 years has proved that at the
Dirac point in graphene, electrons and holes have zero effective
mass. This occurs because the energy movement relation (the

spectrum for excitations) is linear for low energies near the 6

individual corners of the Brillouin zone. These electrons and holes
are known as Dirac fermions, or Graphinos, and the 6 corners of
the Brillouin zone are known as the Dirac points. Due to the zero
density of states at the Dirac points, electronic conductivity is
actually quite low. However, the Fermi level can be changed by
doping (with electrons or holes) to create a material that is
potentially better at conducting electricity than, for example,
copper at room temperature.
Tests have shown that the electronic mobility of graphene is very
high, with previously reported results above 15,000 cm2 and
theoretically potential limits of 200,000 cm2 (limited by the
scattering of graphenes acoustic photons). It is said that
graphene electrons act very much like photons in their mobility
due to their lack of mass. These charge carriers are able to travel
sub-micrometer distances without scattering; a phenomenon
known as ballistic transport. However, the quality of the graphene
and the substrate that is used will be the limiting factors. With
silicon dioxide as the substrate, for example, mobility is potentially
limited to 40,000 cm2.

Mechanical Strength
Another of graphenes stand-out properties is its inherent
strength. Due to the strength of its 0.142 Nm-long carbon bonds,
graphene is the strongest material ever discovered, with an
ultimate tensile strength of 130,000,000,000 Pascals (or 130
gigapascals), compared to 400,000,000 for A36 structural steel, or
375,700,000 for Aramid (Kevlar). Not only is graphene
extraordinarily strong, it is also very light at 0.77milligrams per
square metre (for comparison purposes, 1 square meter of paper
is roughly 1000 times heavier). It is often said that a single sheet
of graphene (being only 1 atom thick), sufficient in size enough to
cover a whole football field, would weigh under 1 single gram.

What makes this particularly special is that graphene also

contains elastic properties, being able to retain its initial size after
strain. In 2007, Atomic force microscopic (AFM) tests were carried
out on graphene sheets that were suspended over silicone
dioxide cavities. These tests showed that graphene sheets (with
thicknesses of between 2 and 8 Nm) had spring constants in the
region of 1-5 N/m and a Youngs modulus (different to that of
three-dimensional graphite) of 0.5 TPa. Again, these superlative
figures are based on theoretical prospects using graphene that is
unflawed containing no imperfections whatsoever and currently
very expensive and difficult to artificially reproduce, though
production techniques are steadily improving, ultimately reducing
costs and complexity.

Optical Properties

Graphenes ability to absorb a rather large 2.3% of white light is

also a unique and interesting property, especially considering that
it is only 1 atom thick. This is due to its aforementioned electronic
properties; the electrons acting like massless charge carriers with
very high mobility. A few years ago, it was proved that the amount
of white light absorbed is based on the Fine Structure Constant,
rather than being dictated by material specifics. Adding another
layer of graphene increases the amount of white light absorbed by
approximately the same value (2.3%). Graphenes opacity of
2.3% equates to a universal dynamic conductivity value of
G=e2/4 (2-3%) over the visible frequency range.
Due to these impressive characteristics, it has been observed that
once optical intensity reaches a certain threshold (known as the
saturation fluence) saturable absorption takes place (very high
intensity light causes a reduction in absorption). This is an
important characteristic with regards to the mode-locking of fibre
lasers. Due to graphenes properties of wavelength-insensitive
ultrafast saturable absorption, full-band mode locking has been
achieved using an erbium-doped dissipative soliton fibre laser
capable of obtaining wavelength tuning as large as 30 nm.
In terms of how far along we are to understanding the true
properties of graphene, this is just the tip of the iceberg. Before

graphene is heavily integrated into the areas in which we believe

it will excel at, we need to spend a lot more time understanding
just what makes it such an amazing material. Unfortunately, while
we have a lot of imagination in coming up with new ideas for
potential applications and uses for graphene, it takes time to fully
appreciate how and what graphene really is in order to develop
these ideas into reality. This is not necessarily a bad thing,
however, as it gives us opportunities to stumble over other
previously under-researched or overlooked super-materials, such
as the family of 2D crystalline structures that graphene has born.

Applications and uses of graphene

Graphene, the well-publicised and now famous two-dimensional

carbon allotrope, is as versatile a material as any discovered on
Earth. Its amazing properties as the lightest and strongest
material, compared with its ability to conduct heat and electricity
better than anything else, mean that it can be integrated into a
huge number of applications. Initially this will mean that graphene
is used to help improve the performance and efficiency of current
materials and substances, but in the future it will also be
developed in conjunction with other two-dimensional (2D) crystals
to create some even more amazing compounds to suit an even
wider range of applications. To understand the potential
applications of graphene, you must first gain an understanding of
the basic properties of the material.
The first time graphene was artificially produced; scientists
literally took a piece of graphite and dissected it layer by layer
until only 1 single layer remained. This process is known as
mechanical exfoliation. This resulting monolayer of graphite
(known as graphene) is only 1 atom thick and is therefore the
thinnest material possible to be created without becoming
unstable when being open to the elements (temperature, air,
etc.). Because graphene is only 1 atom thick, it is possible to
create other materials by interjecting the graphene layers with
other compounds (for example, one layer of graphene, one layer
of another compound, followed by another layer of graphene, and
so on), effectively using graphene as atomic scaffolding from
which other materials are engineered. These newly created
compounds could also be superlative materials, just like
graphene, but with potentially even more applications.
After the development of graphene and the discovery of its
exceptional properties, not surprisingly interest in other twodimensional crystals increased substantially. These other 2D
crystals (such as Boron Nitride, Niobium Diselenide and Tantalum
(IV) sulphide), can be used in combination with other 2D crystals

for an almost limitless number of applications. So, as an example,

if you take the compound Magnesium Diboride (MgB2), which is
known as being a relatively efficient superconductor, then
intersperse its alternating boron and magnesium atomic layers
with individual layers of graphene, it improves its efficiency as a
superconductor. Or, another example would be in the case of
combining the mineral Molybdenite (MoS2), which can be used as
a semiconductor, with graphene layers (graphene being a
fantastic conductor of electricity) when creating NAND flash
memory, to develop flash memory to be much smaller and more
flexible than current technology, (as has been proven by a team of
researchers at the cole Polytechnique Fdrale de Lausanne
(EPFL) in Switzerland).
The only problem with graphene is that high-quality graphene is a
great conductor that does not have a band gap (it cant be
switched off). Therefore to use graphene in the creation of future
nano-electronic devices, a band gap will need to be engineered
into it, which will, in turn, reduce its electron mobility to that of
levels currently seen in strained silicone films. This essentially
means that future research and development needs to be carried
out in order for graphene to replace silicone in electrical systems
in the future. However, recently a few research teams have shown
that not only is this possible, it is probable, and we are looking at
months, rather than years, until this is achieved at least at a basic
level. Some say that these kinds of studies should be avoided,
though, as it is akin to changing graphene to be something it is
not.
In any case, these two examples are just the tip of the iceberg in
only one field of research, whereas graphene is a material that
can be utilized in numerous disciplines including, but not limited
to: bioengineering, composite materials, energy technology and
nanotechnology.

Biological Engineering
Bioengineering will certainly be a field in which graphene will
become a vital part of in the future; though some obstacles need
to be overcome before it can be used. Current estimations
suggest that it will not be until 2030 when we will begin to see
graphene widely used in biological applications as we still need to
understand its biocompatibility (and it must undergo numerous
safety, clinical and regulatory trials which, simply put, will take a
very long time). However, the properties that it displays suggest
that it could revolutionise this area in a number of ways. With
graphene offering a large surface area, high electrical
conductivity, thinness and strength, it would make a good
candidate for the development of fast and efficient bioelectric
sensory devices, with the ability to monitor such things as glucose
levels, haemoglobin levels, cholesterol and even DNA
sequencing. Eventually we may even see engineered toxic
graphene that is able to be used as an antibiotic or even
anticancer treatment. Also, due to its molecular make-up and
potential biocompatibility, it could be utilised in the process of
tissue regeneration.
Optical Electronics
One particular area in which we will soon begin to see graphene
used on a commercial scale is that in optoelectronics; specifically
touchscreens, liquid crystal displays (LCD) and organic light
emitting diodes (OLEDs). For a material to be able to be used in
optoelectronic applications, it must be able to transmit more than
90% of light and also offer electrical conductive properties
exceeding 1 x 106 1m1 and therefore low electrical
resistance. Graphene is an almost completely transparent
material and is able to optically transmit up to 97.7% of light. It is
also highly conductive, as we have previously mentioned and so it
would work very well in optoelectronic applications such as LCD

touchscreens for smartphones, tablet and desktop computers and

televisions.
Currently the most widely used material is indium tin oxide (ITO),
and the development of manufacture of ITO over the last few
decades time has resulted in a material that is able to perform
very well in this application. However, recent tests have shown
that graphene is potentially able to match the properties of ITO,
even in current (relatively under-developed) states. Also, it has
recently been shown that the optical absorption of graphene can
be changed by adjusting the Fermi level. While this does not
sound like much of an improvement over ITO, graphene displays
additional properties which can enable very clever technology to
be developed in optoelectronics by replacing the ITO with
graphene. The fact that high quality graphene has a very high
tensile strength, and is flexible (with a bending radius of less than
the required 5-10mm for rollable e-paper), makes it almost
inevitable that it will soon become utilized in these
aforementioned applications.
In terms of potential real-world electronic applications we can
eventually expect to see such devices as graphene based epaper with the ability to display interactive and updatable
information and flexible electronic devices including portable
computers and televisions.

Ultrafiltration
Another standout property of graphene is that while it allows water
to pass through it, it is almost completely impervious to liquids
and gases (even relatively small helium molecules). This means
that graphene could be used as an ultrafiltration medium to act as
a barrier between two substances. The benefit of using graphene
is that it is only 1 single atom thick and can also be developed as

a barrier that electronically measures strain and pressures

between the 2 substances (amongst many other variables). A
team of researchers at Columbia University have managed to
create monolayer graphene filters with pore sizes as small as
5nm (currently, advanced nanoporous membranes have pore
sizes of 30-40nm). While these pore sizes are extremely small, as
graphene is so thin, pressure during ultrafiltration is reduced. Cocurrently, graphene is much stronger and less brittle than
aluminium oxide (currently used in sub-100nm filtration
applications). What does this mean? Well, it could mean that
graphene is developed to be used in water filtration systems,
desalination systems and efficient and economically more viable
biofuel creation.
Composite Materials
Graphene is strong, stiff and very light. Currently, aerospace
engineers are incorporating carbon fibre into the production of
aircraft as it is also very strong and light. However, graphene is
much stronger whilst being also much lighter. Ultimately it is
expected that graphene is utilized (probably integrated into
plastics such as epoxy) to create a material that can replace steel
in the structure of aircraft, improving fuel efficiency, range and
reducing weight. Due to its electrical conductivity, it could even be
used to coat aircraft surface material to prevent electrical damage
resulting from lightning strikes. In this example, the same
graphene coating could also be used to measure strain rate,
notifying the pilot of any changes in the stress levels that the
aircraft wings are under. These characteristics can also help in
the development of high strength requirement applications such
as body armour for military personnel and vehicles.
Photovoltaic Cells
Offering very low levels of light absorption (at around 2.7% of
white light) whilst also offering high electron mobility means that

graphene can be used as an alternative to silicon or ITO in the

manufacture of photovoltaic cells. Silicon is currently widely used
in the production of photovoltaic cells, but while silicon cells are
very expensive to produce, graphene based cells are potentially
much less so. When materials such as silicon turn light into
electricity it produces a photon for every electron produced,
meaning that a lot of potential energy is lost as heat. Recently
published research has proved that when graphene absorbs a
photon, it actually generates multiple electrons. Also, while silicon
is able to generate electricity from certain wavelength bands of
light, graphene is able to work on all wavelengths, meaning that
graphene has the potential to be as efficient as, if not more
efficient than silicon, ITO or (also widely used) gallium
arsenide. Being flexible and thin means that graphene based
photovoltaic cells could be used in clothing; to help recharge your
mobile phone, or even used as retro-fitted photovoltaic window
screens or curtains to help power your home.
Energy Storage
One area of research that is being very highly studied is energy
storage. While all areas of electronics have been advancing over
a very fast rate over the last few decades (in reference to Moores
law which states that the number of transistors used in electronic
circuitry will double every 2 years), the problem has always been
storing the energy in batteries and capacitors when it is not being
used. These energy storage solutions have been developing at a
much slower rate. The problem is this: a battery can potentially
hold a lot of energy, but it can take a long time to charge, a
capacitor, on the other hand, can be charged very quickly, but
cant hold that much energy (comparatively speaking). The
solution is to develop energy storage components such as either
a super capacitor or a battery that is able to provide both of these
positive characteristics without compromise.

Currently, scientists are working on enhancing the capabilities of

lithium ion batteries (by incorporating graphene as an anode) to
offer much higher storage capacities with much better longevity
and charge rate. Also, graphene is being studied and developed
to be used in the manufacture of super capacitors which are able
to be charged very quickly, yet also be able to store a large
amount of electricity. Graphene based micro-super capacitors will
likely be developed for use in low energy applications such as
smart phones and portable computing devices and could
potentially be commercially available within the next 5-10 years.
Graphene-enhanced lithium ion batteries could be used in much
higher energy usage applications such as electrically powered
vehicles, or they can be used as lithium ion batteries are now, in
smartphones, laptops and tablet PCs but at significantly lower
levels of size and weight.

Synthesis of grapheme

Synthesis of Single Layer and Few Layered Graphenes(SLG and

FG) have been synthesized by several methods. In Table 1.1, we
have listed some of these methods. The synthesis procedure can
be broadly classified into exfoliation, chemical vapor deposition
(CVD), arc discharge, and reduction of graphene oxide.

Mechanical Exfoliation
Stacking of sheets in graphite is the result of overlap of partially
filled pz or orbital perpendicular to the plane of the sheet
(involving van der Waals forces). Exfoliation is the reverse of
stacking; owing to the weak bonding and large lattice spacing in
the perpendicular direction compared to the small lattice spacing
and stronger bonding in the hexagonal lattice plane, it has been
tempting to generate graphene sheets through exfoliation of
graphite (EG). Graphene sheets of different thickness can indeed
be obtained through mechanical exfoliation or by peeling off
layers from graphitic materials such as highly ordered pyrolytic
graphite (HOPG), single-crystal graphite, or natural graphite.
Peeling and manipulation of graphene sheets have been
achieved through AFM and STM tips. Greater control over folding
and unfolding could be achieved by modulating the distance or
bias voltage between the tip and the sample. Zhang obtained 10
100 nm thick graphene sheets using graphite island attached to
tip of micro machined Si cantilever to scan over SiO2/Si surface.
Folding and tearing of the sheets arise due to the formation of
sp3-like line defects in the sp2 graphitic network, occurring
preferentially along the symmetry axes of graphite. Novoselov et
al pressed patterned HOPG square meshes on a photo resist
spun over a glass substrate followed by repeated peeling using
scotch tape and then released the flakes so obtained in acetone.

Some flakes got deposited on the SiO2/Si wafer when dipped in

the acetone dispersion. Using this method, atomically thin
graphene sheets were obtained. This method was simplified to
just peeling off of one or a few sheets of graphene using scotch
tape and depositing them on SiO2 (300 nm)/Si substrates.
Although mechanical exfoliation produces graphene of the highest
quality (with least defects), the method is limited due to low
productivity. Chemical exfoliation, on the other hand, possesses
the advantages of bulk-scale production.

Chemical Exfoliation

Chemical exfoliation is a two-step process. The first step is to

increase the interlayer spacing, thereby reducing the interlayer
van der Waals forces. This is achieved by intercalating graphene
to prepare graphene-intercalated compounds (GICs). The GICs
are then exfoliated into graphene with single to few layers by
rapid heating or sonication. A classic example of chemical
exfoliation is the generation of single-layer graphene oxide (SGO)
prepared from graphite oxide by ultrasonication. Graphene oxide
(GO) is readily prepared by the Hummers method involving the
oxidation of graphite with strong oxidizing agents such as KMnO4
and NaNO3 in H2SO4/H3PO4. On oxidation, the interlayer
spacing increases from 3.7 to 9.5 A, and exfoliation resulting in
SLG is achieved by simple ultrasonication in a DMF/water (9:1)
(dimethyl formamide) mixture. The SGO so prepared has a high
density of functional groups, and reduction needs to be carried
out to obtain graphene-like properties.

Chemical Vapor Deposition

Simply put, CVD is a way of depositing gaseous reactants onto a
substrate. The way CVD works is by combining gas molecules
(often using carrier gases) in a reaction chamber which is typically
set at ambient temperature. When the combined gases come into
contact with the substrate within the reaction chamber (which is
heated), a reaction occurs that create a material film on the
substrate surface. The waste gases are then pumped from the
reaction chamber. The temperature of the substrate is a primary
condition that defines the type of reaction that will occur, so it is
vital that the temperature is correct.

During the CVD process, the substrate is usually coated a very

small amount, at a very slow speed, often described in microns of
thickness per hour. The process is similar to physical vapour
deposition (PVD), the only difference being that the precursors
are solid compounds, rather than gases, and therefore the
process is slightly different. The solid compound or compounds
is/are vaporized, and then deposited onto a substrate via
condensation.
The benefits of using CVD to deposit materials onto a substrate
are that the quality of the resulting materials is usually very high.
Other common characteristics of CVD coatings include
imperviousness, high purity, fine grained and increased hardness
over other coating methods. It is a common solution for the
deposit of films in the semiconductor industry, as well as in
optoelectronics, due to the low costs involved compared to the
high purity of films created.
Although there are a number of different formats of CVD, most
modern processes come under two headings separated by the
chemical vapour deposition operating pressure: LPCVD, and
UHVCVD. LPCVD (low pressure CVD) is the CVD procedure
carried out under sub-atmospheric pressures. This low pressure
helps to prevent unwanted reactions and produce more uniform
thickness of coating on the substrate. UHVCVD (ultra-high
vacuum CVD) is a process is which CVD is carried out under
extremely low atmospheric pressures; usually in the region of 106 Pascals.
The disadvantages to using CVD to create material coatings are
that the gaseous by-products of the process are usually very
toxic. This is because the precursor gases used must be highly
volatile in order to react with the substrate, but not so volatile that
it is difficult to deliver them to the reaction chamber. During the

CVD process, the toxic by-products are removed from the

reaction chamber by gas flow to be disposed of properly.
Fundamental Processes in the Creation of CVD Graphene
CVD graphene is created in two steps, the precursor pyrolysis of
a material to form carbon, and the formation of the carbon
structure of graphene using the disassociated carbon atoms. The
first stage, the pyrolysis to disassociated carbon atoms, must be
carried out on the surface of the substrate to prevent the
precipitation of carbon clusters (soot) during the gas phase. The
problem with this is that the pyrolytic decomposition of precursors
requires extreme levels of heat, and therefore metal catalysts
must be used to reduce the reaction temperature.
The second phase of creating the carbon structure out of the
disassociated carbon atoms, also requires a very high level of
heat (over 2500 degrees Celsius without a catalyst), so a catalyst
is imperative at this stage to reduce the temperature needed for a
reaction to occur to around 1000 degrees Celsius. The problem
with using catalysts is that you are effectively introducing more
compounds into the reaction chamber, which will have an effect
on the reactions inside the chamber. One example of these
effects is the way the carbon atoms dissolve into certain
substrates such as Nickel during the cooling phase.
What all this means is that it is vitally important that the CVD
process is very stringently co-ordinated, and that controls are put
in place at every stage of the process to ensure that the reactions
occur effectively, and that the quality of graphene produced is of
the highest attainable.

Problems Associated with the Creation of CVD Graphene

In order to create monolayer or few layer graphene on a
substrate, scientists must first overcome the biggest issues with
the methods that have been observed so far.
The first major problem is that while it is possible to create high
quality graphene on a substrate using CVD, the successful
separation or exfoliation of graphene from the substrate has been
a bit of a stumbling block. The reason for this is primarily because
the relationship between graphene and the substrate it is grown
on is not yet fully understood, so it is not easy to achieve
separation without damaging the structure of the graphene or
affecting the properties of the material. The techniques on how to
achieve this separation differ depending on the type of substrate
used. Often scientists can choose to dissolve the substrate in
harmful acids, but this process commonly affects the quality of the
graphene produced, so other methods are currently being
researched.
One alternative method that has been researched involves the
creation of CVD graphene on a copper (Cu) substrate (in this
example, Cu is used as a catalyst in the reaction). During CVD a
reaction occurs between the copper substrate and the graphene
that create a high level of hydrostatic compression, coupling the
graphene to the substrate. It has been shown to be possible,
however, to intercalate a layer of copper oxide (which is
mechanically and chemically weak) between the graphene and
the copper substrate to reduce this pressure and enable the
graphene to be removed relatively easily (also, in this instance,
the substrate can be reused).
Scientists have also been looking into using Poly(methyl
methacrylate) (PMMA) as a support polymer to facilitate the
transfer of graphene onto an alternate substrate. With this
method, graphene is coated with PMMA, and the previous

substrate is etched. Then, the coated graphene is strong enough

to be transferred to another substrate without damaging the
material. Other support polymers that have been tested include
thermal release tape and PDMS (Polydimethylsiloxane). However,
PMMA has been shown to be the most effective at transferring the
graphene without excessive damage.
Another major hurdle is creating a completely uniform layer of
graphene on a substrate. This is difficult to achieve as the kinetic
transport dynamics of gas is affected by diffusion and convection,
meaning that these values change within the space of a reaction
chamber, in turn affecting the chemical reactions on the substrate.
Also, due to fluid dynamics, there might be a depletion of
reactants by the time gas reaches the further ends of the
substrate, meaning that no reaction will occur. Some scientists
have reported overcoming this issue by modifying the
concentration of gases and also by incorporating spin coating
methods.
Current and Potential Solutions
In terms of overcoming these issues, scientists have been
developing more complex techniques and guidelines to follow in
order to create the highest quality of graphene possible. One
introductory technique to reducing the effects of these issues is by
treating the substrate before the reaction takes place. A copper
substrate can be chemically treated to enable reduced catalytic
activity, increase the Cu grain size and rearrange the surface
morphology in order to facilitate the growth of graphene flakes
that contain fewer imperfections.
This point of treating the substrate prior to deposition is something
that will continue to be researched for a long time, as we slowly
learn how to modify the structure of graphene to suit different
applications. For example, in order to enable graphene to be
effectively used in superconductors, doping must be carried out

on the material in order to create a band-gap. This process could

potentially be something that is carried out on a substrate before
deposition occurs rather than treating the material after CVD.

Arc Discharge

Synthesis of graphene by the arc evaporation of graphite in the

presence of hydrogen has been reported. This procedure yields
graphene arc discharge graphene in H2 atmosphere (HG) sheets
with two to three layers having flake size of 100200 nm. This
makes use of the knowledge that the presence of H2 during arc
discharge process terminates the dangling carbon bonds with
hydrogen and prevents the formation of closed structures. The
conditions that are favorable for obtaining graphene in the inner
walls are high current (above 100 A), high voltage (>50 V), and
high pressure of hydrogen (above 200 Torr). In figure.TEM and
AFM images of HG sample are shown, respectively. This method
has been conveniently used to dope graphene with boron and
nitrogen. To prepare boron-doped graphene (B-HG) and nitrogendoped graphene (N-HG), the discharge is carried out in the
presence of H2 + diborane and H2 + pyridine or ammonia,
respectively. Later, based on these observations, some
modifications in the synthetic conditions also yielded FG in bulk
scale. Cheng et al. used hydrogen arc discharge process as a
rapid heating method to prepare graphene from GO. Arc
discharge in an air atmosphere resulted in graphene nanosheets
that are 100200 nm wide predominantly with two layers. The
yield depends strongly on the initial air pressure. Li et al. have
synthesized N-doped multilayered graphene in He and NH3
atmosphere using the arc discharge method. Arc discharge
carried out in a helium atmosphere has been explored to obtain
graphene sheets with different number of layers by regulating gas
pressures and currents

Graphene Composites
Composites-Composite materials (also called composition
materials or shortened to composites) are materials made from
two or more constituent materials with significantly
different physical or chemical properties, that when combined,
produce a material with characteristics different from the
individual components. The individual components remain
separate and distinct within the finished structure. The new
material may be preferred for many reasons: common examples
include materials which are stronger, lighter or less expensive
when compared to traditional materials.

Typical engineered composite materials include:

Composite building materials such as cements, concrete

Reinforced plastics such as fiber-reinforced polymer

Metal Composites

Ceramic Composites (composite ceramic and metal

matrices)

How are composite materials made?

The three main factors that help mold the end composite material
are the matrix, reinforcement and manufacturing process. As

matrix, many composites use resins, which are thermosetting or

thermo softening plastics (hence the name reinforced plastics
often given to them). These are polymers that hold the
reinforcement together and help determine the physical properties
of the end composite.
Thermosetting plastics begin as liquid but then harden with heat.
They do not return to liquid state and so they are durable, even in
extreme exposure to chemicals and wear. Thermo softening
plastics are hard at low temperatures and but soften with heat.
They are less commonly used but possess interesting advantages
like long shelf life of raw material and capacity for recycling. There
are other matrix materials such as ceramics, carbon and metals
that are used for specific purposes.
Reinforcement materials grow more varied with time and
technology, but the most commonly used ones are still glass
fibers. Advanced composites tend to favor carbon fibers as
reinforcement, which are much stronger than glass fibers, but are
also more expensive. Carbon fiber composites are strong and
light, and are used in aircraft structures and sports gear (golf
clubs and various rackets). They are also increasingly used to
replace metals that replace human bones. Some polymers make
good reinforcement materials, and help make composites that are
strong and light.
The manufacturing process usually involves a mould, in which the
reinforcement is first placed and then the semi-liquid matrix is
sprayed or poured in to form the object. Moulding processes are
traditionally done by hand, though machine processing is
becoming more common. One of the new methods is called
pultrusion and is ideal for making products that are straight and
have a constant cross section, like different kinds of beams.
Products that of thin or complex shape (like curved panels) are
built up by applying sheets of woven fiber reinforcement,
saturated with matrix material, over a mould. Advanced

composites (like those which are used in aircraft) are usually

made from a honeycomb of plastic held between two sheets of
carbon-fiber reinforced composite material, which results in high
strength, low weight and bending stiffness.

Graphene and composite materials

As was stated before, graphene has a myriad of unprecedented
attributes, any number of which could potentially be used to make
extraordinary composites. The presence of graphene can
enhance the conductivity and strength of bulk materials and help
create composites with superior qualities. Graphene can also be
added to metals, polymers and ceramics to create composites
that are conductive and resistant to heat and pressure.

Graphene composites have many potential applications, with

much research going on to create unique and innovative
materials. The applications seem endless, as one graphenepolymer proves to be light, flexible and an excellent electrical
conductor, while another dioxide-graphene composite was found
to be of interesting photocatalytic efficiencies, with many other
possible coupling of materials to someday make all kinds of
composites. The potential of graphene composites includes
medical implants, engineering materials for aerospace and
renewables and much more.

Applications of Graphene-Based Nanocomposites

Graphene has a great number of applications encompassing
engineering, electronics, medicine, energy, industrial, household
design, and many more . A previous review search yielded
several review papers that examined field-oriented and specific

applications of graphene. Majority of the papers dealt with

electronic/sensor-oriented applications, to generalize the broad
applications of graphene and graphene-based nanocomposite
into their respective disciplines. Shen et al. (2012) extensively
reviewed the biomedical applications of graphene including drug
delivery, gene delivery, cancer therapy, biosensing and
bioimaging, GO-based antibacterial materials, and scaffolds for
tissue/cell culturing. Similarly, Huang et al. (2011) and Choi et al.
(2010) explained various phenomena associated with graphene
and graphene-based materials and their applications in the field of
memory devices for electronics, ranging from electrochemical
sensors to instrumentation.

1. Biological Applications of Graphene and Graphene-Based

Nanocomposites
Graphene in various derivatives and in its precursor form has also
shown potential applications in biological/medical fields,
especially related to toxicity. Hu et al. (2010) demonstrated the
antibacterial activity of two types of water dispersible graphene
against E. coli with minimum cytotoxic effects on the human
participants. The group concluded that GO paper can one day be
effectively used in various environmental and biological
applications . Liao et al. (2011) demonstrated the cytotoxicity
effect of graphene and graphene oxide (GO) materials under
controlled physicochemical parameters. The results showed that
GO was more severely hemolytic than graphene and showed high
activity under extremely small size. They observed that, when
chitosan was coated on GO, the hemolytic activity disappeared
completely, showing the biocompatibility of the composite for
erythrocytes. They concluded that the biological or toxicological
responses of the material were dependent on the particle size,

quality, and state, the surface charge, and the oxygen threshold.
Similarly, Liu et al. (2011) compared four different types of
graphene materials (graphite (Gt), graphite oxide (GtO), GO, and
reduced graphene oxide (rGO)) against E. coli, to study the
toxicity effects. The membrane and oxidative stress signals were
used to measure the intensity of toxicity. Their results showed that
GO was the most severely toxic, followed in descending order by
rGO, Gt, and GtO. Santos et al. reported the design, fabrication,
and antimicrobial application of a graphene-poly-N-vinyl carbazole
(P1VK) nanocomposite, resulting in more than 80% microbial
inhibition and toxicity toward a broad array of bacteria. Carpio et
al. (2012) studied the toxicity effects of PVK-GO nanocomposite
onplanktonic microbial cells, E. coli, C. metallidurans B.
subtilis and R. opacus, biofilms, and mammalian fibroblast cells
(NIH 3T3). Their results showed that PVK-GO presented a
stronger antimicrobial effect than pristine GO. They also found
that the PVK-GO was significantly neutral toward the fibroblast
cells, indicating a huge potential of the composite material in
biomedical and industrial applications . Peng et al. (2012) studied
an Mn-ferrite (MnFe2O4)-decorated GO nanocomposite for
biomedical applications. They observed that the magnetic
property of the ferrites can be effectively used as an ideal
hyperthermia and contrast MRI agent. The nanocomposite when
PEGylated showed excellent biocompatibility. Recently, Liu et al.
(2013) synthesized a hydroxyapatite-GO nanocomposite as
biocompatible prosthetic. They found that the (300) and (002)
plane hydroxyapatite nanorods in the graphene matrix played a
crucial role in maintaining the composites mechanical properties.
Given its superior mechanical property, the authors suggested the
nanocomposites potential in composite and biomedical industries
. Many other applications of graphene nanocomposites in the field
of electronics and other disciplines have been reported.
Generalized applications of various kinds of graphene-based
nanocomposites have been described in the literature. These
include sensors, Li-Ion batteries, fuel cells solar, field emission ,

super capacitors, thermal transport and stability , packaging

industry , corrosion , fire packaging and resistance, and many
more. We expect that, very soon, all these applications will be
available from manufacturers to end users at common
commercial stores.

2. Ceramic Reinforced Graphene Nanocomposites and Their

Application
The recent use of ceramics in grapheme-based nanocomposite
has sparked a global interest. The introduction of ceramic
materials in few-layered graphene results in the formation of a
composite yielding exceptional electrochemical performance with
high charge carrier properties. The exploitation of such properties
is a boon to the energy industry . Several ceramic-graphene
composites like SiC-Graphene , Si3N4-graphene , Al2O3graphene , ZrB2-graphene , ZrO-Al2O3-graphene, BN-Graphene,
and many more are known to enhance not only electrical
properties but also thermal conductivity, refractory, mechanical,
antifriction, anticorrosive and biocompatibility properties for
diverse applications. Use of ceramics within graphene matrix can
help overcome the brittle nature, lower fracture toughness, and
limited thermal shock resistance in the composite industry. The
use of ZrB2-graphene is presently known to be used in aerospace
industry as a high temperature barrier for space vehicle during the
reentry event. These materials (ultrahigh temperature ceramic
composites) are consistently used as the primal infrastructure for
the nose caps in space shuttles and military ballistic equipment.
Several other ultrahigh temperature ceramic composites have
shown promising results. A few ultrahigh temperature ceramic
composites are known to exist, for example, carbides of Ta, Zr, Hf,
Nb, and borides of Hf, Zr, and Ti, respectively. Recently, Lahiri et
al. (2013) have shown that with the introduction of short CNTs as
reinforcement within the TaC ceramics, one can induce the

formation of mulitlayers of graphene within the host matrix during

the spark plasma sintering. This procedure helps in offering high
resistance to pullout which results in higher strength material with
delayed fracture . Similarly, Pejakovi et al. (2010) reported the
synthesis of carbon rich-hafnia thin films using PLD technique.
The NMR results showed that the sample contained graphene
aromatically bonded carbon atoms presumably in graphene
phase . TiN-graphene composites, on other hand, have shown
promising results as a selective permeable membrane for
hydrogen. The composite material according to Kim and Hong
(2012) was prepared by hot press process. The disc obtained was
used to study the hydrogen gas permeability between 0.1 and 0.3
MPa and at 473, 573 and 673K, respectively, using a Knudsen
diffusion model. The results obtained showed that the hydrogen
permeability of TiN-graphene composites was better than the PdAg amorphous membrane at 1.67, 2.09, and 2.83 10 7
mol/msPa1/2 at 673K under 0.3MPa, respectively . Almost similar
results (2.62 107mol/msPa1/2 at 673K under 0.3MPa) of
hydrogen permeation were obtained recently by Lee et al. (2013)
with the use of Al2O3/CeO2/graphene (ACG) composite
membranes prepared by hot-press method. By exploiting the pore
size distribution, surface area, and elasticity, one can use such
kinds of membranes for high purity separation and filtration of
chemicals, biomolecules, petroleum products, and many more .

Field emission properties

Field emission (FE) (also known as field electron
emission and electron field emission) is emission
of electrons induced by an electrostatic field. The most common
context is field emission from a solid surface into vacuum.
However, field emission can take place from solid or liquid
surfaces, into vacuum, air, a fluid, or any non-conducting or
weakly conducting dielectric. The field-induced promotion of
electrons from the valence to conduction band of semiconductors
(the Zener effect) can also be regarded as a form of field
emission. The terminology is historical because related
phenomena of surface photoeffect, thermionic
emission (or RichardsonDushman effect) and "cold electronic
emission", i.e. the emission of electrons in strong static (or quasistatic) electric fields, were discovered and studied independently
from the 1880s to 1930s. When field emission is used without
qualifiers it typically means "cold emission".
Field emission in pure metals occurs in high electric fields: the
gradients are typically higher than 1 gigavolt per metre and
strongly dependent upon the work function. Electron sources
based on field emission have a number of applications, but it is
most commonly an undesirable primary source of vacuum
breakdown and electrical discharge phenomena, which engineers
work to prevent. Examples of applications for surface field
emission include construction of bright electron sources for high-

resolution electron microscopes or to discharge spacecraft from

induced charges. Devices which eliminate induced charges are
termed charge-neutralizers.
Field emission was explained by quantum tunneling of electrons
in the late 1920s. This was one of the triumphs of the
nascent quantum mechanics. The theory of field emission from
bulk metals was proposed by Ralph H. Fowler and Lothar
Wolfgang Nordheim. A family of approximate equations, "Fowler
Nordheim equations", is named after them. Strictly, Fowler
Nordheim equations apply only to field emission from bulk metals
and (with suitable modification) to other bulk crystalline solids, but
they are often used as a rough approximation to describe field
emission from other materials.
In some respects, field electron emission is a paradigm example
of what physicists mean by tunneling. Unfortunately, it is also a
paradigm example of the intense mathematical difficulties that can
arise. Simple solvable models of the tunneling barrier lead to
equations (including the original 1928 FowlerNordheim-type
equation) that get predictions of emission current density too low
by a factor of 100 or more. If one inserts a more realistic barrier
model into the simplest form of the Schrdinger equation, then an
awkward mathematical problem arises over the resulting
differential equation: it is known to be mathematically impossible
in principle to solve this equation exactly in terms of the usual
functions of mathematical physics, or in any simple way. To get
even an approximate solution, it is necessary to use special
approximate methods known in physics as "semi-classical" or
"quasi-classical" methods. Worse, a mathematical error was
made in the original application of these methods to field
emission, and even the corrected theory that was put in place in
the 1950s has been formally incomplete until very recently A
consequence of these (and other) difficulties has been a heritage
of misunderstanding and disinformation that still persists in some

current field emission research literature. This article tries to

present a basic account of field emission "for the 21st century and
beyond" that is free from these confusions.

Practical applications: past and present

Field electron microscopy and related basics

After Fowler-Nordheim theoretical work in 1928, a major advance

came with the development in 1937 by Erwin W. Mueller of the
spherical-geometry field electron microscope(FEM) (also called
the "field emission microscope"). In this instrument, the electron
emitter is a sharply pointed wire, of apex radius r. This is placed,
in a vacuum enclosure, opposite an image detector (originally a
phosphor screen), at a distance R from it. The microscope screen
shows a projection image of the distribution of currentdensity Jacross the emitter apex, with magnification
approximately (R/r), typically 105 to 106. In FEM studies the apex
radius is typically 100 nm to 1 m. The tip of the pointed wire,
when referred to as a physical object, has been called a "field
emitter", a "tip", or (recently) a "Mueller emitter".
When the emitter surface is clean, this FEM image is
characteristic of: (a) the material from which the emitter is made:
(b) the orientation of the material relative to the needle/wire axis;

and (c) to some extent, the shape of the emitter endform. In the
FEM image, dark areas correspond to regions where the local
work function is relatively high and/or the local barrier field F is
relatively low, so J is relatively low; the light areas correspond to
regions where is relatively low and/or F is relatively high, so J is
relatively high. This is as predicted by the exponent of FowlerNordheim-type equations.
The adsorption of layers of gas atoms (such as oxygen) onto the
emitter surface, or part of it, can create surface electric
dipoles that change the local work function of this part of the
surface. This affects the FEM image; also, the change of workfunction can be measured using a Fowler-Nordheim plot (see
below). Thus, the FEM became an early observational tool
of surface science. For example, in the 1960s, FEM results
contributed significantly to discussions on heterogeneous
catalysis. FEM has also been used for studies of surface-atom
diffusion. However, FEM has now been almost completely
superseded by newer surface-science techniques.
A consequence of FEM development, and subsequent
experimentation, was that it became possible to identify (from
FEM image inspection) when an emitter was "clean", and hence
exhibiting its clean-surface work-function as established by other
techniques. This was important in experiments designed to test
the validity of the standard Fowler-Nordheim-type equation
.These experiments deduced a value of voltage-to-barrier-field
conversion factor from a Fowler- Nordheim plot , assuming the
clean-surface value for tungsten, and compared this with
values derived from electron-microscope observations of emitter
shape and electrostatic modeling. Agreement to within about 10%
was achieved. Only very recently has it been possible to do the
comparison the other way round, by bringing a well-prepared
probe so close to a well-prepared surface that approximate
parallel-plate geometry can be assumed and the conversion

factor can be taken as 1/W, where W is the measured probe-to

emitter separation. Analysis of the resulting Fowler-Nordheim plot
yields a work-function value close to the independently known
work-function of the emitter.

Field electron spectroscopy (electron energy

analysis)
Energy distribution measurements of field-emitted electrons were
first reported in 1939. In 1959 it was realized theoretically by
Young, and confirmed experimentally by Young and Mueller that
the quantity measured in spherical geometry was the distribution
of the total energy of the emitted electron (its "total energy
distribution"). This is because, in spherical geometry, the
electrons move in such a fashion that angular momentum about a
point in the emitter is very nearly conserved. Hence any kinetic
energythat, at emission, is in a direction parallel to the emitter
surface gets converted into energy associated with the radial
direction of motion. So what gets measured in an energy analyzer
is the total energy at emission.
With the development of sensitive electron energy analyzers in
the 1960s, it became possible to measure fine details of the total
energy distribution. These reflect fine details of the surface
physics, and the technique of Field Electron Spectroscopy
flourished for a while, before being superseded by newer surfacescience techniques.

Field electron emitters as electron-gun sources

To achieve high-resolution in electron microscopes and other
electron beam instruments (such as those used for electron beam
lithography), it is helpful to start with an electron source that is
small, optically bright and stable. Sources based on the geometry
of a Mueller emitter qualify well on the first two criteria. The

first electron microscope (EM) observation of an individual atom

was made by Crewe, Wall and Langmore in 1970, using
a scanning electron microscope equipped with an early field
emission gun.
From the 1950s onwards, extensive effort has been devoted to
the development of field emission sources for use in electron
guns. [e.g., DD53] Methods have been developed for generating
on-axis beams, either by field-induced emitter build-up, or by
selective deposition of a low-workfunction adsorbate (usually Zirconium oxide - ZrO) into the flat
apex of a oriented Tungsten emitter.
Sources that operate at room temperature have the disadvantage
that they rapidly become covered with adsorbate molecules that
arrive from the vacuum system walls, and the emitter has to be
cleaned from time to time by "flashing" to high temperature.
Nowadays, it is more common to use Mueller-emitter-based
sources that are operated at elevated temperatures, either in
the Schottky emission regime or in the so-called temperature-field
intermediate regime. Many modern high-resolution electron
microscopes and electron beam instruments use some form of
Mueller-emitter-based electron source. Currently, attempts are
being made to develop carbon nanotubes (CNTs) as electron-gun
field emission sources.
The use of field emission sources in electron optical instruments
has involved the development of appropriate theories of charged
particle optics, and the development of related modeling. Various
shape models have been tried for Mueller emitters; the best
seems to be the "Sphere on Orthogonal Cone" (SOC) model
introduced by Dyke, Trolan. Dolan and Barnes in 1953.
[42]
Important simulations, involving trajectory tracing using the
SOC emitter model, were made by Wiesener and
Everhart. Nowadays, the facility to simulate field emission from

Mueller emitters is often incorporated into the commercial

electron-optics programmes used to design electron beam
instruments. The design of efficient modern field-emission
electron guns requires highly specialized expertise.

Atomically sharp emitters

Nowadays it is possible to prepare very sharp emitters, including
emitters that end in a single atom. In this case, electron emission
comes from an area about twice the crystallographic size of a
single atom. This was demonstrated by comparing FEM and field
ion microscope (FIM) images of the emitter. Single-atom-apex
Mueller emitters also have relevance to the scanning probe
microscopy and helium scanning ion microscopy (He
SIM). Techniques for preparing them have been under
investigation for many years. A related important recent advance
has been the development (for use in the He SIM) of an
automated technique for restoring a three-atom ("trimer") apex to
its original state, if the trimer breaks up.

Applications
The development of large-area field emission sources was
originally driven by the wish to create new, more efficient, forms
of electronic information display. These are known as "field
emission displays" or "nano-emissive displays". Although several
prototypes have been demonstrated, the development of such
displays into reliable commercial products has been hindered by a
variety of industrial production problems not directly related to the
source characteristics [En08].
Other proposed applications of large-area field emission sources
include microwave generation, space-vehicle neutralization, Xray generation, and (for array sources) multiple e-beam
lithography. There are also recent attempts to develop large-area

emitters on flexible substrates, in line with wider trends towards

"plastic electronics".
The development of such applications is the mission of vacuum
nanoelectronics. However, field emitters work best in conditions of
good ultrahigh vacuum. Their most successful applications to date
(FEM, FES and EM guns) have occurred in these conditions. The
sad fact remains that field emitters and industrial vacuum
conditions do not go well together, and the related problems of
reliably ensuring good "vacuum robustness" of field emission
sources used in such conditions still await better solutions
(probably cleverer materials solutions) than we currently have.

Field emission properties of

graphene
Graphene has grabbed appreciable attention due to its
exceptional electronic and optoelectronic properties .One of the
potential applications of graphene is in fieldemission (FE)
displays. Malesevic et al. synthesized verticallyaligned few-layer
graphenes (FLGSs) using plasma-enhancedchemical vapor
deposition (PECVD) on titanium substrate,and turn-on field of the
field emission from the graphene layer was as low as 1 V/m . Qi
et al. prepared FLGSs byradio-frequency PECVD on Si(100)
substrates without anycatalyst, and turn-on field of its emission
was 3.91 V/m .

Field emission characteristics

Fowler and Nordheim (FN) first derived a semiclassical theory of
field emission currents from cold metals in 1928 (Fowler &
Nordheim, 1928). In this theory, the system is simplified
as a one-dimensional structure along the direction of the external
field. The emission tip is modeled as a semi-infinite quantum well.
By employing the Wentzel-Kramers-Brillouin approximation,
following FN plot is given. ln (I/V2) -1/V (1) where I is in
amperes per square centimeter of emitting surface and V is the
applied voltage.

Current-voltage characteristics for a mechanically sharpened

carbon rod (open
circles) and a GNS cathode (solid circles). Inset shows the
Fowler-Nordheim plots (ln(I/V2)
vs 1/V) for the I-V characteristics of the GNS cathode. (Reprinted
with permission,
Matsumoto et al. 2007, American Institute of Physics.)
The above FN theory should not be applied to nanometer sized
emitters such as GNS and
CNT because the geometrical size of the tip is comparable to the
electron wavelength. Much sophisticated emission theory is
developed by several authors (He et al., 1991; Liang &
Chen, 2008; Forbes, 2001), and these theories will explain the
difference between the straight line obtained by the simple FN
plot and the experimentally obtained slightly curved feature
(dotted line) in the inset of Fig. 3. For the precise fitting by using
these sophisticated theories, it is necessary to determine physical
values such as a shape and a size as well as the electronic
properties; e.g. the defect density and work function of the tip.
However, as shown, it is difficult to determine these values for our
tip. Therefore, here we estimate the field emission characteristics
by using the FN plots. Shows typical logarithmic current-voltage
(I-V) characteristic of the GNS field emitter. The figure also shows
I-V characteristic of a sharpened graphite rod without
nanostructure. The currents were collected on a 3 mm diameter
aluminum anode, which was located at 100 m in front of the
cathode. The measurements were carried out in a vacuum
chamber with a residual pressure of 1 x 10-6 Pa. The
mechanically sharpened graphite rod without nanostructure
showed little field emission current (open circles), while

the GNS emitter starts to emit electrons at an average electric

field of about 3 V/m and the emission current exceeds 2 mA at
an applied electric field of 11 V/m (solid circles). The FN
plot of the emission current from the GNS emitter is shown in the
inset of Fig. Linear dependence of the Fowler-Nordheim plot
suggests that the electron emission is dominated
by the Fowler-Nordheim tunneling process as described .