Engineering Department

Industrial Engineering
Material Science

An introduction to Graphene

Prepared by: Alerda Matrisi

Accepted by: PhD Klodian Dhoska

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1.INTRODUCTION.................................................................................................................................... 3

2. PREPARATION OF GRAPHENE ............................................................................................................. 4

2.1 THE SCOTCH TAPE METHOD ................................................................................................................. 4

2.2 DISPERSION OF GRAPHITE ....................................................................................................................... 4
2.3 GROWTH ON SURFACES ......................................................................................................................... 5
2.4 EPITAXIAL GROWTH .............................................................................................................................. 5

3. FUNDAMENTAL CHARACTERISTICS ..................................................................................................... 6

3.1 STRENGTH AND STIFFNESS ........................................................................................................................ 6

3.2 ELECTRICAL CONDUCTIVITY ....................................................................................................................... 6
3.3 ELECTRONIC PROPERTIES.......................................................................................................................... 7
3.4 OPTICAL PROPERTIES .............................................................................................................................. 8

4. GRAPHENE PRICE ................................................................................................................................ 8

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1.Introduction
Graphene is a one-atom-thick layer of carbon atoms arranged in a hexagonal lattice shape. It is
the building-block of Graphite (which is used, among others things, in pencil tips,
lubricants,batteries), but graphene is an astonishing substance on its own - with a multitude of
amazing properties which repeatedly earn it the title wonder material.

Graphene is the thinnest material known to man at one atom thick, and also incredibly strong -
about 200 times stronger than steel. Besides that, graphene is an excellent conductor of heat
and electricity and has interesting light absorption abilities. It is truly a material that could
change the world, with unlimited potential for integration in almost any industry.

Graphene is an extremely diverse material, and can be combined with other elements (including
gases and metals) to produce different materials with various superior properties. Researchers all
over the world continue to constantly investigate and patent graphene to learn its various
properties and possible applications, which include:

touchscreens (for LCD or OLED displays)

transistors
computer chips
batteries
energy generation
supercapacitors
DNA sequencing
water filters
antennas
solar cells
Spintronics-related products

Graphene is an exciting material that is getting a lot of attention - especially since the 2010
Nobel prize in physics went to Andre Geim and Konstantin Novoselov, who first isolated
Graphene in 2004 netting themselves a pot of 10 million Swedish kroner (about $1.49 million).
(Mertens, R. 2017, January)

A rendering of graphenes uniform structure, at the

molecular scale.

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2. Preparation of Graphene

There are two different approaches to preparing graphene. On the one hand graphene can be
detached from an already existing graphite crystal, the so-called exfoliation methods, on the
other hand the graphene layer can be grown directly on a substrate surface. The first reported
preparation of graphene was by Novoselov and Gaim in 2004 by exfoliation using a simple
adhesive tape.

2.1 The Scotch Tape Method

In this micromechanical exfoliation method, graphene is detached from a graphite crystal using
adhesive tape. After peeling it off the graphite, multiple-layer graphene remains on the tape. By
repeated peeling the multiple-layer graphene is cleaved into various flakes of few-layer
graphene. Afterwards the tape is attached to the substrate and the glue solved, e.g. by acetone, in
order to detach the tape. Finally one last peeling with an unused tape is performed.

The obtained flakes differ considerably in size and thickness, where the sizes range from
nanometers to several tens of micrometers for single-layer graphene, depending on the
preparation of the used wafer. Single- 1 layer graphene has a absorption rate of 2%, nevertheless
it is possible to see it under a light microscope on SiO2 /Si, due to interference effects.( Casiraghi
C, 2007)

However, it is difficult to obtain larger amounts of graphene by this method, not even taking into
account the lack of controllability. The complexity of this method is basically low, nevertheless
the graphene flakes need to be found on the substrate surface, which is labour intensive. The
quality of the prepared graphene is very high with almost no defects.

2.2 Dispersion of Graphite

Graphene can be prepared in liquid-phase.This allows upscaling the production, in order to

obtain a much higher amount of graphene. The easiest method would be to disperse the graphite
in an organic solvent with nearly the same surface energy as graphite (LotyaM, 2010). Thereby,
the energy barrier is reduced, which has to be overcome in order to detach a graphene layer from
the crystal. The solution is then sonicated in an ultrasound bath for several hundred hours or a
voltage is applied.
After the dispersion, the solution has to be centrifuged in order to dispose of the thicker flakes.
The quality of the obtained grapheme flakes is very high in accordance with the
micromechanical exfoliation. Its size however is still very small, neither is the controllability

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given. On the other hand, the complexity is very low, and as mentioned above this method
allows preparing large amounts of graphene.

2.3 Growth on Surfaces

A totally different approach to obtaining graphene is to grow it directly on a surface.

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

2.4 Epitaxial Growth

Graphene can be prepared by simply heating and cooling down an SiC crystal (Forbeaux I, 1998)
Generally speaking single- or bi-layer grapheme forms on the Si face of the crystal, whereas few-
layer graphene grows on the C face (Cambaz ZG, 2008). The results are highly dependent on the
parameters used, like temperatur, heating rate, or pressure. In fact, if temperatures and pressure
are too high the growth of nanotubes instead of graphene can occur.
The graphitization of SiC was discovered in 1955, but it was regarded as unwelcome side effect
instead of a method of preparing graphene (Cambaz ZG, 2008). The Ni(111) surface has a lattice
structure very similar to the one of graphene, with a missmatch of the lattice constant at about
1.3% (Enderlein, C; Dissertation (2010). Thus by use of the nickel diffusion method a thin Ni
layer is evaporated onto a SiC crystal. Upon heating the carbon diffuses through the Ni layer and
forms a graphene or graphite layer on the surface, depending on the heating rate. The thus
produced graphene is easier to detach from the surface than the graphene produced by the growth
on a simple SiC crystal without Ni.
The growth of graphene starts at several locations on the crystal simultaneously and these
graphene islands grow together. Therefore the graphene is not perfectly homogeneous, due to
defects or grain boundaries. Its quality therefore is not as good as that of exfoliated graphene,
except the graphene would be grown on a perfect single crystal. However, the size of the
homogeneous graphene layer is limited by the size of the crystal used. The possibility to produce
large amounts of graphene by epitaxial growth is not as good as by liquid-phase exfoliation,

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though the controllability to gain reproducible results is given. Also the complexity of these
methods is comparatively low.

3. 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. (Jesus de La Fuente, 2016)

3.1 Strength and stiffness

Graphene is believed to be the strongest material yet discovered, some 200 times stronger
than steel. Remarkably, it's both stiff and elastic (like rubber), so you can stretch it by an
amazing amount (20-25 percent of its original length) without it breaking. That's because the flat
planes of carbon atoms in graphene can flex relatively easily without the atoms breaking apart.(
Joseph M. Longo, Spring 2014).

3.2 Electrical conductivity

Materials that conduct heat very well also conduct electricity well, because both processes
transport energy using electrons. The flat, hexagonal lattice of graphene offers relatively little
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resistance to electrons, which zip through it quickly and easily, carrying electricity better than
even superb conductors such as copper and almost as well as superconductors (unlike
superconductors, which need to be cooled to low temperatures, graphene's remarkable
conductivity works even at room temperature). Scientifically speaking, we could say that the
electrons in graphene have a longer mean free path than they have in any other material (in other
words, they can go further without crashing into things or otherwise being interrupted, which is
what causes electrical resistance). Imagine a strong, light, relatively inexpensive material that
can conduct electricity with greatly reduced energy losses: on a large scale, it could revolutionize
electricity production and distribution from power plants; on a much smaller scale, it might
spawn portable gadgets (such as cell phones) with much longer battery life.

3.3 Electronic properties

Electrical conductivity is just about "ferrying" electricity from one place to another in a relatively
crude fashion; much more interesting is manipulating the flow of electrons that carry electricity,
which is what electronics is all about. As you might expect from its other amazing abilities, the
electronic properties of graphene are also highly unusual. First off, the electrons are faster and
much more mobile, which opens up the possibility of computer chips that work more quickly
(and with less power) than the ones we use today. Second, the electrons move through graphene
a bit like photons (wave-like particles of light), at speeds close enough to the speed of light
(about 1 million meters per second, in fact) that they behave according to both the theories of
relativity and quantum mechanics, where simple certainties are replaced by puzzling
probabilities. That means simple bits of carbon (graphene, in other words) can be used to test
aspects of those theories on the table top, instead of by using blisteringly expensive particle
accelerators or vast, powerful space telescopes.( Chris Woodford, 2017)

Wearable technology

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3.4 Optical properties

As a general rule, the thinner a material, the more likely it is to be transparent (or translucent),
and it's easy to see why: with fewer atoms to battle, photons are more likely to penetrate through
thin objects than thick ones. As expected, super-thin graphene, being only one atom thick, is
almost completely transparent; in fact, graphene transmits about 9798 percent of light
(compared to about 8090 percent for a basic, single pane of window glass). Bearing in mind
that graphene is also an amazing conductor of
electricity, you can start to understand why
people who make solar panels, LCDs, and
touch screens are getting very excited: a
material than combines amazing transparency,
excellent electrical conductivity, and high
strength is a perfect starting point for
applications like these.( Chris Woodford, 2017)

4. Graphene price

The price of graphene is linked to its quality, and not all applications require superb material
quality. For example, graphene oxide powder (graphene functionalized with oxygen and
hydrogen) is inexpensive and has been used to make a conductive graphene paper, for DNA
analysis, and for other advanced composite and biotechnology applications. Graphene oxide in
solution sells for 99 euros per 250 mL from Graphenea. However, the electronic properties of
graphene oxide at the moment are not sufficiently good for batteries, flexible touch screens, solar
cells, LEDs, smart windows, and other advanced opto-electronic applications.

Mechanically exfoliated graphene (obtained with the famous scotch tape technique) comes in
small, high-quality flakes. Exfoliated graphene has so far shown to hold the best physical
properties, reaching towards theoretically predicted current conduction, mechanical strength, etc.
The coverage of mechanically exfoliated graphene, however, is only on the order of a few small

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flakes per square centimeter, not nearly enough for applications. In addition, the price of such
graphene can be on the order of several thousands of dollars per flake.

CVD graphene, available with high quality from Graphenea, offers sufficient quality for almost
any graphene application. The price of CVD graphene is linked to production volume and costs
of transferring from the copper substrate, on which it is grown, onto another substrate.
Graphenea's industrial scale graphene technology leads to low CVD graphene cost for bulk
orders (see graph). Bulk orders of such graphene can be cheaper than, for example, silicon
carbide, an important semiconductor. Graphenea has filed a patent for a low cost industrial scale
CVD growth and transfer process. (Marko Spasenovic, 2017)

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REFERENCE PAGE

1. The Nobel Prize in Physics 2010". Nobelprize.org. Nobel Media AB 2014. Web. 30 May 2017
2. Mertens, R. 2017, January What is Graphene? Retrieved from: www.graphene-info.com)
3. LotyaM, et al.; ACS Nano 4, 3155-3162 (2010)
4. Su CY, et al.; ACS Nano 5, 2332-2339 (2011)
5. Forbeaux I, et al.; Phys. Rev. B 58, 16396-16406 (1998)
6. Cambaz ZG, et al.; Carbon 46, 841-849 (2008)
7. Enderlein, C; Dissertation: Graphene and its Interaction with Di erent Substrates Studied by Angular-
Resolved Photoemission Spectroscopy, Freie Universitaet Berlin (2010)
8. Marko Spasenovic, The Quality Of The Graphene Affects The Price, 2017 Retrieved from:
www.graphenea.com
9. Chris Woodford. Graphene January 30, 2017

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