3. Introduction
• Graphene : Carbon in 2D
• 2-dimensional, crystalline
allotrope of carbon.
• Carbon atoms are densely
packed in a regular sp2-
bonded atomic-scale
hexagonal pattern.
.
Fig1: High resolution TEM images
of graphene
http://en.wikipedia.org/wiki/Graphene
4. Properties
• Electronic properties
– High electrical conductivity
– Semi metal/zero gap semiconductor
– High electron mobility
• Mechanical properties
– One of the strongest material
– Ultimate tensile strength is 130GPa (0.4 GPa-Steel)
– Very light
– High surface area to volume ratio.
– Has elastic properties too (Young’s modulus – 0.5TPa)
5. Properties
• Optical properties
– Single layer of graphene absorbs spectrum as high as 2.3%
of white light
– Saturation absorption under strong excitation
• Wetting properties
– Super hydrophobic property
– Super hydrophilic property
6. Applications
• Electrochemical storage devices
Super-capacitors, graphene-enhanced lithium ion batteries.
• Biological Engineering
Tissue regeneration- potential biocompatibility.
• Aerospace applications
Integration into other composite materials.
• Water purification systems
Monolayer graphene- ultrafilteration.
Some of the major applications of graphene are:
7. Applications
• Opto-Electronic applications
Replacing Indium Tin Oxide.
• Photovoltaic Cells
Replacing Si Solar cells and ITO in DSSC.
• Various other applications which involve enhancing electrical, mechanical
and various other properties of devices or materials as such.
8. Methods Used
• Chemical Vapour Deposition (CVD).
• Mechanical Exfoliation.
• Epitaxial Growth of Graphene on SiC.
• Chemical Methods such as Hummers Method.
• Electrochemical Exfoliation.
Various Methods used till date are as follows:
9. CVD (Chemical Vapour Deposition)
• A way of depositing gaseous reactants on a substrate.
• The process is similar to PVD (Physical Vapour Deposition) the
only difference being the use of solid reactants instead of
gaseous reactants as in CVD.
• The carrier gases are combined in a reaction chamber which
is maintained at certain temperature and pressure (as
required by reaction).
• The reaction occurs on the substrate on which one of the
product (carbon) is deposited and the by products are
pumped out.
• Substrate is usually a transition metal (Ni/Cu) or some
ceramic such as glass.
• The selection of substrate depends upon the feasibility of
transferring the graphene onto the required material.
10. • The gases used are generally Methane (source of carbon)
Hydrogen and Argon are also used along with methane as
reaction stabilizers and enhancing the film uniformity.
• Although there are various types of CVD processes but most
modern processes (regarding CVD pressure) are as follows:
-> LPCVD (Low Pressure CVD): Carried out under sub-atmospheric
pressures. Low pressure prevents unwanted reactions and also
increase the uniformity of the films on the substrate.
-> UHVCVD (Ultra High Vacuum CVD): Carried out under extremely
low atmospheric pressures (6-10 Pa).
CVD (Chemical Vapour Deposition)
12. CVD (Chemical Vapour Deposition)
ADVANTAGES-
• High quality, impervious, and harder graphene is obtained.
• Producing large domains of graphene is easy.
• High growth rates possible.
• Good reproducibility.
LIMITATIONS-
• High temperatures (greater than 900 °C) leads to wrinkled
graphene due to difference in Coefficient of Thermal Expansion.
• Complex process.
• Production of corrosive and toxic gases.
• Difficulty in controlling the thickness in some cases (number of
layers).
• Difficulty in transferring the film to other surface (exfoliation).
• Difficulty in achieving the uniform deposition of the carbon.
13. Mechanical Exfoliation
Process:
• A fresh piece of Scotch tape is taken (about six inches long).
• The adhesive side is pressed onto the HOPG (Highly Ordered
Pyrolytic Graphite) for about ten seconds.
• The tape is gently peeled away with thick shiny layers of graphite
attached to it.
• The part of the tape with layers from the HOPG was refolded
upon a clean adhesive section of the same piece of the tape and
then the tape is unfolded.
• This process is repeated several times until the end of the tape is
no longer shiny but becomes dark/dull and grey.
• These graphite layers on the tape are transferred onto the
surface of the Si/SiO2 wafers by gently pressing them onto the
tape for some time and then peeling off.
• The wafers are then examined using various characterization
techniques.
14. Mechanical Exfoliation
(a) Adhesive tape is pressed onto the HOPG.
(b) The tape is peeled off when some layers stick to the surface.
(c) This tape is pressed onto the surface of the target substrate.
(d) The tape is peeled off when the layers stick to the target surface.
Fig3: Schematic diagram for the mechanical exfoliation of graphene from graphite using Scotch tape.
K S Novoselov and A H Castro Neto 2012 Phys. Scr. 2012 014006, Two-dimensional crystals-based heterostructures: materials with tailored
properties.
15. Mechanical Exfoliation
Advantages:
• Safe and simple process.
• Few layer graphene can be easily obtained.
• The chances of impurity in the graphene so obtained are less.
• Sample preparation is simplified.
Limitations:
• Yield obtained may not meet the requirements.
• Requires skilled manual labour.
• Despite the fact that tape residue does not seriously affect the
quality of the graphene flake samples, it does make those
samples more difficult to find on the substrate.
16. • The main concept behind the process is that the vapour pressure
of Silicon is higher, as a result on heating the SiC wafer, the Si
evaporates leaving behind the graphene layers on the SiC.
• The theoretical studies show the various stable structures of
carbon that grow on SiC which determines the mechanism for
growth of carbon layers on SiC substrate.
• The evaluation of number of graphene layers is done by
observing the quantized oscillations of the electron reflectivity.
• Multilayer, bilayer or single layer graphene can be grown on the
SiC substrate by controlling various parameters such as SiC
temperature and pressure.
• Graphene single crystals can also be synthesized using this
process since few layer graphene (FLG) always maintains it’s
epitaxial growth with the SiC substrate.
Epitaxial Growth of Graphene on SiC
17. Epitaxial Growth of Graphene on SiC
Fig4: Schematic illustration of the
thermal decomposition method.
Hiroki Hibino†, Hiroyuki Kageshima, and Masao
Nagase, “Graphene Growth on Silicon Carbide”,
NTT Technical review.
• The SiC substrate is heated at a temperature (around 1200 °C)
and the conditions of the chamber are set accordingly.
• UHV (Ultra High Vacuum) technique hinders the uniform
growth of MLG (Multi Layer Graphene) and favor the bilayer
graphene.
• The Si atoms evaporate due to thermionic emission leaving
behind the carbon atoms on the remaining substrate.
• The carbon layers accumulating on the substrate are
controlled by controlling the temperature and pressure.
• The final SiC substrate is covered with the carbon layers
which can be either bilayer, monolayer or multilayer
graphene.
• The type is distinguished by using the suitable
characterization techniques (such as TEM), the shade of the
layer in the images can be used as the classifying method for
recognizing the type of graphene.
18. Epitaxial Growth of Graphene on SiC
Advantages:
• High quality graphene.
• Easy method for growing single crystals of graphene.
• The layers of graphene can be controlled conveniently.
• Higher temperatures ensure reproducible, clean and ordered graphene.
• Patterning of graphene is easier due to the use of insulating SiC
substrate.
• Further advantage is that SiC is already a large bandgap semiconductor
already used in electronic applications.
Limitations:
• High temperature.
• Difficulty in growing uniform MLG in UHV conditions (impurity
free conditions).
• Lattice constant mismatch and difference in coefficient of
thermal expansion of SiC - C can lead to various defects.
19. • The Hummers method is used for producing graphene by oxidising graphite to
GO by using suitable oxidising agents such as KMnO4.
• The GO so produced is again then chemically reduced to get graphene.
• The modified Hummers method introduces a way to get a more stable GO
colloidal solution.
• Ultra-sonication is used for stabilizing the GO solution and enhancing the
exfoliation in the GO solution.
Hummers Method (modified)
Fig5: A typical illustration of the difference between the graphite and the GO so formed.
Mateusz CISZEWSKI, Andrzej MIANOWSKI, “Survey of graphite oxidation methods using oxidizing mixtures in inorganic acids”, CHEMIK International Edition,
CHEMIK 2013, 67, 4, 267-274
20. The modified hummers method can be carried out in three major steps as follows:
Oxidation
• Natural graphite flake is mixed with a strong acid such as H2SO4 /HNO3 followed by
continuous stirring in ice bath.
• Then KMnO4 is added and stirred at room temperature.
• Then the solution is kept overnight after adding DI water and H2O2.
• Centrifugation is used for dilution until the pH is around 7.
• Ultra-sonication is carried out to get monolayer GO.
Reduction
• Addition of certain reducing agents such as hydrazine or NaBH4 is made to the measured
solution.
• The attached functional groups are removed and to enhance the exfoliation certain polar
aprotic solvents can be used along with organic compounds.
• Although thermal reduction gives a better quality graphene but has its own disadvantages.
Post-treatment
• Then the solution is filtered and washed with DI water until neutrality.
• The product is dried and grinded.
• The graphene so produced can then be send for characterization tests.
Hummers Method (modified)
21. Hummers Method (modified)
Advantages:
• High yield.
• Scalable to industrial level.
Limitations:
• The defects on graphene sheets are inevitable.
• The process is time consuming and can be laborious.
• The thickness control is not as promising as in the epitaxial graphene
growth or the CVD process.
22. Electrochemical Exfoliation
• The electrochemical exfoliation method is an eco-friendly method fro producing high quality
graphene.
• The electrochemical exfoliation of graphite due to the ions present in the solution give the
FLG or GO depending upon the nature of electrolyte.
• The choice of electrolyte is based on the requirement of the oxidizing environment and
more importantly on the size of the intercalating ion.
• The setup includes two electrodes one of them being graphite or HOPG the other can be Cu,
Pt or can be HOPG/graphite also.
• A voltage of +/- 10V is applied generally for an unequal period of time.
• The intercalating ion in the solution exfoliates the graphite into FLG by penetrating in
between the sheets due to the applied voltage.
• The need for negative voltage is to bring the intercalated ions back into the solution along
with the sheets, hence the need of unequal application time for the voltages.
• The electrolyte used is often diluted with DI water and then at the end of the process the
solution is taken for centrifugation to separate the graphite particles from graphene/GO.
• The solution can also be subjected to ultra-sonication for enhancing the exfoliation and
some stabilizers can also be used for the solution.
• The final solution is either dried or taken directly for characterization.
23. Electrochemical Exfoliation
AC voltage/555 timer
Graphite rod Graphite rod
Electrolyte
Fig6: A basic setup for the process is illustrated in the following figure.
Fig7: Schematics of the exfoliation mechanism for the peroxide electrolyte. The mechanism may
differ depending upon the nature of ions/electrolyte.
K.S.Rao , J.Senthilnathan, Y.F.Lui, M.Yoshimura, Role of peroxide ions in formation of graphene nanosheets by electrochemical exfoliation of graphite, Scientific
reports 4, Article number:4237, 2014
24. Electrochemical Exfoliation
Advantages:
• High yield.
• Scalable to industrial level.
• Easy to operate and relatively a faster approach.
• Eco-friendly.
• FLG can be easily obtained.
• The graphene obtained can be functionalised depending upon
electrolyte and hence can be more compatible with certain organic
compounds or polymers.
Limitations:
• The impurities may be present in the form of unwashed salts in
between the graphene layers.
• This may affect the conductivity of the graphene.
• The thickness control is not as promising as in the epitaxial graphene
growth or the CVD process.
25. N-doped Graphene
• The electronic properties of graphene doped with
nitrogen or boron are enhanced similar to the case of
doped Si.
• The doping depends upon the type of graphene used,
hence depends upon the initial process used for the
synthesizing the graphene.
• Till now various methods are used for synthesizing N-
doped graphene, some of them are as follows:
1) Co-growth of ammonia and methane by CVD.
2) Arc discharge of graphite.
3) Annealing of GO with ammonia.
4) Treating graphene with nitrogen plasma.
Manipulation of these properties via chemical functionalization / surface modification makes it rapid growing field in material science.
Graphene can be saturated readily under strong excitation over the visible to near-infrared region, due to the universal optical absorption and zero band gaps. This has relevance for the mode locking of fiber lasers, where full band mode locking has been achieved by graphene-based saturable absorber. Due to this special property, graphene has wide application in ultrafast photonics. Moreover, the optical response of graphene/graphene oxide layers can be tuned electrically.
n epitaxial method in which graphene results from
the high temperature reduction of silicon carbide
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The process is relatively straightforward, as
silicon desorbs around 1000°
C in ultrahigh vacuum. This
leaves behind small islands of graphitized carbon
The furnace (reaction chamber) is quickly cooled to keep the deposited carbon layer from
aggregating into bulk graphite, which crystallizes into a contiguous graphene
layer on the surface of the metal.