Graphene
DEPARTMENT OF CHEMISTRY
COLLEGE OF BASIC SCIENCE AND HUMANITIES
ORISSA UNIVERSITYOF AGRICULTURE AND TECHNOLOGY
BHUBANESWAR 751003
2024
A DISSERTATION SUBMITTED
TO “ORISSA UNIVERSITY OF AGRICULTURE AND TECHNOLOGY”
IN PARTIAL FULFILLMENT OF THE REQUIREMENT FOR THE
DEGREE
OF BACHELOR IN SCIENCE IN CHEMISTRY (HONOURS)
By
Ananya Anuska Nanda
ROLL NO. BS-21-16
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CERTIFICATE
Ther is to certify that the dissertation entitled “Graphene” submitted in partial
fulfilment of the requirements for the award of the degree of BACHELOR OF
SCIENCE IN CHEMISTRY (HONOURS) to the Orissa University of Agriculture and
Technology, Bhubaneswar is an authentic record of project work made by
ANANYA ANUSKA NANDA under my supervision.
It is further certified that the assistance and help obtained by her from various
sources during the work has been duly acknowledged.
HEAD OF THE DEPARTMENT SUPERVISIOR
EXTERNAL EXAMINER
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ACKNOWLEDGEMENT
It is a genuine pleasure to express my deep sense of thanks and gratitude to my
guide DR. NANDITA SWAIN, DIRECTOR, HEAD OF DEPARTMENT OF CHEMISTRY,
College of Basic Science and Humanities, OUAT, Bhubaneswar for her valuable
guidance and supervision. Her dedication and keen interest above all her
overwhelming attitude to help her students had been solely and mainly
responsible for the completion of the project.
I take this opportunity to record my sincere thanks to all faculty members of
DEPARTMENT OF CHEMISTRY for their help and encouragement.
Ananya Anuska Nanda
Dt:
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CONTENT:
1. Abstract
2. Introduction
3. Properties of Graphene
4. Applications of Graphene
5. Synthesis of Graphene
6. Reference
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ABSTRACT:
Graphene has attracted intense scientific interest due to its exceptional
electrical, mechanical, and chemical properties over the last couple of
years. Ther strictly two-dimensional (2D) material has potential
applications in advanced electronic devices and composite materials. The
challenge is to produce large area defect-free graphene necessary for
electronic applications while bulk-production at gram scale of graphene
with defects enabling anchoring sites for nanoparticles is required for
applications like catalysis. Herein, we report the Ni-catalysed ambient
pressure chemical vapor deposition of (APCVD) synthesis of few-layer
graphene, the spatial characterization of the few layered transparent
graphene by micro-Raman spectroscopy, its electrical characterization
showing p-semiconductor behaviour, as well as studies on the gas-sensing
properties towards low concentrations of CO and H2. Moreover, APCVD
and low-pressure CVD (LPCVD) growth of graphene have been carried on
Cu-catalyst surfaces. Effect of metal catalyst thickness and CVD growth
parameters (concentrations of the gases, growth time, cooling effect etc.)
were studied in detail to optimize the quality of graphene with respect to
the number of layers and defects. Chemical synthesis of graphene was
established by oxidation of graphite-to-graphite oxide (GO) and followed by
reduction process. Different methods (Staudenmaier’s, Hummers’,
Modified Hummers’ and Tour’s Methods) to synthesize GO were studied
comparatively to have highly oxidized GO. Various reduction techniques
were studied to improve the quality of chemically derived graphene (CDG).
Metal nanoparticles (NPs of Au, Ni and Pd) were successfully supported on
CDG and employment of Pd/CDG as catalysts in the dehydrogenation and
hydrolysis of ammonia borane (AB). Moreover, metal oxide NPs of titanium
dioxide (by UV-assisted method and hydrothermal method), tungsten oxide
(by son chemical method) and zinc oxide (via thermal decomposition
method), were successfully deposited on CDG. Composites of CDG with
TiO2 and WO3 were applied successfully in photodegradation reactions of
methylene blue (MB) under UV-light. Sensing measurements of ZnO/CDG
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INTERODUCTION:
Background and Discovery of Graphene
Graphite of which the term was derived from the Greek word
“graphene” (to write) in, is a layered planar structure composed of
carbon atoms that are arranged in a honeycomb lattice. The separation
between carbon atoms in the lattice is 0.142 nm, and the distance
between planes is 0.335 nm in graphite structure. In graphite, isolated
single layer that is composed of sp2 hybridized carbon atoms is called
graphene. The term of graphene originates from the combination of
graphite and suffix –ene that is earlier used in the nomenclature and
terminology of polycyclic aromatic hydrocarbons. The possibility of
wrapping up graphene into 0D fullerenes, rolling it into 1D carbon
nanotubes (CNTs) and stacking of it into 3D graphite makes graphene
the central building block of all graphitic materials (see Figure).
Graphene, 2D
Fullerenes, 0D Graphite, 3D
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Despite the discovery of fullerenes in 1985 by Kroto, Curl, and Smalley and
shortly thereafter of CNTs in 1991 by Iijima, graphene had already been studied
theoretically for the first time in 1947 by P.R. Wallace, later in 1956 by J.W.
McClure and in 1984 by G.W. Semenoff. The isolation of graphene was thought
to be not possible thermodynamically according to Peierls, Landau, and later
Mermin reporting that a 2D lattice melts due to thermal fluctuations and long-
range crystalline order is prevented. However, A.K. Geim and K. Novoselov in
2004 isolated the graphene by adhesive Scotch tape and characterized it
successfully. They used mechanical exfoliation method to produce single
graphene sheet from graphite. Then, graphene was transferred onto silicon
dioxide substrate, characterized by optical microscopy and AFM as well as
electrical measurements were conducted for it. These two Russian scientists
both from Manchester University were awarded the 2010 Nobel Prize in Physics
for these “ground-breaking experiments regarding the two-dimensional
material graphene”. However, it should be noted that graphene like structures
(graphite intercalation compounds GICs, graphite oxide GO and reduced
graphene oxide rGO) have been already known since 1840s by German scientist
Schafhaeutl who reported the insertion of acid or alkali metal between the
carbon lamellae (intercalation) and exfoliation of graphite with sulfuric and
nitric acids [11]. After Schafhaeutl, Brodie (in 1859), Staudenmaier (in 1898) [13]
and Hummers (in 1958) also produced GO by exfoliating the graphite via high
oxidizing reagents. In 1962, Boehm (he originally coined the term “graphene” in
1986) and co-workers for the first time reported thin, lamellar carbon
containing small amount of hydrogen and oxygen via chemical reduction of
dispersions of GO in dilute alkaline media with hydrazine, hydrogen sulphide, or
iron (II) salts. Just after ther report, thermal reduction of GO was also published
by the same group in 1962[15]. Boehm et al. assumed that thinnest lamella
consisted of a single carbon layer and tried to prove that the thinnest lamella by
transmission electron microscopy (TEM) micrograph densitometry
measurements. Experimental error due to the thickness calibration standards,
however prevented the exact identification of monolayer carbon at that time
[15]. It is worth to note that graphene (reduced graphene oxide rGO or
chemically derived graphene CDG) not pristine graphene (without heteroatomic
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contamination) was for the first time described by H. P. Boehm and co-workers.
Besides RGO sample synthesized by Boehm, ultrathin graphitic films and even
monolayer pristine graphene was grown epitaxially on metal substrates (Ru, Rh
and Ni in 1970) [17], on insulating carbides (SiC in 1975 and TiC, TaC in 1993) [18]
and on graphite in 2001.
Not only the production of pristine graphene was known by epitaxial growth in
pre-2004 graphene research, paper from the Kurz’s group had shown that a
tape method (mechanical exfoliation) to get ultra-thin graphite films had been
already used in 1990.
After peeling optically thin layers of graphite from highly ordered pyrolytic
graphite (HOPG) with transparent tape, carrier dynamics of the sample was
studied as well. Then after, visualization of few-nm thick graphite was reported
in 1995 using atomic force microscopy (AFM) on top of HOPG and using a
scanning electron microscope (SEM) in 1999.
Besides production and visualization of ultra-thin graphite samples, electrical
properties were also analysed for the samples with thickness down to 60 layers
in 1997-2001 [23]. Graphene monolayers for their cleavage on top of HOPG in
2003 [24] by STM and ultrathin epitaxial growth of graphite films composed of
typically 3 graphene sheets from SiC in 2004 were reported by W. A. de Heer
and co-workers.
Geim declared her awareness of such earlier reports on the ultra-thin
graphitic films and even the monolayers of graphene production,
visualization, and measurements (Figure 3). However, he finds all the
previous reports as observational with the lack of reporting distinguishing
properties of graphene [16]. He explains further that not only the ease of
method (Scotch tape) that they have used to produce graphene, but also the
isolation, identification, characterization, and electronic measurements
showing the astonishing electronic quality of graphene took researchers by
surprise. Therefore, their work did not disappear into oblivion to previous
literature.
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PROPERTIES OF GRAPHENE:
Graphene is composed of sp2 hybridized carbon atoms arranged in a 2D
honeycomb crystal lattice. Three valence electrons of carbon atoms in
graphene form bonds (σ) with their next neighbours while the fourth
electron of each carbon atom localized in the p z (π) orbitals perpendicular
to the planar sheet form highly delocalized bonds (π) with the others.
Graphene is a zero-band gap semiconductor and charge carriers in
graphene have very small effective mass so that carrier mobilities are as
high as up to 200000 cm2V-1s-1 at a carrier density of 1012 cm−2 [27].
Electrons can flow through graphene more easily than even through
copper. Edges of graphene are called as an armchair or a zig-zag edge due
to the individual lattice arrangement on the atomic scale.
The opacity of a single layer graphene is 2.3 % so its optical transparency is
97.7 % observed in the visible range decreases linearly as the number of
layers increases (Figure 5). Graphene, however, becomes visible when it is
transferred onto a silicon wafer with a silicon dioxide layer (usually 300
nm). Therefore, detection of the number of graphene layers is possible via
the colour shifts due to the thickness variations on the silicon wafer.
The mechanical properties of graphene have been investigated by
numerical simulations and experimental measurements using Atomic
Force Microscopy (AFM) [31]. Graphene is found to be one of the strongest
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materials with a mechanical strength higher than diamond and over 300
times greater than a steel film of the same thickness [31b]. Reported values
for defect-free graphene are young’s modulus of 1.0 TPa and a fracture
strength of 130 GPa that are higher than CNTs [31]. Graphene is flexible and
stretchable up to 20% of its initial length. Besides those outstanding
properties, graphene has a thermal conductance (>5000 W/m K) [32] that is
also higher than all the other carbon structures and theoretical surface
area of 2600 m2/g [33].
Adsorption and desorption of gases such as hydrogen and carbon
monoxide are possible on graphene surface like on graphite [34]. Besides
forming weak adsorbate on graphene surface, graphite can be also oxidized
to graphene oxide (GO) that is the functionalized form graphene with
functional groups like epoxy and carboxyl [35]. Further chemical or thermal
reduction of so-called graphene oxide yields chemically derived graphene
(CDG or reduced graphene oxide; rGO).
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APPLICATIONS OF GRAPHENE:
Application oriented attractive properties of graphene such as its high
carrier mobilities which are 40 times higher than the typical electron
mobility for Si and its high current carrying capability makes graphene
relevant to be used in electronic devices. Moreover, owing the huge
thermal conductivity that is important for electronic devices shrinking as
circuit density increases, graphene keeps the devices cool by dissipating
heat efficiently. However, large-scale growth of graphene is necessary and
crucial to exploit those properties of graphene further. Figure 6 shows the
state-of-the art evolution of the size of synthesized graphene from µm to
inch levels. After isolation of only µm size monolayer graphene for the first
time by Geim and Novoselov , 30 inch size of single layer graphene was
produced by chemical vapor deposition (CVD) method. The largest
monolayer graphene reported so far is in 24’’ by 300’’ size grown on
copper with CVD technique. Graphene was used in touch panels [36] by
utilizing its high transparency, flexibility, and high conductivity
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Not only for electronics, graphene is one of the most promising materials
for gas-sensors as well. As gas molecules land on graphene, its electronic
properties are affected in a measurable way that enables the detection of
a gas . Graphene also finds potential applications as support material in
catalysis field due to its huge surface area [38], as an electrode material in
electrochemical applications such as batteries and supercapacitors.
Layered nature of graphene acts as a barrier against aggregation of
nanoparticles in the catalyst or electrode material. The use of chemically
derived graphene (or reduced graphene oxide (CDG or RGO)) based
materials as anode or cathode in Li-ion battery technology promotes the
improvement in the recent field due to the large surface-to-volume ratio
and highly conductive nature of graphene. The formation of nanopores
and disorders in the CDG through chemical synthesis promotes as lithium
insertion active sites that are crucial in Li battery technology. So, the
process fastens in the presence of graphene in the electrode (Figure 7, A).
In addition, both anode and cathode of a battery might become bendable
due to the flexibility feature of graphene (Figure 7, B).
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SYNTHESIS OF GRAPHENE:
There are currently four main approaches to synthesize graphene. These
are mechanical exfoliation, liquid phase exfoliation of graphite, epitaxial
growth, and chemical synthesis methods. Here three methods have been
explained in detail.
1.Mechanical Exfoliation of Graphite (Scotch-tape method):
Ther simple tape method was reported for the first time by Heinrich Kurz
et al. in 1990 to get ultra-thin films of graphite from HOPG that refers to
graphite with an angular spread between the graphite sheets of less than
1°. However, Novoselov and Geim succeeded to produce and identify
monolayer graphene by using that method in 2004 [10]. That method starts
with sticking HOPG onto adhesive tape and folding the two sticky sides
against the tiny crystals (Figure 8). After pulling the tape apart, flakes are
cleaved in two individual flakes. By repeating that splitting process a
couple of times, thinner slices can be achieved. Finally, tape with the
pieces is stuck on the silicon wafer with silicon dioxide layer on and tape is
pulled away. At the end, one can see graphene by naked eye due to the
optical contrast differences.
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Figure 8: Step by step formation of graphene via Scotch-tape method (a
to d) and overview of the process using ther method
Despite the ease of the method, it is not likely to produce large quantities.
Using ther technique, however, Chen J. et al has recently reported a study
called “Continuous mechanical exfoliation of graphene sheets via three-roll
mill” suggesting a scale up process for effective fabrication of
polymer/graphene (single to few layers) nanocomposites ].
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2.Liquid Phase Exfoliation of Graphite:
Hernandez and co-workers carried out the dispersion of graphite typically
in Nmethylpyrrolidone (NMP) followed by ultrasonication to separate the
non-exfoliated graphite. Graphene dispersions with concentrations up to
0.01 mg ml-1 were achieved. The reason for production of graphene flakes
is attributed to the solvent-graphene interaction. The energy necessary for
exfoliation is balanced by that interaction for solvents if surface energies
match that of graphene [43]. Furthermore, Mariani et al. improved the
concentration of graphene in NMP (2.1 mg/ml) by exfoliating polymer
graphite composite and further enhanced it (5.33 mg/ml) by exfoliating
the graphite in ionic liquids . Although ther technique has the advantage of
low cost and scalability, graphene flakes tend to restack and scroll easily.
3.Chemical Vapour Deposition of Graphene:
The chemical vapor deposition technique is based on the chemical thermal
decomposition of a precursor (the compound that provides the feedstock
to produce the desired material), so their individual constituents can build
up a solid film or nanostructure into a specified substrate. In general, a
common CVD equipment is composed of three main modules:
1) a precursor injection module,
2) the reaction site or chamber, and
3) the gas ejection module .
Although these three modules can be arranged either vertically or
horizontally, the horizontal configuration is the most widely used. The
reaction site consists of a region subjected to high temperatures where the
thermal decomposition of the precursor can be triggered. A very common
setup consists of a tubular furnace with a borosilicate/quartz/alumina tube
inside serving as reaction chamber, see Figure 1, the nature of the tube
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would depend on the temperature conditions used in the process. If the
process requires a catalyst, it can be placed inside the reaction chamber,
such is the case for the CVD synthesis of graphene as will be reviewed in
detail below. Depending on the mechanism used for the delivery and the
type of precursor, the pressure conditions employed, different CVD
configurations can be considered . Each one of these alternatives can
undergo the same tasks, but each will use a different approach to fulfil it. In
the following sections, some of the most common and popular
configurations will be exposed.
Figure 1:Schematic representation of a horizontal CVD setup, specifying the
three constituent modules (top) and diagram of an LPCVD setup for the synthesis
of graphene on copper foil and methane as precursor (bottom), dashed
rectangles highlight the corresponding modules.
Some different types of CVD are :-
1. APCVD
The atmospheric pressure chemical vapor deposition (APCVD) is one of the
simplest configurations found for a CVD system since it operates in normal
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conditions (atmospheric pressure), making ther option more affordable and
easier to implement at laboratories. However, due to these conditions,
problems related to the dispersion of the gases within the chamber have
been considered as one of its major disadvantages, because the
decomposed particles will not cover the substrate homogeneously as
expected.
For ther approach, different precursors can be used. In the case of liquids
or solids dissolved in solution, a bubbler or an evaporation system will be
required to stimulate the particles to be expulsed and consequently be
transferred into the chamber by the action of a carrier gas, provoking its
decomposition in the reaction site.
2. LPCVD
The low-pressure chemical vapor deposition (LPCVD) is based on the use of
vacuum for the outgassing of the system to achieve low pressures
throughout the deposition process. In comparison with the last approach,
with ther technique, the dispersion and the deposition are enhanced,
making it possible to obtain better coverage within the substrates and a
higher quality. The pressures commonly used are between 10−1 and 10−2
torr and are reached with the use of mechanical and molecular vacuum
pumps connected to the gas ejection module.
3. AACVD
The aerosol-assisted chemical vapor deposition (AACVD) is characterized
for using fine sub-micrometre-sized aerosol droplets of precursor dispersed
throughout a gaseous medium, which eventually are transported into the
reaction zone to be decomposed and deposited in the target substrate. The
atomization of the liquid precursor can be achieved by different routes, as
it could be the use of an ultrasonic aerosol generation, a pneumatic aerosol
jet, or via an electrostatic atomization. The AACVD possesses the advantage
that thermally unstable and non-volatile precursors can be employed for
the synthesis of CVD products at lower cost. In addition, ther variant is
considered a more flexible option since it can be carried out under low
pressure, atmospheric pressure, and in open atmosphere [8].
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4. Roll-to-roll CVD
Roll-to-roll CVD is one of the most recent approaches developed, and it
consists of a continuous process that can carry out the deposition of the
material on a substrate and its withdrawal or a sequential process such as a
further transference into another suitable substrate (in some cases it is
required). Ther CVD variant is equipped with conveyor belts that oversee
the transport of the substrates into the reaction site, where a continuous
inlet of gases throughout the chamber leads to a constant deposit built up
in the incoming substrate without interruption. Subsequently, the conveyor
belts either introduce the material into a second stage, where a transfer
procedure can be done automatically, or take the substrate out of the
system. Ther CVD configuration can be developed for different process
conditions, such as ambient pressure, low pressure, or a plasma-enhanced
CVD.
Synthesis of graphene via CVD:
Regardless of the CVD equipment configuration, almost all graphene
synthesis procedures share the following requirements: a transition metal
sheet that acts as a catalyst for carbon dissociation and as a substrate for
graphene growth, which is placed inside the reaction chamber; a carbon-
based precursor material [18]; temperatures around 1,000°C capable of
decomposing the precursor material and dissociating the carbon [19, 20],
at such temperatures a borosilicate tube is not convenient, the regular
choice is a quartz tube, its transparency allows direct monitoring of the
interior of the reaction chamber; a flow of hydrogen (H2) that provides a
reducing atmosphere and influences growth behaviour; and a flow of inert
or carrier gas, argon (Ar) being the privileged option [18]. A diagram of a
typical LPCVD setup for the synthesis of graphene is depicted in Figure 1. A
characteristic of CVD-produced graphene films is the polycrystalline nature
of the atom-thick membrane, as will be detailed below.
1. Copper foils as substrates:
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Although the deposition of graphene on metal substrates by CVD was
reported for the first time on other metals such as Ni and platinum (Pt), Cu
is currently the most widely used metal as a catalyst substrate for the
growth of graphene by CVD.
Ther preference can be explained by the growth mechanism of graphene
on these substrates. The difference in mechanisms was elucidated by the
group of R.S. Ruoff in 2009 [21] using carbon isotope labelling and Raman
spectroscopy mapping of graphene films grown on Ni and Cu. The
difference is due to the carbon solubility of each metal. For metals with
high solubility (9,000 ppm at 900°C in Ni, and 11,000 ppm at 1,000°C in Pt)
[22], carbon atoms infiltrate the metal matrix at high temperatures, and
ther solubility tends to increase with temperature. When the temperature
drops, the solute is precipitated from the matrix, leading to the formation
of graphene. Ther saturation and precipitation process results in the
formation of MLG regions [17, 22]. In contrast, for metals with low carbon
solubility (7.4 ppm at 1,020°C in Cu) [22], the solubility is relatively low
despite high temperatures. Therefore, the process of carbon saturation and
precipitation does not occur. Graphene is formed on the surface of Cu,
limited to it; hence, the size of the graphene films will be correlated with
the copper films in the reaction chamber. Ther process promotes the
formation of SLG [17, 22]. Common Cu foil thicknesses for the growth of
graphene films are 25 and 50 micrometres; moreover, the purity of the foil
varies among commercial suppliers.
1.1 Growth mechanism:
In general, the growth mechanism of graphene by CVD on a copper
substrate can be divided into three stages: (1) The precursor molecules
collide with the surface of the Cu substrate. As a result, they can be
absorbed on the surface, disperse back to the gas phase, or go to the next
reaction step. (2) The molecules dehydrogenate totally or partially, or
eliminate any element other than carbon (denitrogenation,
deoxygenation), and active carbon species are formed. (3) The active
species diffuse over the surface, cluster, generate nucleation sites, and
begin to grow on graphene islands on the Cu substrate [15, 23]. These
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graphene islands are grains of honeycomb arranged carbons, they possess
a particular orientation with respect to each other, when the grains are
large enough and meet carbon atoms from a nearby grain, they coalesce,
forming a grain boundary where the mismatch orientation is overcome by
the presence of 5-, 6-, 7-, and 8-membered rings [24].
1.2 Annealing:
An important step prior to the CVD synthesis of graphene is the thermal
treatment of the micrometre-thick Cu foils. Cu substrates undergo an
annealing process that consists of heating them at high temperatures close
to the Cu melting point, but lower than it (<1,085°C) for a certain period of
time [25]. The surface of copper has some roughness, grain boundaries,
surface defects, and impurity particles. Ther process is carried out in order
to smooth the copper surface, reduce surface oxides, remove volatile
impurities and surface contaminants, and favour the formation of graphene
on the surface [26]. In addition, a reorganization of the copper atoms on
the surface is promoted, which produces a release of internal stresses and
an increase in the size of the Cu microcrystalline structure.
2. Precursors:
The synthesis of graphene using the CVD technique can be carried out with
a large catalogue of carbon-based compounds used as precursors. These
precursors can be categorized by their physical state or by their chemical
structure. By physical state, they can be classified as gaseous, liquid, and
solid. While based on its chemical structure, they are separated as aliphatic
and aromatic compounds. The use of an appropriate precursor with the
right conditions can improve the efficiency of the production process and
the quality of the final product.
2.1 Gases:
Gaseous carbon precursors are the main source used for graphene
synthesis by CVD. The most used are hydrocarbons such as methane (CH4)
and acetylene (C2H2), followed by ethylene (C2H4) [27, 28, 29]. A gaseous
precursor occupies less space than a liquid or solid one, because they can
be stored in certain specialized containers. Some precursors are produced
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as a by-product of industrial processes, such as biogas, which is constituted
essentially of methane and carbon dioxide [15].
2.2 Liquids:
Liquid carbon precursors are less commonly used in CVD methods. The
most common precursors used in CVD are hexane (C6H14), ethanol
(C2H5OH), and benzene (C6H6) [30, 31, 32]. These liquid carbon precursors
are easy to use and relatively inexpensive compared with gaseous ones.
2.3 Solids:
Solid carbon precursors are equally rarely used. They are more complex in
terms of chemical and biological structure. Any organic material that works
as a carbon source can be used, including plant waste, plastics, animal
waste, insect parts, even food. Therefore, solid precursors occupy more
space in the reaction chamber than gaseous or liquid precursors.
3.3 Gases:
Molecular hydrogen has a fundamental role in the synthesis of graphene by
CVD since it acts as an activating gas. It acts by cleaning the surface of the
substrate, reducing impurities and defects during the annealing process, as
well as reducing surface oxides. It behaves as a co-catalyst, along with the
substrate, promoting the growth of graphene, as well as an etchant to
control the growth and its properties . It controls the adsorption, stability,
thickness or number of layers, the population on the catalyst surface, the
configuration of the edges, and the morphology of the domains of the
grown graphene. The flow of H2 has been considered as an important
factor for the quality of graphene during synthesis. By using a gaseous
precursor, the radius of H2 with respect to the precursor gas can be studied
. It has been observed that when the H2/CH4 volume ratio in a process is
greater than 0.5, the graphene remains in small separate islands and does
not coalesce to form a large film. Ther may happen because excess H2 can
limit graphene growth by removing weak carbon-carbon bonds despite
acting as a co-catalyst. If the ratio of H2 to CH4 is too high, the etching of
carbon species becomes much faster than the formation of graphene
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layers, destroying the integrity of the network and reducing the quality of
graphene.
Regarding the flow of the precursor gas, it has been reported that, for
methane, the number of layers does not depend on the CH4 flow rate,
although an increase in defects was observed with the increase in flow.
Similarly, the use of an inert gas can help the synthesis process. The inert
gas can be used to dilute the carbon feedstock to achieve high H2 to
precursor ratios, to increase the total pressure of the reaction chamber, or
to dilute flammable or explosive material below its lower explosive limit.
The concentration of each gas can range between 0 and 100%. The
explosive limits of H2 in air range between 18 and 60%, and the flammable
limits between 4 and 75%. Pure H2 and H2 mixture beyond the flammable
limit are dangerous. Furthermore, it can be used as a carrier gas for
precursor molecules in certain cases. Gases such as Ar and nitrogen (N2)
have been used to fulfil ther function. Ar is chemically inert under the
conditions used during the synthesis. N2 is inert as well, although more
abundant and cheaper than Ar. Since it exists as a diatomic molecule, there
is a risk that N2 will dissociate during synthesis. The dissociation product
could act as a substituent in the graphene film, causing a doping or
interruption of the network. However, the triple bond present has a very
large binding energy, so the rate of N2 dissociation should be extremely
small at the temperatures used. Furthermore, Cu is an inefficient catalyst
for the dissociation of N2.
Transfer procedures:
Once graphene has been synthesized on Cu foils, its transfer to more
suitable substrates for its study or to be used in different applications is
necessary. There are several procedures that have been developed for ther
transfer step, having as purposes: a) to separate the graphene film from
the original metal substrate where it was deposited and b) to protect the
graphene after the transference.
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http://dictionary.cambridge.org/dictionary/britis
h/graphene
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