Journal of Semiconductors

(2022) 43, 061101

REVIEWS doi: 10.1088/1674-4926/43/6/061101

Graphene synthesis, fabrication, characterization based on

bottom-up and top-down approaches: An overview
Agbolade Lukman Olatomiwa1, 3, 4, Tijjani Adam1, 3, †, Subash C. B. Gopinath2, 3, 5, Sanusi Yekinni Kolawole4,
Oyeshola Hakeem Olayinka4, and U. Hashim3
1Faculty of Electronic Engineering Technology, Universiti Malaysia Perlis, 02600 Arau, Perlis, Malaysia
2Faculty of Chemical Engineering Technology, Universiti Malaysia Perlis, 02600 Arau, Perlis, Malaysia
3Institute of Nano Electronic Engineering, Universiti Malaysia Perlis, Perlis, Malaysia
4Pure and Applied Physics, Ladoke Akintola University of Technology, Nigeria
5Centre of Excellence for Nanobiotechnology and Nanomedicine (CoExNano), Faculty of applied Sciences, AIMST University, Semeling, 08100
Kedah, Malaysia

Abstract: This study presents an overview on graphene synthesis, fabrication and different characterization techniques util-
ized in the production. Since its discovery in 2004 by Andre Geim and Kostya Novoselov several research articles have been pub-
lished globally to this effect, owing to graphene’s extraordinary, and exclusive characteristics which include optical transpar-
ency, excellent thermal, and mechanical properties. The properties and applications of this two-dimensional carbon crystal com-
posed of single-layered material have created new avenues for the development of high-performance future electronics and
technologies in energy storage and conversion for the sustainable energy. However, despite its potential and current status glob-
ally the difficulty in the production of monolayer graphene sheet still persists. Therefore, this review highlighted two ap-
proaches in the synthesis of graphene, which are the top-down and bottom-up approaches and examined the advantages and
failings of the methods involved. In addition, the prospects and failings of these methods are investigated, as they are essen-
tial in optimizing the production method of graphene vital for expanding the yield, and producing high-quality graphene.
Key words: two-dimensional material; nanomaterial; carbon material; nanostructure
Citation: A L Olatomiwa, T Adam, S C B Gopinath, S Y Kolawole, O H Olayinka, and U Hashim, Graphene synthesis, fabrication,
characterization based on bottom-up and top-down approaches: An overview[J]. J. Semicond., 2022, 43(6), 061101. https://doi.org/
10.1088/1674-4926/43/6/061101

1. Introduction ive future application of graphene as an alternative to silicon

in new generation electronics commercially is the absence of
Graphene is an exceptional carbon crystal composed of an energy band gap due to its symmetry, which unites two
single-layered materials made up of six bonded sp2 carbon types of distinct carbon atoms. Therefore, there is a need to
atoms, configured in a honeycomb lattice nanostructure with open a finite gap of graphene in the energy dispersions at K-
an atomic spacing of 1.42°. It is the underlying element point through several techniques. These techniques should
present in graphitic materials: fullerene (0D), nanotubes (1D), be cost effective in manufacturing or fabricating high quality
graphite (3D). Andre Geim, and Kostya Novoselov discovered and large area graphene sheets[6, 7]. However, the most com-
this material in 2004 at Manchester through a method called monly used techniques nowadays include chemical vapor de-
“Scotch tape peeling” by using adhesive tape to separate an position (CVD)[8], chemical via reduction of graphene oxide
isolated monolayer graphene from graphite. Hence, the (GO)[9], epitaxial growth[10], and mechanical exfoliation[11].
graphene layers produced are greatly ordered; possess Furthermore, in recent reports (CVD) and epitaxial meth-
unique and excellent electrical, mechanical, optical and ods are adopted in the synthesis of graphene to open the
thermal properties and this has meant that it has drawn lots band gap and are promising in the generation of monolayer
of attention to itself[1–3]. Furthermore, it has a high specific sur- area quality graphene on a large scale. These methods are
face area of 2630 m2/g, a high intrinsic electron mobility of not without its challenges, because the reduction of
2.5 × 105 cm2/(V·s), a superior thermal conductivity with a graphene oxide chemically includes the use of hydrazine, di-
value ranging from 3000 to 5000 W/(m·K). In addition, it has methyl hydrazine and its derivatives that are highly poison-
an extremely good Young’s Modulus with a value of 1 TPa, a ous and harmful to humans and the environment. In addi-
high current density, 108 A/cm2 and a good optical transmit- tion, other negatives of CVD are that these chemicals have ad-
tance of 97.7%[4, 5]. verse effect on biomaterials, electrochemical storage device
Since its discovery, the major challenge to the product- and polymers and these contributes to increase in the cost of
production of graphene on an industrial scale[12, 13].
Correspondence to: T Adam, [email protected] Hence, most recently the biological reduction of
Received 17 NOVEMBER 2021; Revised 23 DECEMBER 2021. graphene through plants extracts and microorganisms are de-
©2022 Chinese Institute of Electronics veloped as alternative to the use of hydrazine as a natural re-
2 Journal of Semiconductors doi: 10.1088/1674-4926/43/6/061101

Fig. 1. (Color online) Structures of (a) 3D graphite, (b, c) 2D graphene and its edge, (d, e) graphene oxide, (f) reduced graphene oxide[22].

ducing agent in the reduction of graphene oxide to manufac- reported that graphene was grown on a crystal substrates of
ture graphene on a large scale[14]. Therefore, the report a transition metals and metal carbides by decomposing hydro-
shows that cocos nucifera L. can serve as reducing agent in carbon gases at elevated temperature. In addition, in 1999
the green synthesis of graphene (Kartick et al., 2013). The ther- the physical properties of the edges of graphene were stud-
mogravimetric analysis showed that the graphene produced ied by growing epitaxial nano-sized films with a ribbon struc-
was thermally stable with lower charge density on the ture on a Ni substrate by Oshima et al.[17]. The success was
graphene surface. It was also determined that phytoextracts few and far between during this period not until 2004 when
have the potential to reduce graphene oxide in an environ- Novoselov et al. was credited to have discovered graphene
mentally friendly process with potentials in diverse areas like through Mechanical Exfoliation of graphite[18, 19].
biomedical applications (Lee & Kim, 2013). Furthermore, the study on graphene synthesis has grown
Besides, the preparation of graphene at the macroscale since the early studies of graphene on Pt substrates; this is be-
by liquid phase exfoliation to form a graphene oxide (GO) cause it is believed that it can herald the development of
halfway, which is followed by reduction to maintain the next generation electronics and technologies owing to its ex-
graphene structure (RGO). Nevertheless, it was determined traordinary properties[20]. Therefore, its application in novel
that the composition of poor dispersion, sheet defects restack- electronic devices demands high quality large-area single
ing and multilayer thickness could limit the complete realiza- graphene, which can be maneuvered to create complex appli-
tion of the high surface area and electronic properties of ances homogenized into silicon device flows[21]. Moreover,
graphene[9]. Therefore, this overview discussed chemical and the graphene synthesized by mechanical exfoliation from
green methods with their applications on nanomaterials, bio- highly ordered pyrolytic graphite, is recognized as the
materials, and polymers. The advantages and limitations of graphene with the finest electronic properties and highest
these techniques in producing safe, high quality and cost-ef- quality but for large-production, the fabrication method is re-
fective monolayer graphene in large scale with these tech- quired and optimized to synthesize size wafer scale graphene
niques are discussed. (Novoselov et al., 2004). The structures of the different forms
of graphene are illustrated in Fig. 1[22]. However, herein, the re-
2. Production of graphene cent progress in the large-scale production of graphene via
Synthesis of graphene is the process of contingent on the top-down approaches, which include reduction and exfoli-
the preferred purity, size and crystallinity of the individual ation methods and bottom-up approach, which include CVD
by-product. Interestingly, the synthesis of graphite was repor- and epitaxial growth etc., are discussed and both compared
ted in 1975 when Lang showed the formation of single- with green approach in the synthesis of graphene.
and multi-layered graphite by thermal decomposition of However, to circumvent the production of undesirable
carbon crystal on platinum substrates but was not classified and toxic by-product with the adoption of sustainable, depend-
as graphene owing to lack of techniques on characteriza- able and environmental approach. The green synthesis of
tion[15, 16]. graphene is backed to aid several biological materials like
The challenge was the inability to identify the applica- phytoextracts, algae, fungi and bacteria[23]. The plants ex-
tions of the by-product and the properties of the layers pro- tracts is an easy and facile process for mass-production of
duced on the crystal planes of platinum were not uniform, graphene and can also prevent the sizeable aggregation.
this prevented a thorough study on the material in the early Therefore, the green synthesized RGO is highly soluble in wa-
days. However, after a long while, in 1997 respectively, it was ter and suitable for practical application[9].

A L Olatomiwa et al.: Graphene synthesis, fabrication, characterization based on bottom-up ......

 Journal of Semiconductors doi: 10.1088/1674-4926/43/6/061101 3

Fig. 2. (Color online) Top-down and bottom-up approaches for synthesis of graphene[23].

2.1. Top-down approach ite[31, 32].

This is the process of breaking down or reducing graph- 2.3. Ball milling
ite into nano sized graphene sheets, which are easily com- Ball milling is an emerging method to fabricate high-qual-
plexed with separate functional materials to produce novel ma- ity graphene by breaking down stacked graphite into
terials[24]. The benefits of top-down methods embody sub- graphene. Interestingly the ball-milling process was reported
strate transfer, price effectiveness and high dependability com- to have started about 150 years ago where it was employed
pare to bottom-up approach. Moreover, it has become very im- in the talc powders, size communications of ore and several
portant to reduce the gap between research findings and com- other applications. However, in the last two decades, the tech-
mercialization of products of top-down approach[25]. As illus- nique is proposed for the creation of nano-sized particles at
trated in (Fig. 2), the graphene synthesis is based on two room temperature[33, 34]. Hence, it is facile and very effective
main approaches: bottom-up and top-down techniques[26]. solid-state method of grinding several materials into fine
2.2. Mechanical exfoliation powders, nanocomposites synthesis and for oxides making it
This is the first and one of the most widely utilized meth- a promising method for mass generation of graphene at low-
od employed to synthesize graphene from graphite, which cost[35]. During milling, the large graphite sheets are subject
uses mechanical forces to separate the layers from each oth- to shear forces, while normal force is exerted to reduce the
er to obtain graphene. However, within the graphite sheets graphite flakes into nano-sized materials and present a fault
are Van der Waals bonds, which can be broken down when ex- in the basal plane. The milling technique can be done using
foliating graphene using normal or lateral forces[27, 28]. The wet and dry conditions. As shown in Fig. 3 below, Lv et al.
gap between successive planes was said to 3.35 Å by Coulson used Na2SO4 salt to create graphene nanosheets with ripple-
in 1961 in his book titled Valence, a value so huge that it can like corrugations in the hundreds of square nanometers
only stem out of Van der Waals forces. In addition, the force re- range[36, 37]. In contrast, in the presence of graphite, dry ice,
quired to break Van der Waals bonds is 25% less than the and stainless-steel balls, ball milling was conducted in a planet-
force required to restack graphite layers, and twice less than ary ball-mill machine as illustrated in Fig. 4[38]. Hence, the size
the force for splitting graphite layers by breaking covalent and quality of the materials produced depend on the media
bonds. However, the exfoliation technique can lead to adhe- used[36]. However, Zhao et al. gave a new outlook to ball
sion in the sheets of the graphite which results in the restack- milling process by exfoliating graphite into graphene flakes
ing of the layers rather than separating the graphene layers in a liquid medium using wet ball milling. The result ob-
as exfoliation progresses[29, 30]. In summary, mechanical exfoli- tained revealed a thickness of about 0.8–1.8 nm, which corres-
ation can produce single layer graphene of high quality from ponds to discrete monolayer and few-layer graphene (≤ 3 lay-
highly ordered pyrolytic graphite but this has only been ers). Hence, this result has encouraged a lot of research activ-
proved in the laboratory and not in production on a large ity in ball milling recently[39]. Subsequently, Dash et al. also
scale. The different mechanical techniques include ball presented a facile, cost effective and environmentally friendly
milling, sonication while the adoption sonication as a mechan- approach for synthesizing graphene oxide from high pure nat-
ical wave is the most widely used technique to separate graph- ural graphite flake powder using the new horizontal high-en-

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4 Journal of Semiconductors doi: 10.1088/1674-4926/43/6/061101

Fig. 3. Schematic diagram of the soluble salt assisted (Na2SO4) wet ball milling approach for synthesis of graphene nanosheet powder[36].

Fig. 4. (Color online) (a) Pure graphene. (b) Dry ice. (c) Edge-carboxylated graphite prepared by ball milling for 48 h. (d) Schematic view of physic-
al cracking and edge-carboxylation of graphite by ball milling in the presence of dry ice, and protonation[38].

Fig. 5. (Color online) Schematic view: preparation of graphene oxide in laboratory designed ball mill[40].

ergy dry planetary ball milling approach without the use of from graphite (Figs. 3–5). It was discovered that the degree of
catalyst or toxic chemicals as schematized in Fig. 5. Here, the oxidation increased as the milling time increases. In addition,
specific surface area of the resulting GO samples increased the effects of the oxidation were examined based on the grind-
(188.25 m2/g) as the milling time of the FEED enhances[40]. ing time intervals (6, 12, 18, 24, 30 h) in this approach and
The sample obtained after 16 h of milling showed better the obtained samples in the ball milling are compared with
level of oxidation, time and energy usage factors. Hence, as the outcome of the Hummers methods. Hence, the sample
the milling time increases the amount of oxygen increased showed better dispersion and a darker color after 18 h of
without changing the structure of the lattice. milling which is due to removal of functional groups like
In addition, Casallas Caicedo et al. reported the oxida- carboxyl, hydroxyl and epoxy[41]. Here, the sample obtained
tion of graphite by the ball-milling method with the aid of po- after 16 h of milling is considered the best sample in terms of
tassium perchlorate and purified water to exfoliate graphene the level of oxidation, duration and energy usage factors are

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 Journal of Semiconductors doi: 10.1088/1674-4926/43/6/061101 5

Ultrasonic probe
Specimen container

Shock waves
Dispersant solvent

Cold water
GNPs agglomerates

Cavitation bubbles
Sonication bath

Cavitation bubbles-GNPs interactions zone

(c) Defect/Disorders Phenomenon (b) Exfoliation Phenomenon (a) Fragmentation Phenomenon

(Evolution of disorders and defects in CNPs) (Thinning of multilayer graphene to monolayer or Few-layer graphene) (Shortening and consequent dispersion of GNPs)
Edge defects (Active

Vacancies in GNPs Shock waves

sp3 Carbon)

Hot spots

Thin GNPs

dis-integrated Imploding bubble Dispersed GNPs

Open edges in GNPs
cavitation bubble (Reduced Lateral domain size, La)

Fig. 6. (Color online) Schematic view of tip sonication processing with parameters that influence graphene nanoplatelets dispersion in a liquid me-
dium with obtained phenomena. (a) Fragmentation. (b) Exfoliation. (c) Defect[46].

examined. Finally, the attractions of the ball milling tech- graphite) to determine the disorders in graphene structures.
nique are its ability to produce low-cost and high-quality However, during the dispersion or exfoliation stages, stacked
graphene. It is an effective tool in functionalizing graphene 2D graphene is prone to significant damage, which results in
and indulge effective exfoliation. However, the long pro- amorphous carbon production and a low aspect ratio of
cessing time has greatly contributed to the reduction in the graphene particles, making it unsuitable for reinforcing. Fig. 6
yield of graphene synthesis. shows a schematic diagram of GNP tip sonication in a dispers-
2.4. Sonication ing solvent (ethanol) utilizing a high-performance horn sonicat-
or[46, 47]. In addition, as the sonication time and amplitude in-
Sonication-assisted liquid-phase exfoliation is an effi-
crease the more graphene nanoplatelets were produced due
cient method, which can synthesize mass production of high-
to increasing effect of the shearing force.
quality single- or few-layer graphene[42]. However, sonication
Krishnamoorthy and his group also reported a simple
is of two types bath sonication and tip sonication. Hence,
sonochemical method of the reduction of graphene oxide in-
they are used singly or concurrently to synthesize single- or
to graphene nanosheets in a small reaction time. However,
few-layer graphene. However, the low efficiency and low en-
graphene oxide was reduced to graphene nanosheets, which
ergy input associated with bath sonication has made it not
resulted in the agglomeration of graphene oxide, which inhib-
suitable for large-scale production of graphene. In contrast, re-
its the efficiency of reduction; thereby the removal of oxygen-
search shows that high-power tip sonication method is an effi-
ated functional group was not entirely realized. Hence, ultra-
cient or rather by combining shear mixing can scale-up
sonication is used to exfoliate graphitic oxide into graphene
graphene production in a short time though may cause break-
oxide, as indicated in Figs. 7 and 8[48]. In summary, the effi-
down in the structure of the graphene. There are three
ciency of the exfoliated graphene nanosheets relies on the son-
phases associated with liquid-phase exfoliation which in-
ication time, temperature, liquid medium and the power of
clude dispersion of graphite in a solvent, exfoliating graphite
the sonication. Scientists to ensure the graphene solution is
and purification[43]. Coleman et al. first investigated this meth-
stable by improving on the dispersion in the graphene sheets
od (liquid phase exfoliation) using a bath sonicator to sonic-
have used surfactants. Hence, so far, the downside of this tech-
ate graphite in an organic solvent. Sonication occurs be-
nique is low yield, poor dispersion, high-energy consump-
cause of gap (small sized bubbles) in pressure fluctuations,
tion and the use costly layer[49].
which acts on the bulk material to create exfoliation[44, 45].
Baig et al. investigated tip sonication effects on the character- 2.5. Electrochemical exfoliation
istics of structural qualities of graphene nanoplatelets by modi- Electrochemical method is increasingly gaining attention
fying the sonication time and individual energy time at three in the production of graphene. It is different from wet chemic-
distinct amplitudes (60%, 80%, and 100%). In their work, al exfoliation method, as it does not require the use of harm-
graphene nanoparticles were characterized with the aid of Ra- ful oxidants[50]. However, a fixed potential applied on a
man spectroscopy (highly sensitive in detecting defects in stacked graphitic material force the ions to intercalate into

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6 Journal of Semiconductors doi: 10.1088/1674-4926/43/6/061101

graphene sheets are majorly two to five layers thick, nonoxidat-

ive and are free of defect. Permeable graphene layers ob-
tained by activating few layers graphene layers in potassium
hydroxide revealed improved electrochemical process.
Hence, it can be utilized in fields like energy conversion and
storage[56]. Dalal and his group also presented a new ap-
proach on cathodic exfoliation for mass production of
graphene nanoplatelets. However, this work still requires fur-
ther study to improve the properties of aqueous cathodic exfo-
liated graphene. In addition, a relatively high yield and low de-
fect graphene of ~10–13 layers of high quality ACEGNPs in
aqueous solution of alkali metal salt electrolytes with suit-
Fig. 7. (Color online) Separation of graphitic oxide by sonication for
able cation size[53]. Li et al. presented a new electrolysis to pro-
0.5 h.
duce high-quality graphene applying a dual foil as an elec-
trode and alternating currents to power the system Fig. 9.
This report supported that a decrease in temperature would
potentially control free radicals[57]. This approach is really gain-
ing attention in the synthesis of graphene owing to its poten-
tial in mass production of environmentally friendly, cost effect-
ive and high-quality graphene.
2.6. Bottom-up approach
This approach is a layer-by-layer method that begins
with the formation of small molecular carbon atoms to de-
rive graphene. However, epitaxial growth of graphite on SiC,
chemical vapor deposition, chemical reduction are the promin-
ent method used[58, 59]. However, these methods use harmful
Fig. 8. (Color online) Sonochemical synthesis of graphene oxide into
oxidizers or carboxylic acid and organic solvents, which are
graphene nanosheets in the presence NaOH[48].
not ecofriendly. Hence, the use of phytoextracts and microor-
graphene layer reducing the Van der Waals forces between ganisms are viable alternatives employed in this approach
the surfaces, which separates, and exfoliate discrete due to its green nature and eco-friendly in production[60]. The
graphene layers. This operation holds in a liquid medium or or- advantage of bottom-up approach is the controlled thick-
ganic solvents, and it can be pegged in to anodic, cathodic ness of the graphene layer achieved with the aid of separate
surface catalysts and growth criteria[61, 62].
and double-electrode exfoliation that is contingent on exfoli-
ation plate[51, 52]. Pervez et al. studied a highly efficient electro- 2.7. Epitaxial growth on SiC
chemical anodic exfoliation of graphite in different aqueous in- In this approach monolayer and few layers graphene
organic salts which include the following ((NH4)2SO4, Na2SO4, sheet can be grown by the depletion of the surface of Si on
K2SO4). Hence, the oxidation level was reduced which en- SiC substrates at a high temperature in a vacuum[63]. How-
hanced the chemical and electronic properties of graphene. beit, the nature of the obtained graphene in ultrahigh vacu-
In addition, this approach is scalable and suggests it can be um is poor due to high sublimation rates at low temperature.
utilized for large-scale production of graphene because high Therefore, multiple layer graphene epitaxial layers formed on
yield graphene nanoplatelets with large graphene flake size SiC(0001) face can orient in the 30 phase or the 2 phase with
was obtained as shown in Fig. 8[53]. Munuera et al. investig- respect to the substrate, as shown in Fig. 9[64]. Badami investig-
ated how NaCl (table salt) can be an effective additive (co-elec- ated the graphitization of α-Silicon Carbide that can be trace
trolyte) based on ordinary sulfate-based electrolytes produ- the method back to as early as 1962. Consequently, Van Bom-
cing anodically exfoliated graphene with a negligible oxida- mel and his group presented that low-energy diffraction
tion (O/C ratio ~ 0.02–0.03) the synthesis of high quality and (LEED) experiments reveal the structure of graphite was crystal-
√ √
low-oxidized graphene nanoplatelets with a high structural lized on a hexagonal SiC(0001) surface by (6  × 6  ) R 30°
grade. The resulting low-oxidized graphene showed a remark- structure. It was discovered that separate graphitization of
able ability to absorb towards organic dyes in a solvent (e.g., the two discrete polar force. The initial state of Si-face pro-
~0.450 g/g for methyl orange), a considerable potential to ab- duces monocrystalline sheets while C-face produce. Hence,
sorb non-polar substances and non-polar solvents (15–30 the study could not reveal the presence of 2D crystals[65, 66].
g/g) and showed a reliable capacitive energy storage re- In 2011, De-Heer and his group presented confinement-con-
sponse. In contrast with previous study, this work presents a fa- trolled sublimation method to produce high quality epitaxial
cile, a relatively cheap with easily accessible materials as a sub- single or multi-layer graphene on either the polar faces of the
stitute oxidation-inhibiting co-electrolyte[54, 55]. Yang et al. SiC crystal with applications in electronics. The Georgia Insti-
presented a cathodic electrochemical technique employing tute of Technology initiated this study of graphene electron-
ionic liquid, N-butyl, methylpyrrolidinium, bis(trifluoromethyl- ics: they started and presented a serious pursuit on epitaxial
sulfonyl)imide at room temperature (BMPTF2N) was pro- graphene for graphene-based electronics. The method al-
duced for few-layer graphene layers. The as-produced lows that the graphitization temperature to be regulated

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 Journal of Semiconductors doi: 10.1088/1674-4926/43/6/061101 7

Fig. 9. (Color online) Image of graphite flakes after electrochemical exfoliation. (b) Dispersed EG in DMF solution (concentration 2.5 mg/mL). (c)
EG size on a bulk scale (163 g). (d) Diagrammatic representation of the principle of electrochemical exfoliation[53].

between SiC(0001) surface and the corresponding surface in

contact. It was discovered that it restricts the sublimation of
Si by ensuring the formation of the graphene is regulated
and uniform Fig. 10. The results obtained revealed that
FTF/FTG approach is essential for producing single-layer EG
growth at very high temperature and 101-kPa Ar pressure[70].
Zimbone et al. investigated the properties of cubic silicon
carbide (3C-SiC) epitaxially produced on a patterned silicon
substrate compressed of squared inverted silicon pyramids
(ISP). This compliant substrate inhibits stacking faults associ-
ated with SiC/Si bond from contacting the surface. Be that as
it may, a hole which appear on the epitaxial layer is caused
by anti-phase boundaries created at the highest point of the
pyramid. Along these lines, it was shown that by controlling
the growth parameters permit the reduction of the height of
the vacancy and the thickness of APBs, which enhances the
Fig. 10. (Color online) (a) Schematic view of the configuration used for SiC epitaxy quality. Howbeit, the thermal decomposition of
face-to-face growth technique setup; (b) magnified view of the 3C-SiC should beat the constraints of cost, wafer sizes, and mi-
sample set up highlighted in panel (c) enlarged view of mounted SiC cromachining operations[71, 72].
substrates highlighted by red lines in panel[64].
2.8. Chemical vapor deposition (CVD)
which is an improvement to growth at low temperatures The CVD method is a bottom-up approach and is one of
plagued with production of defects in the graphene layers. the main techniques utilized for preparing large-area high qua-
Despite the success recorded in this research, production of lity graphene. Graphene is created on surfaces of various tran-
graphene-based is yet to be realized[67, 68]. In 2011, Srivast- sitions metals surfaces for example, Ni and Cu foils used as
ava and Feenstra examined the effect of the annealing environ- substrates from different vapor classes as a carbon source
ment on the structure, shape and thickness of graphene pro- through chemical reactions. Optimizing the parametric
duced on SiC(0001) surface. The graphene produced via this growth process like energy, pressure, flow of carrier gas has
process can be applied in future electronic devices[69]. Real et been utilized to regulate the growth process[73−75]. Juang et
al. also reported the use of Face-face and face-graphene pro- al. are among the earliest, which synthesized single layer
cess, the rate of diffusion is reduced by trapping the vapor graphene (SLG) to few layer graphene (FLG) films by the CVD

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8 Journal of Semiconductors doi: 10.1088/1674-4926/43/6/061101

Fig. 12. (Color online) The graph of the sheet resistance versus the trans-
Fig. 11. (Color online) (a) Roll-to-roll process for the transfer of FLG mittance of the FLG/EVA/PET samples[76].
from Ni foil to EVA/PET metal surface[76].

method on Ni foils. The transfer of centimeter scale FLG by

means of Ni foil to transparent flexible polyethylene terephthal-
ate substrates using an efficient roll-roll-process[76, 77].
Moreover, the result obtained indicate that regulating the cool-
ing rate of the CVD technique will not be a suitable paramet-
er for controlling the size of the graphene films, because of de-
position and precipitation procedure will take place simultan-
eously in the graphene growth. The roll-to-roll technique for
transferring FLG from Ni foil to EVA/PET substrates is depic-
ted in Fig. 10 and a translucent flexible FLG/EVA/PET sample
measuring 2 × 3 cm2 and transferred samples of 1 cm2 with
varied transmittances. In addition, the sheet resistance versus
transmittance plot of the FLG/EVA/PET samples is shown in
Fig. 11.
In 2011, Hesjedal investigated the continuous growth of
few-layer, and potentially single-layer, graphene on Cu foils,
which run through an atmospheric CVD system in a roll-to-
roll process[78]. Here, Cu was chosen as the substrate material
because the low solubility of carbon in copper led to self-lim-
ited few-layer graphene growth. Hence, it was determined
that the few-layer graphene films on Cu reveal a sizeable
scale of few-layer graphene and the process can enable the
fabrication of graphene for the diversity of electronics applica-
tions.
Zhao et al.[79] demonstrated in 2013 that low-pressure
CVD on Cu surface from a carbon precursor aside methane
and examined the growth of graphene through ethanol and
self-limiting behavior over the copper surfaces compared in
less than 30 s growth time. The timing used was to keep the
framework from yielding multilayer graphene. More so, the
choice of Cu here as the catalytic substrate is premise on the
low solubility of carbon in copper, which limits the growth of
graphene to the outer layer of the material to facilitate yield-
ing of high-quality graphene. The graphene grown on the Cu
Fig. 13. (a) Pure VCCD-MWNT revealed the graphene helices released
foil exhibits properties related to that grown on methane un-
from the walls. (b) Milled for 1 h. (c, c’) Milled for 120 min[83].
der low-pressure conditions. Hence, arrangement of the
graphene domains isn’t reliant on the structures of the precurs-
or (ethanol and methane) when the carbon flux is moder- hanced with Cu while Ni presented a good catalytic activity.
ately low. Hence, a uniform and great quality wafer-scale graphene film
In the same vein, Dong et al.[80] investigated the growth was obtained from the SiO2/Si substrate at low temperature
of Graphene by plasma improved CVD at a low temperature (600 °C) due to the enhanced growth parameters and join-
(600 °C). The Ni–Cu alloy was chosen to work on the homogen- ing them with in-situ growth process. It was likewise found
eity and nature of graphene. The carbon diffusion rate was en- that plasma had a tremendous impact on the nature of

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 Journal of Semiconductors doi: 10.1088/1674-4926/43/6/061101 9

Table 1. Indicating the different graphene produced using CVD method.

Methods or annealing Mobility
Metal surface Pressure Temp. (K) Size & shape H2/CH4(/Ar) Growth time Reference
pretreatment (cm2/(V·s))
Cu foil LPCVD 1308.15 0.5 × 10–3 m, 2/1.3 Inside surface of 4000 (e) [87] (2011)
dendrites copper-foil enclosures
Cu foil APCVD 1323.15 ~15 μm H2/Ar, 10/300 H2/Ar, 10/ 300 sccm, <103–104 ~0.167 h [88] (2011)
hexagonal CH4 in Ar 8 1323.15 K, 30 min
ppm annealing
Cu foil LPCVD 1350.15 ~2.3 × 10–3 m, 70/0.15 High pressure ~11000 2.083 h [89] (2012)
~4.5 × 10–6 m annealing (1500 torr,
500 sccm H2, 1350.15
K, electrochemical
polishing
Ni (111) UHV 873.15–10 Millimeter size Propylene Ni(111) hetero- – 0.0833 h [90] (2011)
73.15 ga(C3H6) epitaxially grown on
MgO(111)
Cu foil LPCVD 1273.15 100 μm, six- 12.5/1 0.667 h; vapor 4200; 20000 0.5 h [91] (2012)
lobed flower trapping (hbn)
Liquid foil APCVD 1433.15 >100 μm, 300/6 200 sccm H2, 1373.15 1000–2500 0.5 h, 10–50 [92] (2012)
hexagonal K, 0.5 h μm/min
Liquid foil APCVD 1363.15 >200 μm, 80/10, CH4:Ar, 100 sccm (1.3 H2/Ar – – [93] (2012)
hexagonal 1.99 mix) 1090 °C, 0.5 h
Cu foil LPCVD 1308.15 Centimeter 10/0.1 0.1 torr H2, 1308.15, 40000-65000 12 h [94] (2013)
size 0.5 h; 1 × 10–3 (1.7 K);
15000–30000
(r.t)
Cu foil APCVD 1273.15 25 × 10–3 m 10–15 sccm Ar, 600 10–3700 0.333–0.16 h [95] (2011)
diameter sccm for H2, and (1273.15)
quartz 10–50 sccm for CH4
Cu foil LPCVD 1308.15 ~2 × 10–3 m 10/0.1 Inside surface of Cu 5200 6h [96] (2013)
tube electroplating
Cu foil LPCVD 1273.15– 0.25-inch- 10/315 1010 °C and a 25 mm/min 24 h [97] (2015)
1318.15 wide, 0.002 pressure of 533.289 (1273.15–
inch thick pascals with flows of 1318.15)
100 sccm H2 in both
the inner tube were
changed to 300 sccm
H2 for the tube gap

graphene created. al vapor deposition on Cu foil Fig.13. The results show that
Al-Hilfi et al.[81] hypothetically examined, from both a ther- an atmospheric approach can annihilate the difficulties re-
modynamic and a Kinetic viewpoint, the process of CVD lated with low-pressure CVD process while enabling the devel-
growth on Cu–Ni surfaces. In their work, two temperature opment of this innovation to the roll-roll industrial scale
was considered in the gas phase, below 800 °C and beyond graphene generation[84]. Thus, the incombustible nature of
800 °C. Earlier in 2006, Somani likewise researched the synthes- the low concentrations of the mixed flow of stock gases (H2
is of planar few layer graphene (PFLG) films where a cam- and CH4) as the methane source of the atmospheric CVD is
phor pyrolysis on Ni foil[82]. Despite the success recorded in an advantage over the low-pressure CVD method. In this
reducing the layers of the graphene the drawbacks are the in- work, a 40” monolayer graphene with graphene areas mostly
ability to achieve a monolayer graphene. Furthermore, the larger than 100 μm was effectively accomplished.
method of deposition of PFLG on Ni foils utilized in this work Despite the significant progress with the CVD method to
is not appropriate for the fabrication of electronic devices like grow graphene on the transition metal surface to produce
FET. graphene with high quality, fine grained and better hardness
Lee and his group[83] successfully synthesized graphene over other coating methods, a portion of the under recorded
sheets larger than 100 nm2 in an area realized at a plasma-en- difficulties endures. The gaseous by-product of the process is
hanced (PE)-CVD condition. Multi-wall carbon nanotubes (MW- for the most part destructive. This is on the grounds that the
CNTs) were taken for a ball milling process to produce precursor gases used are highly volatile for it to react with
graphene nanopowders. Consequently, the graphene nano- the metal surface, yet it should not be too volatile to trans-
powders are used as the precursor of the PE-CVD process. port them to the reaction chamber[85]. It additionally requires
HRTEM pictures of MWNTs before and after mechanical high temperature in this manner making it an ineffective meth-
milling for varied periods of time are shown in Fig. 12. The od. Thus, the inclusion of plasma in the CVD operation in the
characterization by electron and diffraction, high-resolution production of wafer-sized monolayer graphene films can be ac-
microscopy indicates the presence of high-quality pure mono- complished at lower temperature[86]. In this way, the creation
layer graphene sheets. of graphene with large and uniform grain size with con-
Vlassiouk et al. examined that large-scale high-quality syn- trolled thickness is fundamental in diverse applications in elec-
thesis can be executed utilizing atmospheric pressure chemic- tronics Table 1.

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10 Journal of Semiconductors doi: 10.1088/1674-4926/43/6/061101

Fig. 16. TEM images of graphite oxide[97].

100

80 (b)
Fig. 14. (Color online) Image of powder and the aqueous dispersion of

Weight loss (%)

graphene oxide (0.5 mg/mL) before (left) and after reduction
(right)[104].

60

(a)

40

200 400 600 800

Temperature (°C)

Fig. 17. Plot of thermogravimetric analysis of (a) graphite oxide and

(b) graphene[97]

in an aqueous dispersion of the arising RGO through electro-

static repulsion exchange of the negative charge densities of
the diverse carboxylic group[9]. The plants-based method is pre-
Fig. 15. SEM image of graphite-oxide[97].
ferred to the microorganisms method because it obliterates
the need to have high maintenance cell cultures and can be
2.9. Non-toxic reducing agents
easily utilized for mass production of graphene[104]. Though
The chemical method in the reduction of graphite oxide the plant-based method is very encouraging, there is no re-
(GO) is one of the most important, and generally accepted pro- cord of optimization of reaction conditions and screening of
cess to obtain quality and uniform graphene film. Despite plants to reduce graphene oxide.
this success, the evidence of trace amount of toxic reducing Lee & Kim studied seven plant extracts, which include
agents in the produced graphene film are harmful to hu- cherry, platanus, persimmon, magnolia, maple, pine, and
mans and are not environmentally friendly[98]. Therefore, the ginkgo and compared their potentials to reduce graphene ox-
use of natural reducing agent in the reduction of graphene ox- ide[105]. There was an obvious change in the color of the mix-
ide will serve as a viable alternative, reduce cost and offer a ture on reduction of the graphene oxide as schematized in
green approach in the synthesis of graphene. As of late stud- Fig. 13 below. Furthermore, several characterization tech-
ies shows that caffeine[99], melatonin[100], ascorbic acids[101], niques such as UV–Vis spectroscopy, Raman spectroscopy,
wild carrot root[102] and amino acid[103] can supplant hy- FT-IR, XPS, XRD, TEM and TGA established that cherry leaf ex-
drazine. In lieu of this, the biological reduction of graphene ox- tract reduced graphene oxide.
ide from plants extracts and microorganisms is proposed as In 2011, Kartick et al.[14] demonstrated that C. nucifera (co-
substitutes to the chemical methods. cos nucifera) a natural reducing agent via a green method to
However, the significant qualities of these plant extracts produce graphene by reduction of graphite oxide. X-ray diffrac-
are their superabundance in nature, cost effectiveness with tion, UV–Vis and Raman spectroscopy was utilized to uncov-
their distinct physicochemical attributes. More so, the plant ex- er the formation of graphene. Furthermore, SEM and TEM ana-
tracts contain a few carbolic compounds like chlorogenic lyses were used to evaluate the morphology of the sheet, trans-
acids, gallic acids, salicylic acids and vanillic acids etc. The parent character of graphene as illustrated in Fig. 14 respect-
phytoextracts will assist with turning away the accumulation ively. Furthermore, the thermogravimetric analysis confirmed

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 Journal of Semiconductors doi: 10.1088/1674-4926/43/6/061101 11

Fig. 18. (Color online) Schematic view of the oxygen functionalities in GO and RGO [108].
Table 2. Different strategies on green synthesis of graphene.
Source Preparation Morphology Advantage Properties Application Ref.
RGO was prepared
Low cost, facile, Sharp diffraction
from graphite Stabilized
citrullus colocynthis green method for peak [110]
powder using the reduced graphene Anticancer drugs
(leaf extract) deoxygenation of increase in interlayer (2017)
modified sheets
GO. spacing of GO
hummers method
Graphite oxide was
SEM and TEM
prepared by
images showed
oxidation of
transparent and Environmentally
graphite with a
c. nucifera (cocos stable layers friendly Low surface charge [111]
mixture of sodium Biological materials
nucifera l.) towards electron non-toxic reducing density (2013)
nitrate,
beam. AFM showed agent
concentrated
the bi-layer
ssulfuric acid and
graphene.
potassium chlorate
Graphene oxide was Increase in
Plants extracts
prepared using the hydrophilicity which
(cherry, platanus,
modified hummers Reduced graphene Environmentally was caused by the Biomedical [110]
magnolia,
method, which was oxide friendly reduction in polar applications (2013)
persimmon, maple,
followed by functionality on the
pine and ginkgo).
ultrasonication. surface of the layers
Improved hummers
method was used to
oxidize graphite for
the synthesis of
Presence of several
graphite oxide and
oxygen containing
followed by Single or few layer Facile and green Biological and [109]
Pomegranate juice group in the
reduction of as- graphene sheets method optoelectronics. (2014)
presence of
produced graphene
graphene oxide
oxide by
pomegranate juice
to form graphene
nanosheets
Single layered Low cost, green and
Modified hummers Removal of oxygen [111]
Ascorbic acid graphene is 1 nm efficient method, Water purification
method functional group (2017)
thick. naturally available
Environmentally
friendly reduction
Modified hummers Partial removal of [112]
Wild carrot root Few layers graphene method, cost Electronic devices
method oxygen functionality (2012)
effectiveness, simple
approach
The oxidization of
graphite using The high intensity of
hummers method to the main peak in GO
form GO and then Low cost, shows a sizeable
Lime juice (citrus Reduced graphene [113]
the graphene oxide environmentally number of oxygen Biological materials
aurantifolia) oxide (2019)
was reduced where benign method containing groups,
lime was used as the which occur after
natural reducing the deposition.
agents
Biocompatible,
Mango leaves was
Environmentally photostable, Biomedical
cut down into tiny [114]
magnifera indica Few layers graphene friendly, scalable, far excellent cellular nanotechnology
pieces (1–2 cm) and (2016)
and green method. uptake, good applications
dipped in ethanol
resolution

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12 Journal of Semiconductors doi: 10.1088/1674-4926/43/6/061101

Table 3. Different ways of synthesis for graphene.

Method Size Advantage Disadvantage Application Ref.
Highly expensive, low yield,
High quality, suitable for Field effect transistors,
Epitaxial growth 50 μm wafer size, introduces voids [115,116]
electronics photodetectors
in the transfer process
The use of harmful oxidizer
or carboxylic acids, cost of
High quality and mass
Chemical vapor the substrates may be high. Electronics: light emitting
0.2–10 μm production, easy to transfer [117,118]
deposition The formation of graphene diode, biosensors
to other materials.
via high temperature on
metal surface.
Low cost, facile (simple),
Green method for
deoxygenation of GO,
reduces waste, the use of
Dye removal,
harmless solvent, suitable for
Green synthesis 200–800 nm electrochemical storage, [119,120]
large scale production of
Photocatalysis
graphene nanoparticles,
high temperature and
pressure are not required,
environmentally friendly
Cost effective, high quality Low yield, defects and in the
Mechanical
5–10 nm graphene layers and flakes produce are Space protection, energy [121,122]
exfoliation
laborsaving inconsistent.
Difficulty in removing the
Electrochemical surfactants molecules,
2–3 nm High quality single layer Supercapacitors, batteries [118,119]
exfoliation inconsistency in the
produced graphene layer

that graphene was all the more thermally stable when com- 3. Conclusions and perspective
pared with graphite oxide. The schematic diagram of the ther-
mogravimetric study of graphite oxide and graphene in a nitro- The carbon material ‘graphene’ has gained significance
gen atmosphere is shown in Fig. 15. Thus, the graphene pro- in the field of micromanufacturing, nanomaterials, biomedic-
duced through this method gives incredible significance to dif- al, and composite materials owing to its high surface area
ferent applications mostly in bioelectrical materials. thermal, electronic and physical properties. Be that as it
The deoxygenation of GO by means of C. Colocynthis may, the mass production of graphene for its wide range of
leaf extract polyphenols as a reducing agent was presented applications rely on the production techniques and attracted
by Zhu et al.[106, 107]. The change in the color of the suspen- with significant attention recently. Therefore, optimizing the
sion from brown to black in their study indicates successful re- production method is vital for expanding the yield, produ-
moval of oxygen from GO. The different imaging techniques cing high quality graphene and most importantly adopting
employed (Raman spectra, XRD and XPS data) affirmed the ef- facile, cost-effective and environmentally benign method is
fective deoxygenation of GO. The plant extracts played an im- the way forward. Hence, future study should be fixed on work-
portant role to stabilize and prevent the aggregation of re- ing with the measure of yield, biocompatibility as the use of
duced graphene oxide nanosheets. In addition, the cytotox- poisonous chemicals, high energy, pressure and poor trans-
icity tests confirmed that synthesized RGO can be used as anti- fer process in chemical approaches that have contributed
cancer agent and cytotoxicity does not rely on the dose. significantly to high-cost of production, poor yield and imper-
Henceforth, the method revealed the commercial produc- fections in the obtained graphene. All things being equal,
tion of RGO in an environmentally friendly approach using the headway of novel methods and green sources is essen-
plant extracts Fig. 16. tial for synthesis of graphene materials in electronics, nanoma-
Besides, De Silva et al.[108] studied the production of terials and biomaterials. The production creation methods
graphene oxide by oxidizing natural graphite and ascorbic and carbon sources are important in determining the size,
acid. The outcome demonstrates the graphite was success- morphology and optical characteristics of the obtained ma-
fully oxidized to vastly oxygenated and exfoliated layers. The terial. In a nutshell, despite myriads of research on the pro-
different characterization techniques (AFM, XPS) employed in duction of graphene since its discovery, none of the ap-
this study shows the presence of residual oxygen functionalit- proaches fully satisfy its production on an industrial scale.
ies. Nonetheless, XRD results show an absolute removal of This overview provided a comparative study as well as pos-
the GO peak after 50 min[123]. The types of oxygen functionalit- sible applications of graphene and discussed the potential
ies existing in the GO and RGO is schematized in Fig. 17 be- methods.
low. In synopsis, this study provides a green, savvy and scal-
able way in the synthesis of quality graphene from natural gra-
phite with ascorbic acid Tables 2 and 3. Furthermore,
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