Perspective

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Graphene at Fifteen
Ruquan Ye*,†,‡ and James M. Tour*,§,⊥,∥,#
†
Department of Chemistry and ‡State Key Lab of Marine Pollution, City University of Hong Kong, Hong Kong, China
§
Department of Chemistry, ⊥Smalley-Curl Institute and the NanoCarbon Center, ∥Department of Materials Science and
NanoEngineering, and #Department of Computer Science, Rice University, 6100 Main Street, Houston, Texas 77005, United States

ABSTRACT: Graphene is a two-dimensional nanomaterial

composed of 1−10 layers of carbon atoms in a honeycomb
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lattice. It has been 15 years since the first isolation of few-layer

graphene from graphite by the Scotch Tape method. Worldwide
research efforts on graphene have been rewarded with enormous
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breakthroughs in fundamental science and innovative applica-

tions. To achieve an influential impact on society, graphene must
be manufactured at large scales, be superior to existing products,
and be safe to use. In this Perspective, we highlight relevant
issues in the quest for commercialization of graphene-containing
products. We showcase achievements in improving graphene
synthesis while also discussing concerns regarding graphene standardization and graphene’s impact on the environment
and human health.

S ince the isolation of few-layer graphene (FLG) by

mechanical exfoliation in 2004,1 there have been
significant advances in graphene research, ranging from
fundamental science to applied technologies. The ability to
prepare high-quality single-layer graphene (SLG) and FLG has
enabled successive discoveries that capitalize on the fascinating
properties of graphene. In the early years of research, SLG was
demonstrated to have high mechanical strength, with a Young’s
modulus of 1 TPa, high electron mobility at 2.5 × 105 cm2 V−1
s−1, high optical transparency at 97.4% transmittance at 550
nm, high chemical stability, and a high thermal conductivity of
3000 W mK−1.2 More recently, additional breakthroughs have
been achieved by manipulating the graphene structure, such as
band gap opening of layered graphene,3 quantum tunneling by
vertical heterogeneous stacking,4 and the superconductivity of
twisted bilayer graphene.5 With all these merits arising from
one material, graphene demonstrates potential advantages over
many existing market products, and it has been suggested as
the leader of the next generation of revolutionary materials
technologies.2 For example, FLG has a transparency and sheet
resistance comparable to that of indium tin oxide (ITO), a
widely used material in electronics.6 Yet, graphene’s superior
mechanical flexibility makes it more suitable than ITO for
flexible electronics applications.
Research on graphene continues to expand, and the topics
have extended from the synthesis and applications of graphene
to the exotic properties of its derivatives. A majority of past
research was at the laboratory scale, and concerns exist
regarding the feasibility of commercializing graphene. For
industrial applications, graphene manufacturing must be
scalable while addressing the trade-offs between quality and
the cost of the graphene product. Further, the feasibility of
using graphene to replace existing products and whether
graphene can meet product performance specifications while
overcoming price pressure from competing materials must be
evaluated. So far, graphene products have shown advantages in
several fields ranging from aerospace to supporting equip-
ment.2,7,8 With the goal of promoting and lobbying for the
commercialization of graphene, the National Graphene
Institute in Europe and the National Graphene Association
in the United States have been established. The commercial-
ization of graphene calls on the standardization of different
grades, the development of technologies pertaining to the cost-
effective production of those grades of graphene, and the
assessment of risks to the environment and health, all of which
we will highlight in this Perspective.
Graphene Standardization. The first introduction of
graphene in 2004 referred to FLG bound in a honeycomb
structure.1 Since then, hundreds of methods have been
developed to replace the low-yielding Scotch Tape method.
Depending on the number of stacking layers, different names
have been adopted to describe the available graphene, such as
SLG, FLG, multilayered graphene (MLG), and graphene
nanoplatelets (GNPs). To address the discrepancy in
definitions, the International Organization for Standardization
(ISO) released its chosen terminologies for graphene and
graphene derivatives in 2017, which stringently define the layer
numbers of graphene, bilayer graphene (BLG), and FLG to be
1, 2, and 3−10, respectively.9 The definition was based on the
finding that SLG is a semimetal with zero band gap,1 and its
stacking changes the physical and electronic properties.10 The
layers could be in the form of Bernal, rhombohedral, or

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Figure 1. Analysis of commercial graphene products in terms of (a) graphene layers and (b) average lateral size. Adapted with permission
from ref 11. Copyright 2018 John Wiley and Sons.
turbostratic stacking, which refers to AB stacking, ABC
stacking, or stacking with relative rotational angles that cannot
be described by the classic atomic plane families. As the AB-
arranged stacking layers go beyond 10 layers at room
temperature, the nanosized assembly becomes graphite-like
and is termed GNPs.9,11
The graphene standardization suggested by ISO directs the
classification and comparison of different synthetic techniques
with respect to product structure. However, the graphene
products on the market remain ill-defined. There are hundreds
of graphene suppliers worldwide.7,11 In the global graphene
market, there are three major available products: graphene
films, graphene oxide (GO), and GNPs. However, serious
concerns have been raised regarding the lack of standardization
of these commercial samples.7,11 Most of the commercial
products with the label of “graphene” were found to be either
FLG with an average lateral size smaller than 100 μm, or GNPs
(Figure 1).11 The misnaming of graphene of different grades
will slow its commercialization due to customer confusion and
their probable lack of analytical resources to confirm product
structure. For example, not all applications require the use of
SLG with the best transparency, electron mobility, and
conductivity. At the same time, the use of inferior graphene
grades could lower performance and lead to inaccurate
assessments of graphene suitability for the product. Even
here, in this Perspective, we will continue to use the general
term graphene when the actual materials may be SLG, FLG, or
GNPs.
Standardization of graphene products on the market is
nontrivial. Graphene prepared by different methods or
companies can possess varied properties, such as in the
number of layers, polymer residues, defect densities, lateral
dimensions, metal contamination, mobility, and conductivity.
These properties are not reflected in the ISO standards, yet
they are important parameters in determining performance in
applications. The method for proper characterization involves
the use of transmission electron microscopy (TEM), Raman
spectroscopy, atomic force microscopy, and other techniques
that will inevitably increase the cost of graphene manufactur-
ing. To establish a robust graphene industry, in addition to the
proper classification of products according to ISO standards,
communication between graphene producers and application
developers needs to be improved.
Graphene Manufacturing. Most fundamental studies use
single-crystal graphene that is mechanically exfoliated from
highly oriented pyrolytic graphite because of the high-quality
B DOI: 10.1021/acsnano.9b06778
Perspective
To establish a robust graphene indus-
try, communication between graphene
producers and application developers
needs to be improved.
graphene obtained using this approach.1 However, this Scotch
Tape method is only feasible in fundamental research, not in
industrial production due to the low yield and poor
reproducibility. The compelling properties of graphene have
stimulated the development of alternative approaches to the
synthesis of graphene, including chemical vapor deposition
(CVD),6,12 conversion of SiC,13 reduction of GO,14 chemical/
liquid/solid/gas/mechanical exfoliation of graphite,15−17 and
laser-assisted manufacturing.18,19 Among these methods, CVD
is the most commonly used to produce high-quality graphene
with good control of layers, even single crystals,20,21 but the
cost is higher and production capacity is lower. The most
popular bulk preparation method involves exfoliation from
graphite, with or without solvent, mechanically or electro-
chemically.15,17,22 The exfoliated product is generally FLG or
GNPs, all AB-stacked. One can induce chemical exfoliation
through oxidation to GO, and subsequent reduction affords a
FLG product with damaged graphene planes.14 Bottom-up
synthesis using small halogenated molecules as precursors can
create graphene with well-defined structure and properties, but
the scales are far too low for commercial applications.23
Chemical vapor deposition provides a
scalable method to produce graphene
with quality comparable to that of
mechanically exfoliated graphene.
Chemical Vapor Deposition. Graphene grown by CVD on
a nickel substrate was reported in 2006.12 Although the
graphene was FLG, CVD provides a scalable method to
produce graphene with quality comparable to that of
mechanically exfoliated graphene. Since then, enormous
advances have been made in this field. The CVD growth of
graphene involves several parameters, and the graphene
properties can be affected by the growth conditions including
the substrate,6,12 carbon source,24 mass transport of gas,21 and
partial pressure.25 Further, the graphene transfer process can
greatly affect the final properties of the graphene (Figure
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2).26,27 For substrates, metals, such as nickel,12 copper,6
platinum,27 and their alloys,21 as well as nonmetals, such as
Figure 2. Scheme for continuous chemical vapor deposition
growth of graphene.
germanium,28 silicon oxide,29 and hexagonal boron nitride,4
have been used. Each of the substrates has their advantages,
such as faster growth rates,21,27 easier detachment from
substrates,28 and better graphene crystallinity.21 Copper has
been the most popular substrate because it is more affordable
and has low carbon solubility, a critical property for the growth
of SLG. With thorough studies on the effect of surface
roughness,30 oxygen content,31 and liquidized copper,32 wafer-
scale high-quality SLG has been successfully grown. For carbon
sources, most of the studies use gas precursors with methane at
99.999% purity for single-crystal SLG.30−32 Growth of
graphene from solid precursors is also feasible, but the
formation of single-crystal graphene is not currently possible
from solid sources.24 Other parameters such as chamber
pressure, flow rate, and direction of gaseous precursors control
the nucleation densities and the carbon solubility in substrates,
which are also important for the growth of wafer-scale single-
crystal graphene.20,21,25
Although the CVD process resolves the scalability and
production capacity problems encountered by mechanical
exfoliation, it is expensive because of high energy consumption
and the lengthy and costly transfer process required. Therefore,
there is sustained interest in reducing the cost of CVD-grown
graphene. For example, the use of a plasma-enhanced CVD
process helps the dissociation of gas precursors and achieves
graphene growth at much lower temperatures.33 Wrinkle-free
single-crystal graphene can be grown on germanium, and the
easy detachment of graphene due to the weak interaction
Figure 3. Schemes for the exfoliation of graphite by (a) oxidative and (b) nonoxidative intercalation approaches.
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Perspective
between germanium and graphene simplifies the transfer
process and affords easier reuse of the substrate.28 The
development of roll-to-roll automated processes can manu-
facture graphene films continuously and increase productiv-
ity.26 However, these methods generally produce lower-grade
graphene, with some flaws in qualities such as thickness, sheet
resistance, and defects. Nonetheless, these developments are
important advances toward the cost-effective production of
graphene, and future optimization of these methods are
expected.
A number of methods are used to remove the graphene from
the substrate. Substrate etching is a common method (vide
infra) but is costly in terms of materials usage. A number of
intermediate carrier substrates have been developed for
mechanical transfer.34,35 More recently, electrochemical
methods have been used to create hydrogen bubbles between
the graphene and the substrate, which preserves the substrate
in its entirety and does not expose the graphene to possible
contaminants from the intermediate carrier substrate.27,36 Such
transfer methods could also be applied to graphene grown by
other processes.
Exfoliation of Graphite. The exfoliation of graphite could
date back to the 1960s, when it was first introduced by the
often unsung pioneer Hanns-Peter Boehm, who reduced GO
derived from graphite and showed TEM images of the material
and even named it “graphene”.37 This oxidation−reduction
process for the production of graphene remains popular
(Figure 3a). Graphene oxide, as the terminology indicates,
refers to oxidized graphene that contains functionalities such as
ketones, epoxides, alcohols, and carboxylic groups. The
oxygenated functionalities make GO water-dispersible and
even water-soluble and thus easy to process. The structure of
GO is not static, but dynamic, especially in water where it
continues to degrade into smaller fragments, becoming more
like humic acid.38 In the presence of environmentally
ubiquitous reducing bacteria, GO is converted back to
graphene, which agglomerates into a natural-mineral-like
graphite structure.39 This feature could be a harbinger for its
environmental friendliness. Therefore, the use of GO as a
precursor to graphene continues to capture the interest of
many.
Graphene oxide is generally prepared from graphite with
strong oxidants and concentrated acid, which was demon-
strated by Brodie40 in 1859 and optimized by Staudenmaier,41
Hummers,42 and Tour43 in 1899, 1958, and 2010, respectively.
In the 2010 method, the process adds phosphoric acid and
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Figure 4. Laser-assisted manufacturing of graphene (a) with and (b) without the use of metal catalysts.
excludes the commonly used nitrate or chlorate salts, thereby
avoiding the generation of toxic gases while affording a much
higher yield to the GO, making it a popular approach.43
Afterward, reducing GO by means of chemical,14 thermal
(∼190−210 °C),44 and microwave45 methods can remove the
oxygenated functionalities and regenerate graphene. The
reduced GO (rGO) is usually defective due to the irreversible
destruction of the contiguous aromatic structure. These
methods have been widely adopted to produce graphene for
applications such as in thermal dissipation, batteries, and fillers
that do not need high-quality graphene.46 In addition,
manganese impurities are difficult to remove and trace
manganese has been suggested to be responsible for the
catalytic properties seen in many electrocatalysis experi-
ments.47,48
There are also nondestructive exfoliation methods to
prepare FLG or GNPs. The process involves the insertion of
small molecules between the layers of graphene, such as CO2,17
organic solvents,15 and iron(II) acetate,16 that weaken the
interlayer van der Waals interactions, thereby easing the
exfoliation step that uses shearing force or thermal expansion
to separate the graphene layers (Figure 3b). These processes
cause little damage to the aromatic lattice, and the graphene
structure is preserved. The graphene is usually thicker, being
FLG or GNPs, but this strategy has already translated to large-
scale manufacturing.
Laser-Assisted Graphene Manufacturing. Laser-assisted
graphene manufacturing is a fast-growing method. Conven-
tional methods involve a synthesis and a lithography process to
pattern graphene electronics with desired shapes,49 whereas in
a laser-assisted manufacturing process, it is achieved with a
one-step laser shock.18,19 Compared to the bulk thermal-
heating method, the lasing process confines energy at the
targeted location and reduces parasitic heat loss. In addition,
the lasing process can be performed under ambient conditions
without the need for high-purity gases and fine control of
pressure.18,19 The manufacturing process can easily be scaled
up by adopting roll-to-roll automation, which has great
potential for commercialization.19
There are two types of laser-assisted graphene manufactur-
ing processes. One type mimics the CVD process in that
carbon first dissolves in metal when the solid mixture of metal
and carbon precursors is illuminated. Upon cooling, the carbon
precipitates on the metal surface and forms graphene (Figure
4a).50,51 By using fine metal power and sucrose, three-
dimensional printing of graphene has been demonstrated.51
The graphene prepared in these methods usually uses nickel as
the substrate, and the resulting graphene can be BLG or
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FLG.18,50 After synthesis, an etching process for removal of
metal substrates is typically needed. The second process is
based on the photothermal and photochemical effects induced
by the laser and avoids the use of metal catalysts for the
synthesis of porous graphene (Figure 4b). In early studies,
direct laser writing on GO films was found to transform the
illuminated area into porous graphene.18,52 The resulting
material is termed laser-reduced graphene (LRG) to delineate
the process of the transformation. This method can easily be
integrated into a commercial DVD writer for printable
electronic applications. Yet, the use of a GO film is problematic
because its synthesis involves a wet synthesis process and it
generates significant acidic and oxidant wastes.43 In 2014,
direct laser writing on commercially available polyimide film
under ambient conditions converted the substrate into porous
FLG, which was designated laser-induced graphene
(LIG).19,53,54 The FLG exists as a graphene foam. The process
was further found to be applicable to many substrates,
including naturally occurring and synthetic polymeric materials
such as wood, paper, lignin, cotton, cardboard, and numerous
plastics.55,56 Both the LRG and LIG methods produce porous,
defective, and flexible FLG films, which have found broad
applications in fields such as catalysts and capacitors where
higher surface area and mechanical flexibility are benefi-
cial.19,54,57
Graphene Safety. In addition to technical aspects such as
production and standardization, the potential environmental
impact and the cytotoxicity of graphene materials need to be
thoroughly assessed in the course of graphene commercializa-
tion. For reference, consider the development of carbon
nanotubes (CNTs), for example. Although CNTs were
heralded in the 1990s and early 2000s, multiwalled CNTs
were later found to have some unfortunate toxicity profiles.58,59
Thankfully, to date, graphene has been shown to be less toxic
and even biocompatible. This biocompatibility is affected by its
functionalities, impurities, thickness, and flake sizes.60 There-
fore, the identification of graphene cytotoxicity must be clearly
correlated to the precise structure. Considering the intense
ongoing research on graphene and the growing global
production capacity, the assessment of immediate and long-
term risks of graphene, the development of safety measures in
laboratories and factories, and the regulation for disposal of
graphene products are imperative.
PERSPECTIVES AND OUTLOOK
Since its discovery in 2004, the astonishing properties arising
from graphene have launched an exciting field of materials
science. With worldwide effort, researchers have developed
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numerous methods to synthesize graphene of different grades.
The CVD method aims to produce beyond wafer-scale high-
quality graphene, even by roll-to-roll methods. As this route is
expensive, it is more attractive for use in advanced technologies
such as transparent electronics, transistors, and photonics. The
ability to prepare high-quality graphene is a prerequisite for
advances in fundamental science, and the scalability and
reproducibility will later meet the need for commercial
applications. In recent studies, thanks to the development in
producing large-size and high-quality graphene, additional
breakthroughs in fundamental physics have been reported,
such as the discovery of the superconductivity of BLG at a
“magic twisted angle”5 and advances in the quantum Hall effect
of sandwiched graphene layers.61 Given the diversity in
homogeneous and heterogeneous graphene structures, studies
on stacked graphene remain underexploited and more
discoveries should be forthcoming. There will be opportunities
for researchers to develop the direct synthesis of large-size
BLG or trilayer graphene and reliable and scalable stacking
strategies for the precise control of stacking orientations and
large-scale approaches to turbostratic graphene.
Since its discovery in 2004, the aston-
ishing properties arising from graphene
have launched an exciting field of
materials science.
Other methods, such as exfoliation and reduced GO, are
complementary techniques for graphene production. Although
GO-derived routes produce lower-grade graphene materials
that are defective and have low carrier mobility, exfoliation
methods can produce higher grades, but they are often AB-
stacked FLG or most generally GNPs. Nonetheless, they are
easy to scale up and should have more immediate impact on
the materials industry. For instance, products such as thermal
dissipation films and conductive inks prepared from these
materials have now become commercially available. For bulk
commercial applications, GNPs have been used in composites
to enhance mechanical properties, such as in polyurethane
foams by the Ford Motor Company to improve noise
reduction and heat endurance, or in asphalt by Directa Plus
to enhance mechanical strength.8 The development of bulk
methods to make turbostratic graphene is expected to help the
composites blending and afford great improvements in
materials. In order to put graphene into commodity building
materials such as aluminum, wood composites, and concrete
economically, the commercial cost of bulk graphene will have
to drop significantly. However, caution should be paid when
using lower-grade graphene in areas such as catalysts and
biomedicine that are sensitive to functionality and metal
impurities.47,60 Further attention needs to be paid to the fact
that graphene qualities vary among different producers and
upon aging. The recently developed laser-assisted manufactur-
ing of graphene emerges as a promising technique for the
direct roll-to-roll manufacturing of graphene electronics. Many
innovative applications have been demonstrated in the
laboratory,54 and the viability of technology transfer has also
been demonstrated.62
As the properties of graphene strongly correlate with its
structure, the standardization of commercial graphene is
necessary. Take the successful case of GO, for example. In
the GO market, information such as flake size, oxygen content,
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Perspective
and metal impurities has now become available from some
producers, facilitating its use in commercial applications. The
ISO 2017 standards,9 which merely define graphene according
to the number of layers, might not be sufficient to address the
needs of the graphene market. For instance, SLG electron
mobility, sheet resistance, and thermal conductivity will vary
from different producers and have direct impact on its
applications. The establishment of efficient communication
between graphene producers and buyers to understand
product qualities should help to establish a healthy and
reliable supply chain. To summarize, the promotion of
graphene industrialization requires the development of
affordable manufacturing methods, standardized products,
and transparent communications.
Although graphene is only 15 years old, this young material
has come a long way. Another 15 years will bring graphene into
its prime while translating it into a host of construction,
fabrication, and device products that will be commonplace in
the lives of human beings around the world.
AUTHOR INFORMATION
Corresponding Authors
*E-mail: ruquanye@cityu.edu.hk.
*E-mail: tour@rice.edu.
ORCID
Ruquan Ye: 0000-0002-2543-9090
James M. Tour: 0000-0002-8479-9328
Notes
The authors declare the following competing financial
interest(s): R.Y. declares no competing financial interest.
J.M.T. is an unpaid member of the board of the National
Graphene Association. J.M.T. is also a stockholder in several
companies manufacturing or using graphene, but he is not an
officer, employee, or director in those companies.
ACKNOWLEDGMENTS
R.Y. acknowledges the support from the State Key Laboratory
of Marine Pollution (SKLMP) Seed Collaborative Research
Fund (2019) and the CityU New Research Initiatives/
Infrastructure Support from Central under Grant APRC-
9610426. J.M.T. thanks the Air Force Office of the Scientific
Research for their generous support of his graphene program
(FA9550-19-1-0296).
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