Accepted Manuscript

Graphene: fundamental research and potential applications

Yujia Zhong, Zhen Zhen, Hongwei Zhu

PII: S2452-2627(17)30050-8
DOI: http://dx.doi.org/10.1016/j.flatc.2017.06.008
Reference: FLATC 29

To appear in: FlatChem

Received Date: 11 May 2017

Revised Date: 20 June 2017
Accepted Date: 20 June 2017

Please cite this article as: Y. Zhong, Z. Zhen, H. Zhu, Graphene: fundamental research and potential applications,
FlatChem (2017), doi: http://dx.doi.org/10.1016/j.flatc.2017.06.008

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 Graphene: fundamental research and potential applications

Yujia Zhong, Zhen Zhen, Hongwei Zhu *

State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and
Engineering, and Center for Nano and Micro Mechanics, Tsinghua University, Beijing
100084, China

Corresponding author. *Email: [email protected].

Abstract
Graphene is a representative two-dimensional (2D) material and has been receiving
considerable interest from both academia and industry. In this review, we recollect the latest
development in the synthesis, structural analysis, characteristics, and possible applications of
graphene materials. The discussion helps researchers to better understand the properties of
graphene and design novel graphene-based applications.

Keywords: graphene; two-dimensional materials

1
Introduction
Graphene is the first synthetic two-dimensional (2D) atomic crystal. It has attracted immense
attention because of its excellent properties, including stiffness, strength, elasticity, high
thermal conductivity, extremely high electron mobility, and tunable band gap. Being such a
fascinating all-in-one material, graphene can replace other materials in many applications and
bring about technological breakthroughs. Graphene has been investigated theoretically since
the 1940s1. However, its studies mostly focused on theoretical calculations. It was only until
20042, through exfoliating highly oriented pyrolytic graphite3, that graphene was first
prepared in the laboratory. This experimental success stimulated research in 2D materials.
From 2004 till now, more than one hundred research articles on graphene have been
published in Science and Nature.

Synthesis and transfer

The synthesis of graphene is currently still a key concern in graphene research. Although
several methods, with varying cost and yield, are available, they still pose restraints on the
studies and applications of graphene.

Solid phase method. The synthetic methods can be classified by the phase of carbon source
and the synthetic environment (Figure 1). Solid phase methods include mechanical
exfoliation3 and synthesis on SiC4. Graphene can be acquired by mechanically exfoliating
highly oriented pyrolytic graphite with tape (Figure 1A). The resulting graphene has excellent
quality, but the yield is low and the cost is high3,5.
Alternatively, graphene can also be epitaxially grown on single crystal SiC by vacuum
graphitization4 (Figure 1B). The number of epitaxial graphene layers can be controlled, and
the quality of such graphene is good. However, the carrier scattering at epitaxial graphene on
SiC is induced by geometry. Thus the size of electrically uniform domains is limited6. This
method allows preparing graphene of larger sample size, but it is costly because it requires
high reaction temperature and the very expensive SiC wafers. In addition, the prepared
graphene is inferior to the mechanical exfoliated graphene in quality and crystallite size.

2
Solution phase method. The oxidationreduction reaction is a widely used solution phase
method to synthesize graphene-derived materials, such as graphene oxide (GO). This method
has low cost and gives high yield, but the product has inferior quality. The GO fabricated via
solvent casting can completely exfoliate in water (Figure 1D) to produce suspensions
containing almost entirely individual GO sheets7,8.
The suspension can be deposited as a thin film on many surfaces, and the film can then
be reduced5. Subjecting GO to reducing agent under certain condition gives reduced GO
(rGO). Alternatively, GO can be reduced by heating in an inert atmosphere. Catalysts induce
GO reduction upon illumination or annealing at high temperatures. And it is environmentally
friendly to reduce GO by applying voltage9. The use of heated atomic force microscope
(AFM) tip10, laser beam11 and pulses of microwaves12 allows reducing GO with precision
(Figure 1E). Thermochemical nanolithography with heated AFM tip can pattern the nanoscale
rGO without tip wear or sample tearing. The width of the rGO patterns can be controlled
between 12 nm and 20 m10. Similarly, reduction through laser irradiation can also pattern
rGO11. Both methods are reliable, flexible, clean, and rapid.
Beside the oxidation-reduction method, a non-chemical solution-phase exfoliation of
graphite in organic solvents is developed13,14. Few-layer graphene can be obtained by
dispersion and exfoliation of graphite in N-methyl-pyrrolidone (NMP),
N,N-Dimethylacetamide (DMA), -butyrolactone (GBL) and 1,3-dimethyl-2-imidazolidinone
(DMEU).

Preparation of graphene nanoribbons. Graphene is a 2D zero band gap semimetal.

Therefore, its band gap must be opened up before it can replace Si and be used in electronics.
Because quantum confinement and edge effects can introduce band gaps (Eg) (~1/w, where
w is the width and is near unity) in graphene nanoribbons (GNRs), the GNRs whose width
is less than 10 nm exhibit semiconductor nature and have substantial band gap (Eg > 0.3 eV)15.
Narrow GNRs can be produced through chemical sonication. For example, sonicating the
solution of poly(m-phenylenevinylene-co-2,5-dioctoxy-p- phenylenevinylene) (PmPV) in
1,2-dichloroethane (DCE) gives a suspension of exfoliated graphite, which is further
centrifuged to obtain the GNRs15.
3
 Lithographic patterning16 of graphene film is a conventional technique to acquire GNRs.
GNRs prepared by lithographic patterning are wide, but limited in width and smoothness.
Carbon nanotube (CNT) can be regarded as a GNR rolled up into a seamless tube. As a result,
it is logical to produce GNRs by unzipping CNTs. CNTs partly embedded in a polymer film
can produce GNRs through plasma etching (Figure 1C). If the starting CNTs have small
diameter and certain chirality, the obtained GNRs may have well-defined widths and edges.
Selecting the CNTs and modifying the plasma etching time will manipulate the number of
graphene layers and affect the yield. This method allows large scale production of narrow
(<10 nm) GNRs that have well-aligned morphology, controlled structures, and band gaps
suitable for semiconductivity17. Annett and Cross heated the exfoliated single layer graphene
(SLG) with Si substrate to 150 C for 13 days. The thermal activation lead to the spontaneous
sliding, tearing and peeling of graphene and further formed GNRs18. Solution-based
oxidation can cut multi-walled CNTs lengthwise to yield ribbon structures, and subsequent
chemical reduction can produce GNRs and restore the electrical conductivity. Although this
method is expected to produce GNRs with zigzag edge, in practice it does not generate the
desired structure19.
A bottom-up approach assembles precursor monomers into linear polyphenylenes and
then makes atomically precise GNRs by cyclodehydrogenation (Figure 1F)20,21. Straight
GNRs with armchair edges are made from bianthryl monomers, and Chevron-type GNRs
with armchair edges are made from tetraphenyltriphenylene monomers20. However, two
problems exist, i.e., polymerization can occur via aryl-aryl coupling along the armchair
direction, and cyclodehydrogenation of phenyl subgroups does not always ensure pure zigzag
edges. Zigzag-edged GNRs can be synthesized by the polymerization of U-shaped dibenzo
anthracene monomer with halogen functions at both ends and dimethyl-biphenyl in the
interior, and then subsequent cyclization21. Thus, the topology, edge, and width of GNRs can
be controlled by using different precursors in polymerization and cyclization. Recently, high
quality GNRs are acquired through chemical vapor deposition. h-BN substrates are used as
the templates. The in-plane epitaxy of GNRs ensures smooth edges with controllable width22.

Chemical vapor deposition. Electronic applications require graphene of high quality and
4
large area, which is often not synthetically available from mechanical exfoliation or solution
methods. Chemical vapor deposition (CVD), of CH4 on catalyst substrates can render large
monolayer or bilayer graphene23,24. A typical CVD setup is illustrated in Figure 1G. Since
gaseous carbon source limits the graphene synthesis with different source materials, many
solid carbon sources, including sucrose and polymethyl methacrylate (PMMA)25, have been
exploited to grow large pristine or doped graphene with controllable thickness on Cu or Ni
substrates at 8001000 C25. The main advantages of CVD include lower temperature growth
and flexible choices of raw materials. Large area and good quality graphene is easy to
produce by CVD. However, it always costs several hours to acquire a continuous graphene
film, which means low yields in industrial production. Both CVD growth and subsequent
transfer procedures induce defects in graphene. Growth near 1000 leads to high energy
costs. The subsequent transfer consumes metal substrate and produces defects in graphene
film. The cost of CVD is higher than that liquid-phase methods.
The mechanism of graphene growth in CVD (Figure 1H) depends on the substrate.
Carbon is dissolved in Ni at high temperatures. The dissolved carbons segregate and
precipitate to form graphene during the cooling process with appropriate cooling rates26,27. In
contrast, carbon has negligible solubility in Cu and deposits directly on the Cu surface23.
Wrinkle-free single crystal single layer graphene (SLG) can be synthesized on the reusable
hydrogen-terminated Ge substrate28. The CVD parameters, including C/H ratio, substrate
quality, temperature, and pressure, can all influence the graphene quality. Oxygen on the Cu
surface can passivate Cu and hence decrease graphene nucleus. Besides, the dehydrogenation
effect of oxygen alters the growth behavior of graphene29. The presence of oxygen makes it
easier for carbon to attach on graphene edge, and thus accelerates graphene growth. This
mechanism is diffusion-limited, which corresponds to the shape of the dendritic domain.
Without oxygen, the growth kinetics is limited by edge attachment and the morphology of the
graphene domain is compact.
Beside graphene sheets, three dimensional (3D) graphene architecture carrying periodic
nanopores is also of great interest. As a kind of microporous crystalline aluminosilicate,
zeolite is an ideal a template for making 3D graphene architectures. Lanthanum helps form
3D graphene architectures because adding lanthanum ions to zeolite pores reduces the
5
carbonization temperature of ethylene or acetylene. As a result, graphene can be selectively
grown inside the zeolite template instead of being deposited on the zeolite surface30.

Solid phase methods Solution phase methods

A C F
D

Liquid-phase exfoliation
Mechanical exfoliation

B Graphene E Laser Hot AFM tip

GO
Graphene
SiC

Synthesis on SiC CNT unzipping Reduction of GO Monomer assembly

Chemical vapor deposition (CVD)

CH4 CH4
Graphene Graphene
G H
H H
C C

Ni Cu

Figure 1 Making graphene. (A-C) Schematic illustration of solid phase methods: (A)
mechanical exfoliation5, (B) synthesis graphene on SiC4,5, (C) CNTs unzipping by plasma
etching to make GNRs19. (D-F) Solution phase methods: (D) liquid-phase exfoliation to
produce individual GO sheets5, (E) reduction of GO induced by hot AFM tip10 or laser11, (F)
assembling different monomers to make GNRs with different morphologies18,20,21. (G)
Device of CVD. (H) Growth mechanisms in CVD. (Step 1) Methane decomposition to
produce C. (Step 2) Left panel: surface segregation and precipitation in Ni substrate. Right
panel: surface adsorption in Cu substrate. (Step 3) Graphene nucleation and continued
growth.

Transfer. The high-fidelity transfer of graphene to arbitrary substrates is a key point for its
practical application in electronics. As part of the CVD synthesis of graphene,
polydimethylsiloxane (PDMS) stamp and floating transfer26 were demonstrated in 2009. The
Ni and Cu substrates can be etched by FeCl3, Fe(NO3)3 and (NH4)2S2O8 solutions31. PDMS
can protect graphene film and transfer graphene crystals that do not form a continuous film. If
SiO2/Si is pretreated by N2 plasma to form "bubble seeding", when Cu is etched, N2 can form
a capillary bridge to ensure that the graphene film remains attached to the SiO2/Si substrate32.
This direct face-to-face transfer reduces transfer defects. In addition, spontaneous attachment
of graphene on the SiO2/Si substrate is suitable for semiconductor production line.

6
Transferring SLG from SiC is useful for electronic application. Selective exfoliation
graphene grown on the SiC (0001) via engineered strain layers is based on the binding energy
contrast between graphene and different metals (Ni and Au). This dry exfoliation method
reduces the consumption of SiC wafer and can control the number of transferred graphene
layers33. Dimiev reported another method to remove graphene layers for patterning. When a
patterned layer of Zn is sputtered atop the multilayer graphene, cleaning Zn with aqueous
HCl can simultaneously remove one graphene layer34.

Structure and morphology

Graphene is a single atomic 2D layer of sp2-bonded carbon packed into a honeycomb lattice.
All carbons have sp2 hybridization and the residual electrons in the p orbital form large
bond. The bonds formed by the sp 2-bonded carbon make graphene stable and flexible.
Theoretical studies demonstrated that thermal fluctuations would destroy the long-range order
of 2D lattice. However, graphene with elastic corrugation (Figure 2A) can withstand thermal
fluctuation through modulating bond length35. For bi-layer graphene (BLG), the buckling at
the dislocations can completely delocalize the respective residual compressive and tensile
strains in two graphene layers36. The fabrication of SLG that is flat down to the atomic level
by deposition on cleaved mica surface can help study the impact of ripple on the graphene
properties. When graphene is supported on an atomically flat substrate such as mica, its
intrinsic ripples would be strongly suppressed by the interfacial interactions37.
The edge of graphene can be typically classified as either zigzag or armchair (Figure 2B).
The zigzag edge GNRs show metal properties, whereas the armchair edge GNRs can be of
either metal or semiconductor nature. The behavior of atoms at the edge of the SLG sheet can
be analyzed by comparing the aberration-corrected TEM images with simulation results. The
rearrangement of carbon atoms under prolonged irradiation reveals that the zigzag edge
configuration is more stable38. Single atom energy-loss spectroscopy can also help to get
abundant chemical information of carbon atoms at graphene edge39.
When the orientations of adjacent grains are different, grain boundaries (GBs) are
formed (Figure 2C). The GBs in graphene are formed by integrating islands during the initial
growth stage. It is observed in atomic-resolution aberration-corrected annular dark-field
7
scanning transmission electron microscopy (ADF-STEM) imaging that graphene grains are
stitched together through pentagon-heptagon pairs (Figure 2D)40. The location of graphene
GBs can be conveniently visualizing in optical microscope through water photolysis, in
which the hydroxyl moiety bonds with GBs and oxygen traverses graphene through GBs to
form oxide with the Cu substrate41. Because the structure of grain boundary is different from
the grain structure, the presence of GBs changes the properties of graphene. The defect
density and the strength of polycrystalline graphene are determined by the angle of tilt
boundaries. Graphene with large-angle tilt boundaries, which have a higher density of defects
and can better accommodate strained rings, is much stronger than those with low-angle
boundaries. The strength of large-angle tilt boundaries graphene is nearly the same with
pristine graphene42. AFM nanoindentation results reveal that if the GBs are well stitched, the
elastic stiffness and strength of CVD graphene are comparable to those of pristine graphene.
Hence, well stitched GBs do not impair the mechanical properties of graphene43. If the
graphene grains overlap but do not covalently join, the GBs would be weak, but the electrical
conductance could be higher than that of stitched boundaries. In contrast to overlapped grains,
when gaps exist, the conductance of the well stitched grains and the adjoined grains would
reduce44.
The second law of thermodynamics dictates that disorder should appear in crystalline
materials. Many properties of materials are governed by defects. Defects in graphene can be
useful in adjusting the structure and properties of graphene. The first direct evidence for
atomic defects in graphene layers was obtained by comparing the in-situ HRTEM images of
graphene before and after sputtering with simulated results (Figure 2F)45. The movement of
dislocations is the key mechanism for understanding the deformation in materials. In layered
crystals, the dislocations are restricted to the basal plane. Graphene is a suitable subject to
explore the dislocation movement in layered crystals. Warner et al. studied the dislocation
movement, interaction, and strain fields in graphene. The dislocations in SLG can be seen as
pentagon-heptagon pairs. The edge dislocations lead to CC bond compression or elongation
of 27%, as well as shear strain and lattice rotations. The dislocation pairs (Figure 2E) affect
each other if their distance is less than 1.5 nm. When the area of the dislocation pairs in
graphene is deformed through the electron beam irradiation, the strain field is localized
8
around the core46. Basal-plane dislocations in BLG are real line defects confined between the
two graphene layers. Since BLG has no stacking-fault energy, the dislocations change the
local stacking from AB to AC36.

A C E

B
F

Zigzag edge Armchair edge

Figure 2 Structure and morphology of graphene. (A) Corrugated graphene35. (B) Zigzag
edge GNR and armchair edge GNR. (C) Left panel: grains emanated from a few points. Right
panel: diffraction pattern taken from a region in the left image. The diffraction pattern reveals
that this area is polycrystalline40. (D) Atomic-resolution ADF-STEM images of graphene
crystals40. (E) Dislocation pair in graphene46. (F) Four defects types in graphene: an adatom,
unrelaxed vacancies (V1 and V2) and a 5-8-5 rearrangement45.

Properties
Electrical properties. In graphene, the carbon atoms have sp 2 hybridization as the state,
and the residual p orbital electrons form conjugated bond and move freely. Three states in
one graphene unit cell form the lower valence states, and delocalized and * states form the
highest occupied valence states and the lowest unoccupied conduction band 47. Graphene is a
zero band gap semimetal47,48 whose conduction band and valence band show conical
dispersion and meet in the Dirac point (Figure 3A)49. The linear dispersion of electron results
in an effective mass m* = 0 at the Dirac point. Considering the interactions between
quasiparticles, the Dirac spectrum would reconstruct50. The reconstructed Dirac crossing
includes one crossing between pure charge bands, another between pure plasmaron bands, as
well as a ring-shaped crossing between charge and plasmaron bands51. Charge carriers in
conductors circulate in cyclotron orbits with quantized energies under magnetic field. The
quantized energies, which are called Landau levels, are equally spaced in normal metals and

9
2D electron gases52. Song et al. studied the degenerated graphene Landau level and explored
the detailed features of the quantum states53. Graphene appears different with conductors in
that its charge carrier velocity is independent of the quantized energies, thus the Landau
levels are not equally spaced and include a characteristic zero-energy state (Figure 3A)52.
Since electrons in graphene are confined in a 2D film, anomalous quantum Hall effect (QHE)
(Figure 3B) can be observed 49,54-63.
The edge of the graphene determines its magnetic and electronic properties. GNRs with
zigzag edges show the half-metallicity with zero band gap and provide a platform to explore
spintronics38. Furthermore, their magnetic properties are dominated by the external in-plane
homogeneous electric field across their zigzag edges. In contrast, the energy band of narrow
armchair GNRs indicates that they are a semiconductor with small band gap (Figure
3C)15,17,19-21,64. Tuning the graphene edges to acquire specific crystallographic orientation can
increase magnetic order. The narrow (5 nm) zigzag GNR is an antiferromagnetic
semiconductor, but the wide (>8 nm) zigzag GNR is ferromagnetic with no bandgap 65.
The electrical properties of graphene are also affected by the symmetry of its hexagonal
layer structure. Topological currents can be observed in graphene superlattices that have
broken inversion symmetry66. Because of its parabolic dispersion, the bilayer graphene is
susceptible to the symmetry breaking induced by the interactions among charge carriers even
at zero magnetic fields67. When the BLG has Bernal stacking, the band structure consists of ,
* states and two lower energy bands through the splitting valley from interlayer coupling.
The band gap of the pristine Bernal-stacked BLG is zero. The band gap of BLG can also be
opened or closed by rendering the individual graphene layer, doping through adsorption47, or
strong electrical gating in dual-gate BLG FETs (Figure 3D)68. The electromechanical
properties69,70 are used to explore the electrical properties. Because graphene has massless
Dirac fermions-like band structure and lattice symmetry, the pseudo-magnetic fields induced
by strain can approach 300 T, which offers a method to control the electronic structure of
graphene69.
The sheet resistance5 of highly doped graphene reaches 30/sq. The electron mobility ()
can rise up to 2 105 cm2/ (Vs) at electron densities (n) of 2 1011 cm2 in suspended SLG
(Figure 3E)71. The CVD SLG transferred to SiO2 substrate26 shows electron mobility =
10
3700 cm2/ (Vs) at n = 5 1012 cm2. The conductivity = ne is controlled by both electron
mobility and charge density. Compared with Cu, graphene shows higher electron mobility but
has much lower charge density. Zhao et al. found that the electronic structure of the
individual nitrogen dopant in SLG changed only within a few lattice spacing, and this allows
increasing carrier density while conserving graphene quality72. Under magnetic field,
supercurrent could be observed in encapsulated graphene in contact with superconducting
electrodes73 or in a graphene layer contacted by two closely spaced superconducting
electrodes74. In graphene junction which is contacted by two closely space superconducting
electrodes, a finite supercurrent is observed even at zero charge density74. In some situations,
graphene can show ballistic transport property75-77. Ballistic propagation means that
scattering only occurs at the quantum billiards boundaries, as is observed in the
low-temperature transport spectroscopy of SLG or BLG. Epitaxial GNR (40 nm wide)
features single-channel room-temperature ballistic conductors with a ballistic length more
than 10 m78. Ju et al. observed ballistic valley-polarized conducting channel with a ballistic
length of 400 nm at 4 K79. Rutter et al. found that intravalley and intervalley backscattering
was dominated by the in-plane atomic defect, thus the defect influenced the transport
properties of graphene80. Bandurin et al. demonstrated that electrons in graphene behave like
a viscous liquid (Figure 3F)81, because in graphene electron-phonon scattering is weak but
electron-electron collisions abound. The vicinity resistance is negative over a large range of
carrier density and temperature, and the viscosity of electron Fermi liquid in graphene is ~0.1
m2/s.

11
 A B

D
Rendering graphene layer
Doping through adsorption
Strong electrical gating
SLG BLG

E F

Figure 3 Electrical property of graphene. (A) The electronic structure of graphene with
quantized Landau Levels (LLs) in a magnetic field. The conduction band and valence band
show conical dispersion and meet in the Dirac point ED52. (B) QHE for massless Dirac
fermions in graphene49. (C)Band structure54 of armchair (left) and zigzag (right) GNRs with
width N=20. (D) The electronic structure of single layer graphene (SLG) and symmetric
double layer graphene (BLG) 47. Rendering, doping through adsorption and strong electrical
gating can influence the band gap of graphene. (E) Electrical mobility (left) and
conductivity (right) as functions of carrier density n 71. (F) Vicinity resistance RV (n, T) map
for SLG. The black curves indicate zero RV 81.

Optical properties. The optical transmittance (T) and reflectance (R) of graphene are given
by T (1+2G/c)2 and R 0.2522T, where G = e2/4 ( = h/2, h is the Planck constant, e
is the electron charge) is the high-frequency conductivity for Dirac fermions in graphene, c is
speed of light, and = e2/c 1/137 is the fine structure constant that describes the coupling
between light and relativistic electrons. Reed et al. reported that the value of effective
fine-structure constant is = 0.14, which is smaller than the nominal = 2.2 and suggests
that the strength of interaction between quasiparticles is weaker than previously believed82.
The reflectance of graphene is negligible (<0.1%). Though SLG is only one atom thick, its
opacity can reach (1 T) 2.3%. The opacity can increase another 2.3% for one more

12
graphene layer and is independent of the wavelength of the incident light83. The optical
behavior results from the confinement and low density of states near the Dirac point in
graphene. Thus, optical study can help in studying the graphene band structure. From the
infrared spectroscopy of SLG and BLG, Wang et al. found that optical transitions in graphene
can be modified through electrical gating84. Liu et al. managed the Fermi level by adjusting
the drive voltages and made a graphene-based broadband optical modulator that gave tunable
response85. In normal circumstances, it is hard to control optical fields because photon is
neutral, but tuning the carrier density in graphene allows changing the plasmon polaritons and
the associated optical fields86,87.

Thermal properties. Graphene has high thermal conductivity () value because of the strong
bonding of its carbon atoms. The thermal conductivity of a suspended SLG is determined
from Raman spectroscopy to be 5000 W/mK, which exceeds that of diamond and
graphite88. Suspended graphene has higher than supported SLG, because in the latter
phonons can leak across the graphenesupport interface and strong interface-scattering is
introduced by the contact. Graphene samples grown by thermal decomposition, CVD, and
exfoliation have different interactions with the supporting surfaces. An SLG exfoliated on a
SiO2 support has higher thermal conductivity (about 600 W/mK) than copper89.

Mechanical properties. The mechanical properties of free-standing atomically perfect

nanoscale SLG were measured by nanoindentation in an atomic force microscope. The results
showed that Youngs modulus is E = 1.0 TPa and intrinsic stress is int = 130 GPa90. However,
the mechanical properties of graphene are affected by many factors, such as defects, stitching
quality of adjacent boundaries43, and angle of tilt boundaries42. The dynamic mechanical
behavior of multi-layer graphene (MLG) in the extreme dynamic condition was observed
through supersonic projectile penetration. The MLG deformed into a cone and then formed
radial cracks extending along crystal orientations to the outside of the impact area91.
Superlubricity is important to save energy and enhance device lifetime. Choi et al.
demonstrated the anisotropic friction of graphene, i.e., the friction varies with the angle
between the ripple line of graphene and the force92. The friction force between GNRs and Au
13
substrates fell in the range of 100 pN, which meant superlubricity. The friction behavior was
93
studied in ultrahigh vacuum from the atomically well-defined GNRAu (111) contact .
Recently, the results of atomistic simulations reproduce the experimental frictional
phenomenon of graphene, including layer-dependent friction and transient frictional
strengthening on graphene. The simulations reveal that true contact area governing friction on
two-dimensional materials. Producing wrinkles on suspended graphene can greatly increase
the total friction force without obvious change in the true contact area 94.

Chemical modification. Electrothermal reaction of GNRs in NH3 can render

95
carbonnitrogen bond at the edges and realize N-doping of graphene . Hydrogenation of
graphene can transform the semimetal into an insulator. Hydrogenation leads to a shorter
period than pristine graphene but maintains the hexagonal lattice. This hydrogenation
reaction can be reversible by annealing96. In addition, through the magnetic moment induced
by the adsorption of single hydrogen atom, hydrogenation could also control the graphene
magnetism at atomic scale97.

Applications
Electrical application. Many studies focus on the applications of graphene. Even at the scale
of a few benzene rings, the mechanical, chemical and conducting properties of graphene can
still remain. Thus graphene is suitable in working as molecular-scale electronics98.
Additionally, when the type and density of the carrier in the SLG p-n junction is customized56,
graphene can serve as semiconductor layer in barristor99, field effect transistor (FET)44,100-102,
as well as integrated circuit103,104. Graphene can also work as capacitor11,105-107 and
sensor108,109. When the carrier densities on n- and p- sides of the single graphene p-n junction
are made exactly equal, the electron flow can then focus. Accordingly, graphene can be used
to produce electronic lens110. Inspired by the whispering-gallery mode, Zhao et al. designed
resonators for electronic waves by forming circular p-n junctions in graphene111. Graphene
barristor99 is a triode device with a gate-controlled Schottky barrier that has an on/off ratio of
105. Wu et al. reported a top-gate CVD-graphene transistor on diamond-like carbon (Figure
4A). This transistor has short gate length to help increase the performance, and its
14
performance is relatively stable with the change of temperature101. Based on vertical
graphene heterostructure, a field-effect tunneling transistor device was proposed102. The
device exploits the low density of states in graphene, thus a small change of Vg can lead to a
greater increase in Ef.
Graphene is useful not only in electronic devices, but also in photonics and
optoelectronics that combine the optical and electronic properties112. In most optoelectronic
devices, graphene functions as a transparent conductor for its low sheet resistance and high
transparency. Graphene based transparent conducting films can be used as window electrodes
and hole transport layers in inorganic113, organic114,115 and dye-sensitized solar cells116.
Graphene has a work function of 4.5 eV, which is similar to indium tin oxide (ITO). The
flexibility of graphene makes it suitable in flexible devices. In light-emitting devices117 and
touch screens118, there are many attempts to use graphene to replace ITO. Graphene can
absorb a wide-spectrum light from ultraviolet to terahertz. Therefore, a graphene
photodetector is expected to realize broader spectral detection. For example, Xia et al. have
reported an ultrahigh-bandwidth photodetector based on few-layer graphene119. Furthermore,
graphene has a high carrier mobility, which may also bring an ultrafast response.
Laser reduction graphene has large surface area and fine mechanical and electrical
properties. Therefore, electrochemical capacitors with graphene electrode (Figure 4B) exhibit
high energy density, high power density, and remarkable cycle stability11. Double-layer
capacitors (DLCs) with electrodes of vertically oriented graphene nanosheets have low
electronic resistance, desirable resistor-capacitor (RC) time constants, and excellent AC
line-filtering performance. Using graphene nanosheets to introduce more exposed edge
planes can increase the charge storage of the capacitor92. The a-MEGO is prepared from
microwave exfoliated GO (MEGO) upon KOH activation and has a continuous 3D network
with nanoscale pores. Its structure helps the supercapacitors overcome the limit of low energy
storage density and high series resistance106. Capillary compression of graphene gel films in
liquid electrolyte can produce continuous ion transport network107. Porous
graphene/polyaniline (PANI) nanocomposites is also suitable for supercapacitor
applications120. Gabor et al. used local laser to excite FET and observed the resistance change
with varying top-gate and bottom-gate voltages121. They demonstrated that the intrinsic
15
photoresponse in graphene was nonlocal hot carrier transport. Graphene was also used to
fabricate integrated circuit (Figure 4C) in which graphene FET and inductors were
monolithically integrated on a single SiC wafer103. Lenvendorf et al. proposed a patterned
regrowth method to synthesize lateral junctions between graphene and h-BN or between
pristine and doped graphene104. This method makes it possible to fabricate integrated
circuitry.
The in-plane conductivity of graphene can reflect the atomic-scale information of its
opposing interfaces. This is because the graphene trans-electrode membrane (Figure 4D)
attracts cations and anions from ionic solution to its opposing surfaces. The interaction
between the ions and the membrane is mediated by graphene and electric fields. Since the
in-plane electronic conductance is sensitive to the interfacial environment, the trans-electrode
can serve as a detector. For example, during DNA translocation, the trans-electrode can be
used to identify the type of DNA through different nanopores current blockades versus
108
blockade duration (Figure 4D) . A mid-infrared plasmonic biosensor (Figure 4E) is
designed by exploiting the electro-optical properties of graphene as follows. Protein molecule
is adsorbed on GNRs, and the interaction of the molecule with light is increased by GNRs
under infrared beam. The molecule is identified by the dips of the plasmon resonance spectral
shift, which reflects the vibration bands of proteins96. The nanocomposites of graphene and
Silly Putty display electromechanical behavior122. The resistivity of nanocomposites changes
with strain. The gauge factors of the nanocomposites electromechanical sensors exceed 500.

16
 A C

D E

Figure 4 Electrical applications of graphene. (A) Top-gated graphene transistor101. (B)

Flexible graphene-based electrochemical capacitor. The gelled electrolyte can be used as both
the electrolyte and separator11. (C) Graphene integrated circuit103. (D and E) Graphene sensor:
(D) Trans-electrode108. DNA was driven through a graphene pore by an applied voltage bias.
The nanopore current blockades versus blockade duration during DNA translocation can
characterize DNA. Inset is the cross-section of the trans-electrode device. (E) Graphene
mid-infrared biosensor96.

Mechanical application. The GO structure also shows excellent mechanical properties. GO

nanosheets can arrange as interlocking tile, which results in good flexibility and stiffness
(Figure 5A)8. Bunch et al. made an electromechanical resonator by laying graphene sheet
over a trench in silicon oxide. The vibration of this resonator is driven by optical or electrical
signal, and the device can detect ultralow mass change and ultrasensitive force (Figure 5B)123.
Berman et al. wrapped graphene around nanodiamonds to form nanoscrolls and used them to
decrease the friction between nanodiamonds and diamond-like carbon (DLC) (Figure 5C)124.
The wrapping of graphene was influenced by the humidity of air.

17
 A B Au
Suspended
graphene

SiO2
Si

C D
Small
graphene
Sheets

Large
GO/graphene
Sheets

Figure 5 Mechanical applications of graphene. (A) The schematic draw of the uniaxial and
bend test of interlocking-tile GO sheets8. (B) Suspended graphene resonator123. (C)
Superlubricity between nanodiamonds and DLC realized by graphene-plus-nanodiamonds
nanoscrolls formation124. (D) Highly thermal conductive and mechanically strong graphene
fiber with an intercalated structure of large and small graphene sheets125. (E) Electrical
properties of graphene in-plane kirigami springs before stretching (blue) and when stretched
by 240 % (orange). The conductance G is measured at source-drain bias VSD=100 mV in KCl.
VLG is the liquid-gat voltage126.

Xin et al.125 utilized the mechanical properties of graphene and reported graphene fibers
in which large graphene sheets directionally aligned with some mixture of small graphene
sheets (Figure 5D). These fibers were fabricated through thermally annealing the aligned GO
fibers, and they combine high thermal and electrical conductivity with excellent mechanical
strength. The property of the fibers was affected by the ratio of small and large graphene
sheets and the annealing temperature. Liu et al.127 stack and shear scroll

18
graphene/polycarbonate composites. The scrolled fiber promises strength, elongation and
conductivity.
Seeing that graphene is comparable to paper in the ratio between in-plane stiffness and
out-of-plane bending stiffness, Blees et al. applied ideas from kirigami to graphene sheets
and patterned graphene through optical lithography126. For instance, the graphene in-plane
kirigami springs can be stretched by 240% without a notable change of conductance (Figure
5E).
Besides, graphene is also used as a filter in nanocomposites. Graphene and polymer can
be mechanically mixed. For example, adding 0.7 wt% GO in poly(vinyl alcohol) (PVA) leads
to 76% increase in tensile strength and 62% improvement in Yongs modulus128. Dispersion
of graphene in polymer matrix and the interaction between graphene filter and polymer
matrix are the key concerns of graphene-polymer nanocomposites. Some graphene
nanocomposites are prepared through nucleation and growth, and graphene functions as the
substrate for polymer nucleation.

Utilizing permselectivity. Since graphene with perfect quality shows impermeability, it is

used to seal the water on mica to observe the growing mechanism of water adlayers129.
Selective permeability is also possible when the structure or chemical property of graphene is
adjusted. GO membranes are the first use case of such kind of selective permeability.
Submicron-thick GO membranes, which are even impermeable to helium, allow unimpeded
permeation of water through the capillaries formed by closely spaced GO sheets (Figure 6A
and B)130. Ultrathin GO membranes prepared by facile filtration131 and spin-coating132 can
preferentially sieve gas mixtures. The filtration GO membranes can separate CO2 and H2
because it is permeable only to the gas molecule whose kinetic diameter is small than the
lamellar spacing of GO. When the thickness of the membrane is enhanced, the mechanism of
permeation will change, i.e., the molecule will penetrate the membrane through the defects
and cracks of GO. In addition, the selectivity of spin-coating GO membrane can be controlled
via different stacking methods. According to Joshi133, the velocity of small ions that permeate
through GO membrane is much quicker than the velocity of diffusion, presumably because
the graphene capillaries exert high pressure on small ions. Kim et al.132 studied the selectivity
19
and permeability of graphene/ Poly(1-methylsilyl-1-propyne) (PTMSP) membrane and found
that the existence of SLG does not influence the gas permeability of PTMSP membrane
(Figure 6C). Celebi et al. physically punched pores on bilayer graphene by focused ion
beam134. The drilled pores (Figure 6D) were between 10 nm and 1 m in diameter and
enabled H2/CO2 selectivity and ultimate permeation.

A B

C D

Figure 6 Permselectivity of GO and graphene. (A) Schematic diagram and Electron

micrograph of the GO membranes cross section. Water can permeate through the laminates
of GO sheets130. (B) Permeability of GO paper with respect to water and some small
molecules130. (C) The gas permeability and sheet resistance of graphene/PTMSP membranes.
The existence of SLG does not influence the gas permeability of PTMSP membrane. Inset is
AFM images of graphene/PTMSP membrane surface132. (D) Apertures FIB-drilled on the
freestanding graphene (scale bar, 500 nm) 134.

Using graphene as a substrate. Graphene also helps in preparing and growing other
materials. Using graphene as the substrate in GaN growth resolves the difficulty in
transferring GaN. Since GaN cannot be grown directly on pristine graphene, ZnO nanowall
was used as an interlayer between graphene and GaN. This graphene/ZnO/GaN combination
shows excellent optical characteristics and is used to produce photoelectrical device such as

20
LEDs135. Solvothermal condensation of 1,4- phenylenebis (boronic acid) and 2,3,6,7,10,11-
hexahydroxytriphenylene in the presence of substrate-supported graphene in a vessel
generates a covalent organic frameworks (COF-5) film on the graphene surface and
precipitated powders. Graphene helps improve the crystallinity of the COF-5 film (Figure
7A)136. The substrate-epilayer gap accommodate a monolayer of graphene. Graphene is thin
enough to guide the epitaxial orientation. Thus, graphene assists remote homoepitaxy. The
epilayer is easy to release and transfer. This character overcomes lattice-matching limitation
in epitaxy 137. Xu et al.138 developed a facile method to produce hierarchical nanocomposites
of PANI nanowire arrays on GO sheets. Here GO functions as a component in the
nanocomposite and the substrate for PANI nanowires nucleation and growth.

A B
Fe
BN

Graphene COF-5 Film Graphene

C D
Graphene

Encapsulated solution

Figure 7 Using graphene as a substrate. (A) Vertical growth on graphene substrate136.

Solvothermal condensation of HHTP and PBBA generate COF-5 film and powder in the
presence of substrate-supported SLG surface. (B) Lateral growth on graphene substrate:
schematic view of epitaxial growth of BN onto graphene edges (left) 139 and atomic structures
of a suspended atomic Fe layer in graphene pore (right) 140. (C) Observation substrate: carbon
adatom (black arrow) and hydrogen adatom (red arrow) on graphene membrane. Inset,
configuration of a chemisorbed hydrogen atom (red) 141. (D) Wrapping membrane: idealized
illustration of local graphene liquid cell encapsulating growth solution142.

Monolayer crystalline h-BN can be grown from fresh edges of SLG (Figure 7B). The
growth mechanism is coherence, thus the h-BN lattice orientation only depends on the
orientation of graphene139. In the transfer process of graphene, etching Cu in FeCl3 solution

21
leaves some remnant Fe atoms. Zhao et al.140 found that these Fe atoms form free-standing
single-atom-thick membranes suspended in graphene pores (Figure 7B). These Fe atom
membranes are produced by electron-beam irradiation with the help of dangling bonds, and
they gradually decompose under electron-beam irradiation.
Moreover, graphene helps visualize ultra-low-contrast objects in TEM, thus clean SLG
membrane is a good substrate to observe hydrogen and carbon atoms (Figure 7C)141. Liquid
cell wrapped by graphene (Figure 7D) is employed to explore the mechanism of colloidal
platinum nanocrystal growth142. Similarly, graphene nanocapillaries help to examine water
confined in nanocapillaries (square ice)143. Graphene can be the substrate of polymer
superstructure to help capture the transmission dynamic by ultrafast low-energy electron
diffraction144.

With all fascinating properties that a theoretical graphene material could have, the
application of graphene is considered as the gate to reach some advanced technology such as
biological engineering, advanced electronics, high efficiency energy generation and storage,
flexible wearable sensors, portable water treatment, and superior structural material. This
trend is consistence with the data collected of the latest publications about graphene materials.
According to the pie chart, electrical property and applications are the most famous spots of
graphene research which summed up to 47% of total publications.
In recent years, substantial efforts have been put into developing electrical applications
of graphene thin films, but the progresses are mostly still in the research prototyping stage.
One of the main reasons lays to the difficulty in obtaining high quality graphene with an
affordable cost. Synthesis of inch sized single crystal graphene with ultrahigh mobility
requires extreme conditions and demanding trials which only can be achieved in countable
research labs in the world. On the other hand, most graphene thin film available on the
market has many defects with a resistance around hundreds ohms which is not suitable for
application in high performance electrical devices. Taking touch screen as an example,
graphene film is capable to make qualified pressure sensor for touch screen. However, such
product is simply offered an alternative for the existing ITO touch screen with few
advantages in performance and cost. Similar situation can also be found with graphene
22
wristbands which use the resistance change induced by deformation of graphene thin film to
measure heart rate. The product is innovative but lack consistence and accuracy compare with
current health bands on the market. Moreover, product so called graphene battery has been
advertising from several companies in Spain and China, which is consider as a controversial
naming method that graphene only serves as a conductive materials with little help in
efficiency and no change of mechanism,. The extremely increase in charge speed and storage
seems exciting, but currently review on real product is not available yet.
Beside the electrical applications, with lower threshold of industrialization, graphene has
been applied widely as additive in lubricant, paint, cloth fiber, adsorbents, heat generation
materials and structural materials. The idea behind such applications is using graphene to
substitute other carbon materials such as activated carbon, carbon fiber, amorphous carbon
and graphite paper. Indeed, graphene possess many outstanding properties which could
potentially replace other carbon materials. The booming in production of graphene brought
down the price of graphene with middle or low quality to an acceptable level. In this case,
graphene based lubricant oil, wall paint, filter, heating therapy, tiles and even underwear have
been for sale on the market.
Overall, current industrial applications seem match with the advanced basic research
hotpots of graphene. The difficult in stable mass production of high quality graphene the
development of graphene industry. Therefore, current graphene products mostly focused on
utilizing the property of carbon by substituting other carbon material with graphene for
existing applications, which is reasonable at the early stage of graphene industrialization in
order to digest the oversupply of graphene for now. But the unique property of graphene is
not elaborated in these applications. Graphenes energy band, quantum hall effect and unique
electrical property are the particular features of it. The exhibition of such features is expected
in future graphene devices, with the adequate graphene preparation and fabrication. In both
industry and research areas, mass synthesis of high quality graphene is the first barrier to
overcome.

Conclusions
In the past, graphene was regarded as a theoretical structure that was not stable enough to

23
physically exist. Advancement in research has not only disproved such false notion but also
enabled many other observations to be made and paved way for preparing novel materials
with extraordinary properties. Figure 8 shows the proportion of articles with different themes
in Science and Nature. A large part of existing literature on graphene concerns its electrical
properties, and others focus on the optical, thermal, mechanical properties and chemical
modifications of graphene. As the techniques to synthesize graphene improve, graphene is
increasingly adopted in many applications, spanning from electronics to FET, capacitor, and
sensor. Other applications exploit the mechanical properties and permselectivity of graphene
or GO films, or use graphene as a substrate to inspect other materials. Graphene with
different structures and morphology is needed for different applications and experiments.
Researchers also explore how graphene appears in different experiments and how the defects
and structure affect the properties. The synthesis of graphene is fundamental for all studies.
Simple methods are still needed to readily control the crystalline grain quantity, grain
boundaries, layers and output, and high-fidelity transfer.

Synthesis and transfer 17%

Articles about graphene Structure and morphology 9%

in Science and Nature

Electrical property 34% Properties 46%

Applications 28%

Figure 8 Statistical proportion of graphene research articles in Science and Nature.

24
Acknowledgments
This work was supported by the National Natural Science Foundation of China (51372133,
51672150).

References:
[1] Wallace, P. R., the band theory of graphite. Physical review 71 476 (1947).
[2] Helveg, S. et al., Atomic-scale imaging of carbon nanofibre growth. NATURE 427 426
(2004).
[3] Novoselov, K. S. et al., Electric field effect in atomically thin carbon films. SCIENCE
306 666 (2004).
[4] Berger, C. et al., Electronic confinement and coherence in patterned epitaxial graphene.
SCIENCE 312 1191 (2006).
[5] Novoselov, K. S. et al., A roadmap for graphene. NATURE 490 192 (2012).
[6] Bae, S. H. et al., Unveiling the carrier transport mechanism in epitaxial graphene for
forming wafer-scale, single-domain graphene. P NATL ACAD SCI USA 114 4082
(2017).
[7] Stankovich, S. et al., Graphene-based composite materials. NATURE 442 282 (2006).
[8] Dikin, D. A. et al., Preparation and characterization of graphene oxide paper. NATURE
448 457 (2007).
[9] Faucett, A. C., Flournoy, J. N., Mehta, J. S. & Mativetsky, J. M., Evolution, structure,
and electrical performance of voltage-reduced graphene oxide. FlatChem 1 42 (2017).
[10] Wei, Z. Q. et al., Nanoscale Tunable Reduction of Graphene Oxide for Graphene
Electronics. SCIENCE 328 1373 (2010).
[11] El-Kady, M. F., Strong, V., Dubin, S. & Kaner, R. B., Laser Scribing of
High-Performance and Flexible Graphene-Based Electrochemical Capacitors.
SCIENCE 335 1326 (2012).
[12] Voiry, D. et al., High-quality graphene via microwave reduction of solution-exfoliated
graphene oxide. SCIENCE 353 1413 (2016).
[13] Hernandez, Y. et al., High-yield production of graphene by liquid-phase exfoliation of
graphite. NAT NANOTECHNOL 3 563 (2008).
[14] elik, Y., Flahaut, E. & Suvac, E., A comparative study on few-layer graphene
production by exfoliation of different starting materials in a low boiling point solvent.
FlatChem 1 74 (2017).
[15] Li, X. L., Wang, X. R., Zhang, L., Lee, S. W. & Dai, H. J., Chemically derived,
ultrasmooth graphene nanoribbon semiconductors. SCIENCE 319 1229 (2008).
[16] Han, M. Y., Oezyilmaz, B., Zhang, Y. & Kim, P., Energy band-gap engineering of
graphene nanoribbons. PHYS REV LETT 98 (2007).
[17] Jiao, L. Y., Zhang, L., Wang, X. R., Diankov, G. & Dai, H. J., Narrow graphene
nanoribbons from carbon nanotubes. NATURE 458 877 (2009).
[18] Annett, J. & Cross, G., Self-assembly of graphene ribbons by spontaneous self-tearing
and peeling from a substrate. NATURE 535 271 (2016).
[19] Kosynkin, D. V. et al., Longitudinal unzipping of carbon nanotubes to form graphene
nanoribbons. NATURE 458 872 (2009).
[20] Cai, J. M. et al., Atomically precise bottom-up fabrication of graphene nanoribbons.

25
 NATURE 466 470 (2010).
[21] Ruffieux, P. et al., On-surface synthesis of graphene nanoribbons with zigzag edge
topology. NATURE 531 489 (2016).
[22] Chen, L. et al., Oriented graphene nanoribbons embedded in hexagonal boron nitride
trenches. NAT COMMUN 8 (2017).
[23] Li, X. S. et al., Large-Area Synthesis of High-Quality and Uniform Graphene Films on
Copper Foils. SCIENCE 324 1312 (2009).
[24] Li, X., Colombo, L. & Ruoff, R. S., Synthesis of Graphene Films on Copper Foils by
Chemical Vapor Deposition. ADV MATER 28 6247 (2016).
[25] Sun, Z. Z. et al., Growth of graphene from solid carbon sources. NATURE 468 549
(2010).
[26] Kim, K. S. et al., Large-scale pattern growth of graphene films for stretchable
transparent electrodes. NATURE 457 706 (2009).
[27] Yu, Q. et al., Graphene segregated on Ni surfaces and transferred to insulators. APPL
PHYS LETT 93 (2008).
[28] Lee, J. H. et al., Wafer-Scale Growth of Single-Crystal Monolayer Graphene on
Reusable Hydrogen-Terminated Germanium. SCIENCE 344 286 (2014).
[29] Hao, Y. F. et al., The Role of Surface Oxygen in the Growth of Large Single-Crystal
Graphene on Copper. SCIENCE 342 720 (2013).
[30] Kim, K. et al., Lanthanum-catalysed synthesis of microporous 3D graphene-like
carbons in a zeolite template. NATURE 535 131 (2016).
[31] Kang, J., Shin, D., Bae, S. & Hong, B. H., Graphene transfer: key for applications.
NANOSCALE 4 5527 (2012).
[32] Gao, L. B. et al., Face-to-face transfer of wafer-scale graphene films. NATURE 505
190 (2014).
[33] Kim, J. et al., Layer-Resolved Graphene Transfer via Engineered Strain Layers.
SCIENCE 342 833 (2013).
[34] Dimiev, A. et al., Layer-by-Layer Removal of Graphene for Device Patterning.
SCIENCE 331 1168 (2011).
[35] Meyer, J. C. et al., The structure of suspended graphene sheets. NATURE 446 60
(2007).
[36] Butz, B. et al., Dislocations in bilayer graphene. NATURE 505 533 (2014).
[37] Lui, C. H., Liu, L., Mak, K. F., Flynn, G. W. & Heinz, T. F., Ultraflat graphene.
NATURE 462 339 (2009).
[38] Girit, C. O. et al., Graphene at the Edge: Stability and Dynamics. SCIENCE 323 1705
(2009).
[39] Suenaga, K. & Koshino, M., Atom-by-atom spectroscopy at graphene edge. NATURE
468 1088 (2010).
[40] Huang, P. Y. et al., Grains and grain boundaries in single-layer graphene atomic
patchwork quilts. NATURE 469 389 (2011).
[41] Duong, D. L. et al., Probing graphene grain boundaries with optical microscopy.
NATURE 490 235 (2012).
[42] Grantab, R., Shenoy, V. B. & Ruoff, R. S., Anomalous Strength Characteristics of Tilt
Grain Boundaries in Graphene. SCIENCE 330 946 (2010).

26
[43] Lee, G. H. et al., High-Strength Chemical-Vapor Deposited Graphene and Grain
Boundaries. SCIENCE 340 1073 (2013).
[44] Tsen, A. W. et al., Tailoring Electrical Transport Across Grain Boundaries in
Polycrystalline Graphene. SCIENCE 336 1143 (2012).
[45] Hashimoto, A., Suenaga, K., Gloter, A., Urita, K. & Iijima, S., Direct evidence for
atomic defects in graphene layers. NATURE 430 870 (2004).
[46] Warner, J. H. et al., Dislocation-Driven Deformations in Graphene. SCIENCE 337 209
(2012).
[47] Ohta, T., Bostwick, A., Seyller, T., Horn, K. & Rotenberg, E., Controlling the electronic
structure of bilayer graphene. SCIENCE 313 951 (2006).
[48] Son, Y. W., Cohen, M. L. & Louie, S. G., Half-metallic graphene nanoribbons.
NATURE 444 347 (2006).
[49] Novoselov, K. S. et al., Two-dimensional gas of massless Dirac fermions in graphene.
NATURE 438 197 (2005).
[50] Mayorov, A. S. et al., Interaction-Driven Spectrum Reconstruction in Bilayer Graphene.
SCIENCE 333 860 (2011).
[51] Bostwick, A. et al., Observation of Plasmarons in Quasi-Freestanding Doped Graphene.
SCIENCE 328 999 (2010).
[52] Miller, D. L. et al., Observing the Quantization of Zero Mass Carriers in Graphene.
SCIENCE 324 924 (2009).
[53] Song, Y. J. et al., High-resolution tunnelling spectroscopy of a graphene quartet.
NATURE 467 185 (2010).
[54] Zhang, Y. B., Tan, Y. W., Stormer, H. L. & Kim, P., Experimental observation of the
quantum Hall effect and Berry's phase in graphene. NATURE 438 201 (2005).
[55] Kou, A. et al., Electron-hole asymmetric integer and fractional quantum Hall effect in
bilayer graphene. SCIENCE 345 55 (2014).
[56] Williams, J. R., DiCarlo, L. & Marcus, C. M., Quantum hall effect in a gate-controlled
p-n junction of graphene. SCIENCE 317 638 (2007).
[57] Abanin, D. A. & Levitov, L. S., Quantized transport in graphene p-n junctions in a
magnetic field. SCIENCE 317 641 (2007).
[58] Feldman, B. E., Krauss, B., Smet, J. H. & Yacoby, A., Unconventional Sequence of
Fractional Quantum Hall States in Suspended Graphene. SCIENCE 337 1196 (2012).
[59] Lee, K. et al., Chemical potential and quantum Hall ferromagnetism in bilayer graphene.
SCIENCE 345 58 (2014).
[60] Maher, P. et al., Tunable fractional quantum Hall phases in bilayer graphene. SCIENCE
345 61 (2014).
[61] Wang, L. et al., Evidence for a fractional fractal quantum Hall effect in graphene
superlattices. SCIENCE 350 1231 (2015).
[62] Du, X., Skachko, I., Duerr, F., Luican, A. & Andrei, E. Y., Fractional quantum Hall
effect and insulating phase of Dirac electrons in graphene. NATURE 462 192 (2009).
[63] Bolotin, K. I., Ghahari, F., Shulman, M. D., Stormer, H. L. & Kim, P., Observation of
the fractional quantum Hall effect in graphene. NATURE 462 196 (2009).
[64] Fujita, M., Wakabayashi, K., Nakada, K. & Kusakabe, K., Peculiar localized state at
zigzag graphite edge. J PHYS SOC JPN 65 1920 (1996).

27
[65] Magda, G. Z. et al., Room-temperature magnetic order on zigzag edges of narrow
graphene nanoribbons. NATURE 514 608 (2014).
[66] Gorbachev, R. V. et al., Detecting topological currents in graphene superlattices.
SCIENCE 346 448 (2014).
[67] Weitz, R. T., Allen, M. T., Feldman, B. E., Martin, J. & Yacoby, A., Broken-Symmetry
States in Doubly Gated Suspended Bilayer Graphene. SCIENCE 330 812 (2010).
[68] Zhang, Y. B. et al., Direct observation of a widely tunable bandgap in bilayer graphene.
NATURE 459 820 (2009).
[69] Levy, N. et al., Strain-Induced Pseudo-Magnetic Fields Greater Than 300 Tesla in
Graphene Nanobubbles. SCIENCE 329 544 (2010).
[70] Klimov, N. N. et al., Electromechanical Properties of Graphene Drumheads. SCIENCE
336 1557 (2012).
[71] Bolotin, K. I. et al., Ultrahigh electron mobility in suspended graphene. SOLID STATE
COMMUN 146 351 (2008).
[72] Zhao, L. Y. et al., Visualizing Individual Nitrogen Dopants in Monolayer Graphene.
SCIENCE 333 999 (2011).
[73] Amet, F. et al., Supercurrent in the quantum Hall regime. SCIENCE 352 966 (2016).
[74] Heersche, H. B., Jarillo-Herrero, P., Oostinga, J. B., Vandersypen, L. & Morpurgo, A. F.,
Bipolar supercurrent in graphene. NATURE 446 56 (2007).
[75] Miao, F. et al., Phase-coherent transport in graphene quantum billiards. SCIENCE 317
1530 (2007).
[76] Lee, M. et al., Ballistic miniband conduction in a graphene superlattice. SCIENCE 353
1526 (2016).
[77] Chen, S. et al., Electron optics with p-n junctions in ballistic graphene. SCIENCE 353
1522 (2016).
[78] Baringhaus, J. et al., Exceptional ballistic transport in epitaxial graphene nanoribbons.
NATURE 506 349 (2014).
[79] Ju, L. et al., Topological valley transport at bilayer graphene domain walls. NATURE
520 356 (2015).
[80] Rutter, G. M. et al., Scattering and interference in epitaxial graphene. SCIENCE 317
219 (2007).
[81] Bandurin, D. A. et al., Negative local resistance caused by viscous electron backflow in
graphene. SCIENCE 351 1055 (2016).
[82] Reed, J. P. et al., The Effective Fine-Structure Constant of Freestanding Graphene
Measured in Graphite. SCIENCE 330 805 (2010).
[83] Nair, R. R. et al., Fine structure constant defines visual transparency of graphene.
SCIENCE 320 1308 (2008).
[84] Wang, F. et al., Gate-variable optical transitions in graphene. SCIENCE 320 206
(2008).
[85] Liu, M. et al., A graphene-based broadband optical modulator. NATURE 474 64 (2011).
[86] Chen, J. N. et al., Optical nano-imaging of gate-tunable graphene plasmons. NATURE
487 77 (2012).
[87] Fei, Z. et al., Gate-tuning of graphene plasmons revealed by infrared nano-imaging.
NATURE 487 82 (2012).

28
[88] Balandin, A. A. et al., Superior thermal conductivity of single-layer graphene. NANO
LETT 8 902 (2008).
[89] Seol, J. H. et al., Two-Dimensional Phonon Transport in Supported Graphene.
SCIENCE 328 213 (2010).
[90] Lee, C., Wei, X. D., Kysar, J. W. & Hone, J., Measurement of the elastic properties and
intrinsic strength of monolayer graphene. SCIENCE 321 385 (2008).
[91] Lee, J. H., Loya, P. E., Lou, J. & Thomas, E. L., Dynamic mechanical behavior of
multilayer graphene via supersonic projectile penetration. SCIENCE 346 1092 (2014).
[92] Choi, J. S. et al., Friction Anisotropy-Driven Domain Imaging on Exfoliated Monolayer
Graphene. SCIENCE 333 607 (2011).
[93] Kawai, S. et al., Superlubricity of graphene nanoribbons on gold surfaces. SCIENCE
351 957 (2016).
[94] Li, S. et al., The evolving quality of frictional contact with graphene. NATURE 539 541
(2016).
[95] Wang, X. R. et al., N-Doping of Graphene Through Electrothermal Reactions with
Ammonia. SCIENCE 324 768 (2009).
[96] Elias, D. C. et al., Control of Graphene's Properties by Reversible Hydrogenation:
Evidence for Graphane. SCIENCE 323 610 (2009).
[97] Gonzalez-Herrero, H. et al., Atomic-scale control of graphene magnetism by using
hydrogen atoms. SCIENCE 352 437 (2016).
[98] Ponomarenko, L. A. et al., Chaotic dirac billiard in graphene quantum dots. SCIENCE
320 356 (2008).
[99] Yang, H. et al., Graphene Barristor, a Triode Device with a Gate-Controlled Schottky
Barrier. SCIENCE 336 1140 (2012).
[100] Liao, L. et al., High-speed graphene transistors with a self-aligned nanowire gate.
NATURE 467 305 (2010).
[101] Wu, Y. Q. et al., High-frequency, scaled graphene transistors on diamond-like carbon.
NATURE 472 74 (2011).
[102] Britnell, L. et al., Field-Effect Tunneling Transistor Based on Vertical Graphene
Heterostructures. SCIENCE 335 947 (2012).
[103] Lin, Y. M. et al., Wafer-Scale Graphene Integrated Circuit. SCIENCE 332 1294 (2011).
[104] Levendorf, M. P. et al., Graphene and boron nitride lateral heterostructures for
atomically thin circuitry. NATURE 488 627 (2012).
[105] Miller, J. R., Outlaw, R. A. & Holloway, B. C., Graphene Double-Layer Capacitor with
ac Line-Filtering Performance. SCIENCE 329 1637 (2010).
[106] Zhu, Y. W. et al., Carbon-Based Supercapacitors Produced by Activation of Graphene.
SCIENCE 332 1537 (2011).
[107] Yang, X. W., Cheng, C., Wang, Y. F., Qiu, L. & Li, D., Liquid-Mediated Dense
Integration of Graphene Materials for Compact Capacitive Energy Storage. SCIENCE
341 534 (2013).
[108] Garaj, S. et al., Graphene as a subnanometre trans-electrode membrane. NATURE 467
173 (2010).
[109] Rodrigo, D. et al., Mid-infrared plasmonic biosensing with graphene. SCIENCE 349
165 (2015).

29
[110] Cheianov, V. V., Fal'Ko, V. & Altshuler, B. L., The focusing of electron flow and a
Veselago lens in graphene p-n junctions. SCIENCE 315 1252 (2007).
[111] Zhao, Y. et al., Creating and probing electron whispering-gallery modes in graphene.
SCIENCE 348 672 (2015).
[112] Bonaccorso, F., Sun, Z., Hasan, T. & Ferrari, A. C., Graphene photonics and
optoelectronics. NAT PHOTONICS 4 611 (2010).
[113] Li, X. et al., Graphene-On-Silicon Schottky Junction Solar Cells. ADV MATER 22
2743 (2010).
[114] Li, S., Tu, K., Lin, C., Chen, C. & Chhowalla, M., Solution-Processable Graphene
Oxide as an Efficient Hole Transport Layer in Polymer Solar Cells. ACS NANO 4 3169
(2010).
[115] Van Le, Q., Choi, J. & Kim, S. Y., Recent advances in the application of
two-dimensional materials as charge transport layers in organic and perovskite solar
cells. FlatChem 2 54 (2017).
[116] Wang, X., Zhi, L. & Muellen, K., Transparent, conductive graphene electrodes for
dye-sensitized solar cells. NANO LETT 8 323 (2008).
[117] Wu, J. et al., Organic Light-Emitting Diodes on Solution-Processed Graphene
Transparent Electrodes. ACS NANO 4 43 (2010).
[118] Bae, S. et al., Roll-to-roll production of 30-inch graphene films for transparent
electrodes. NAT NANOTECHNOL 5 574 (2010).
[119] Xia, F., Mueller, T., Lin, Y., Valdes-Garcia, A. & Avouris, P., Ultrafast graphene
photodetector. NAT NANOTECHNOL 4 839 (2009).
[120] Chini, Kumar, Mrinmoy, Chatterjee & Shyambo, Hydrothermally reduced nano porous
graphenepolyaniline nanofiber composites for supercapacitor. FlatChem 1 1 (2017).
[121] Gabor, N. M. et al., Hot Carrier-Assisted Intrinsic Photoresponse in Graphene.
SCIENCE 334 648 (2011).
[122] Boland, C. S. et al., Sensitive electromechanical sensors using viscoelastic
graphene-polymer nanocomposites. SCIENCE 354 1257 (2016).
[123] Bunch, J. S. et al., Electromechanical resonators from graphene sheets. SCIENCE 315
490 (2007).
[124] Berman, D., Deshmukh, S. A., Sankaranarayanan, S., Erdemir, A. & Sumant, A. V.,
Macroscale superlubricity enabled by graphene nanoscroll formation. SCIENCE 348
1118 (2015).
[125] Xin, G. Q. et al., Highly thermally conductive and mechanically strong graphene fibers.
SCIENCE 349 1083 (2015).
[126] Blees, M. K. et al., Graphene kirigami. NATURE 524 204 (2015).
[127] Liu, P. et al., Layered and scrolled nanocomposites with aligned semi-infinite graphene
inclusions at the platelet limit. SCIENCE 353 364 (2016).
[128] Liang, J. et al., Molecular-Level Dispersion of Graphene into Poly(vinyl alcohol) and
Effective Reinforcement of their Nanocomposites. ADV FUNCT MATER 19 2297
(2009).
[129] Xu, K., Cao, P. G. & Heath, J. R., Graphene Visualizes the First Water Adlayers on
Mica at Ambient Conditions. SCIENCE 329 1188 (2010).
[130] Nair, R. R., Wu, H. A., Jayaram, P. N., Grigorieva, I. V. & Geim, A. K., Unimpeded

30
 Permeation of Water Through Helium-Leak-Tight Graphene-Based Membranes.
SCIENCE 335 442 (2012).
[131] Li, H. et al., Ultrathin, Molecular-Sieving Graphene Oxide Membranes for Selective
Hydrogen Separation. SCIENCE 342 95 (2013).
[132] Kim, H. W. et al., Selective Gas Transport Through Few-Layered Graphene and
Graphene Oxide Membranes. SCIENCE 342 91 (2013).
[133] Joshi, R. K. et al., Precise and Ultrafast Molecular Sieving Through Graphene Oxide
Membranes. SCIENCE 343 752 (2014).
[134] Celebi, K. et al., Ultimate Permeation Across Atomically Thin Porous Graphene.
SCIENCE 344 289 (2014).
[135] Chung, K., Lee, C. H. & Yi, G. C., Transferable GaN Layers Grown on ZnO-Coated
Graphene Layers for Optoelectronic Devices. SCIENCE 330 655 (2010).
[136] Colson, J. W. et al., Oriented 2D Covalent Organic Framework Thin Films on
Single-Layer Graphene. SCIENCE 332 228 (2011).
[137] Kim, Y. et al., Remote epitaxy through graphene enables two-dimensional
material-based layer transfer. NATURE 544 340 (2017).
[138] Xu, J., Wang, K., Zu, S., Han, B. & Wei, Z., Hierarchical Nanocomposites of
Polyaniline Nanowire Arrays on Graphene Oxide Sheets with Synergistic Effect for
Energy Storage. ACS NANO 4 5019 (2010).
[139] Liu, L. et al., Heteroepitaxial Growth of Two-Dimensional Hexagonal Boron Nitride
Templated by Graphene Edges. SCIENCE 343 163 (2014).
[140] Zhao, J. et al., Free-Standing Single-Atom-Thick Iron Membranes Suspended in
Graphene Pores. SCIENCE 343 1228 (2014).
[141] Meyer, J. C., Girit, C. O., Crommie, M. F. & Zettl, A., Imaging and dynamics of light
atoms and molecules on graphene. NATURE 454 319 (2008).
[142] Yuk, J. M. et al., High-Resolution EM of Colloidal Nanocrystal Growth Using
Graphene Liquid Cells. SCIENCE 336 61 (2012).
[143] Algara-Siller, G. et al., Square ice in graphene nanocapillaries. NATURE 519 443
(2015).
[144] Gulde, M. et al., Ultrafast low-energy electron diffraction in transmission resolves
polymer/graphene superstructure dynamics. SCIENCE 345 200 (2014).

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 Highlights

Graphene materials residing at the frontier of scientific research offer immense potential for overcoming
the challenges related to the performance, functionality and durability of key functional materials. In this
Review, we recollect the latest development in the synthesis, structural analysis, characteristics, and
potential applications of graphene materials, to address the continued developments and challenges with a
wide scope of interest, highlighting fundamental understanding of the synthesis and characterization
procedures, future outlook, as well as an in-depth discussion of high-end application areas.

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 Graphical Abstract

This Review highlights the latest development in the synthesis, structural analysis, and properties of
graphene materials, with an in-depth discussion of its high-end applications.

Synthesis and transfer 17%

Articles about graphene Structure and morphology 9%

in Science and Nature

Electrical property 34% Properties 46%

Applications 28%

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