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Graphene

Not to be confused with Graphite, Grapheme, Graphane,


or Graphyne.
For an overview of two-dimensional materials such as
graphene, see Single layer materials.
Graphene is pure carbon in the form of a very thin,

possible. Andre Geim and Konstantin Novoselov at the


University of Manchester won the Nobel Prize in Physics
in 2010 for groundbreaking experiments regarding the
two-dimensional material graphene.[5]
The global market for graphene is reported to have
reached $9 million by 2014 with most of these sales being concentrated in the semiconductor, electronics, battery energy and composites.[6]

1 Denition
Graphene is a combination of graphite and the sux
-ene, named by Hanns-Peter Boehm,[7] who described
single-layer carbon foils in 1962.[8]
The term graphene rst appeared in 1987[9] to describe
single sheets of graphite as a constituent of graphite intercalation compounds (GICs); conceptually a GIC is a crystalline salt of the intercalant and graphene. The term was
also used in early descriptions of carbon nanotubes,[10] as
Graphene is an atomic-scale honeycomb lattice made of carbon well as for epitaxial graphene[11] and polycyclic aromatic
atoms.
hydrocarbons.[12] Graphene can be considered an incarbon ring) polycyclic
nearly transparent sheet, one atom thick. It is remark- nite alternant (only six-member
[13]
aromatic
hydrocarbon
(PAH).
ably strong for its very low weight (100 times stronger
than steel[1] ) and it conducts heat and electricity with The IUPAC compendium of technology states: previgreat eciency.[2] While scientists had theorized about ously, descriptions such as graphite layers, carbon layers,
graphene for decades, it was rst produced in the lab or carbon sheets have been used for the term graphene...
in 2003.[3] Because it is virtually two-dimensional, it in- it is incorrect to use for a single layer a term which interacts oddly with light and with other materials. Re- cludes the term graphite, which would imply a threesearchers have identied the bipolar transistor eect, dimensional structure. The term graphene should be
ballistic transport of charges and large quantum oscilla- used only when the reactions, structural relations or other
properties of individual layers are discussed.[14]
tions.
Technically, graphene is a crystalline allotrope of carbon with 2-dimensional properties. In graphene, carbon
atoms are densely packed in a regular sp2 -bonded atomicscale chicken wire (hexagonal) pattern. Graphene can
be described as a one-atom thick layer of graphite. It
is the basic structural element of other allotropes, including graphite, charcoal, carbon nanotubes and fullerenes.
It can also be considered as an indenitely large aromatic
molecule, the limiting case of the family of at polycyclic
aromatic hydrocarbons.

Geim dened isolated or free-standing graphene as


graphene is a single atomic plane of graphite, which
and this is essential is suciently isolated from its
environment to be considered free-standing.[15] This
denition is narrower than the IUPAC denition and
refers to cleaved, transferred and suspended graphene.
Other forms of graphene, such as graphene grown on
various metals, can become free-standing if, for example,
suspended or transferred to silicon dioxide (SiO
2) or silicon carbide (after its passivation with
[16]
Graphene research has expanded quickly since the sub- hydrogen).
stance was rst isolated in 2004. Research was informed When graphene was rst reliably produced in the lab in
by theoretical descriptions of graphenes composition, 2004 by Andre Geim and Kostya Novoselov at the Unistructure and properties, which had all been calculated versity of Manchester, single-atom-thick crystallites were
decades earlier.[4] High-quality graphene also proved to extracted from bulk graphite by lifting graphene layers
be surprisingly easy to isolate, making more research from graphite with adhesive tape then transferred them
1

onto a silicon wafer. What they had isolated was a new


material which is still carbon and it also has the basic
structural features of the element that we see in its other
allotropes that we have known for centuries, such as in
graphite & charcoal and of course more recently carbon
nanotubes and fullerenes etc. What was new though is
that graphene is 2 dimensional and it therefore has the basic structure of a very large and perhaps innite aromatic
molecule. As a result Geim and Novoselov won the Nobel
Prize in Physics in 2010 for their work in revealing this
new two-dimensional material.[17]

HISTORY

mercial applications of these materials. The new 60m


National Graphene Institute will be a research centre
whilst the 60m Graphene Engineering Innovation Centre (GEIC) has been announced to allow for the acceleration of applied research and development in partnership
with other research organisations and industry.[18]

Researchers have continued to work on the properties


of the material and high-quality graphene has proven to
be relatively easy to isolate in ever increasing quantities.
This has not only made more research possible but to also
allow the properties being discovered to be exploited and
practical uses to be developed as conrmed by a urry of
patents.

Large scale manufacture of graphene is beginning to take


place in locations where the chemistry based process industries have the infrastructure needed and can manage the materials, processes and technologies. The processes are moving out of laboratories into locations such
as that in North East England where the North East of
England Process Industry Cluster already have two commercial manufacturers Applied Graphene Materials[19]
& Thomas Swan Limited.[20] The UK Government has
also chosen this chemistry based industrial manufacturing cluster to be the base of the UKs National Graphene
Applications Centre.[21]

1.1

2 History

Properties and Manufacture

Graphene, unlike carbonnanotubes, has edges that can


react chemically. These exposed carbon molecules
have special reactivity, as do any imperfections in the
graphene sheets. Not surprisingly, because of its 2 dimensional structure and the lateral availability of the carbon, graphene is now known to be the most reactive form
of carbon. In addition scientists at Stanford University
have reported in 2013 that sheets of graphene one atom
thick are a hundred times more chemically reactive than
thicker sheets. Consequently controlling the functionalization of graphene sheets will be dicult but may still be
the source of even more specialised properties and uses
that are still unknown to us today.
There are currently several methods to produce graphene
described in the scientic and commercial literature
showing the intensity of development work globally. One
is mechanical cleavage, that is taking layers o multilayered graphite or by depositing one layer of carbon onto
another material. The former is clearly how it was done
using adhesive tape, but it is reported that the latter is
more capable of making a mono-layer with the fewest defects. Graphene platelets can also be created by chemically cutting open carbon nanotubes, one method describing how the nanotubes are cut open in solution by action
of potassium permanganate and sulfuric acid. Chemical, solvent or sonic exfoliation (separation) of graphene
layers from graphite has also been developed. Plasma
deposition techniques, the reduction of graphene oxides
(RGO) and other synthetic methodologies are being introduced as route to scale up manufacture.
After the initial isolation of graphene occurring at The
University of Manchester, the university is aiming to
strengthen its position as 'The home of graphene' through
furthering fundamental research into graphene and other
two dimensional materials and seeking to develop com-

In 1859 Benjamin Collins Brodie was aware of the


highly lamellar structure of thermally reduced graphite
oxide.[22]
The structure of graphite was solved in 1916[23] by the
related method of powder diraction.[24] It was studied in
detail by V. Kohlschtter and P. Haenni in 1918, who also
described the properties of graphite oxide paper.[25] Its
structure was determined from single-crystal diraction
in 1924.[26]
The theory of graphene was rst explored by P. R. Wallace in 1947 as a starting point for understanding the electronic properties of 3D graphite. The emergent massless
Dirac equation was rst pointed out by Gordon Walter Semeno and David P. DeVincenzo and Eugene J. Mele.[27]
Semeno emphasized the occurrence in a magnetic eld
of an electronic Landau level precisely at the Dirac point.
This level is responsible for the anomalous integer quantum Hall eect.[28][29][30]
The earliest TEM images of few-layer graphite were published by G. Ruess and F. Vogt in 1948.[31] Later, single
graphene layers were also observed directly by electron
microscopy.[32] Before 2004 intercalated graphite compounds were studied under a transmission electron microscope (TEM). Researchers occasionally observed thin
graphitic akes (few-layer graphene) and possibly even
individual layers. An early, detailed study on few-layer
graphite dates to 1962.[33][34]
Starting in the 1970s single layers of graphite were grown
epitaxially on top of other materials.[35] This epitaxial graphene consists of a single-atom-thick hexagonal
lattice of sp2 -bonded carbon atoms, as in free-standing
graphene. However, there is signicant charge transfer from the substrate to the epitaxial graphene, and,
in some cases, hybridization between the d-orbitals of

3
the substrate atoms and orbitals of graphene, which a graphite thickness of 0.01 thousandth of an inch. The
signicantly alters the electronic structure of epitaxial key to success was high-throughput visual recognition of
graphene.
graphene on a properly chosen substrate, which provides
Single layers of graphite were also observed by a small but noticeable optical contrast.
transmission electron microscopy within bulk materials,
in particular inside soot obtained by chemical exfoliation.
Eorts to make thin lms of graphite by mechanical exfoliation started in 1990,[36] but nothing thinner than 50
to 100 layers was produced before 2004.

The cleavage technique led directly to the rst observation of the anomalous quantum Hall eect in
graphene,[28][30] which provided direct evidence of
graphenes theoretically predicted Berrys phase of massless Dirac fermions. The eect was reported soon after by Philip Kim and Yuanbo Zhang in 2005. These
experiments started after the researchers observed colleagues who were looking for the quantum Hall eect[41]
and Dirac fermions[42] in bulk graphite.
Even though graphene on nickel and on silicon carbide
have both existed in the laboratory for decades, graphene
mechanically exfoliated on SiO
2 provided the rst proof of the Dirac fermion nature of
electrons.

A lump of graphite, a graphene transistor and a tape dispenser.


Donated to the Nobel Museum in Stockholm by Andre Geim and
Konstantin Novoselov in 2010.

Initial attempts to make atomically thin graphitic lms


employed exfoliation techniques similar to the drawing
method. Multilayer samples down to 10 nm in thickness
were obtained.[37] Old papers were unearthed[33] in which
researchers tried to isolate graphene starting with intercalated compounds. These papers reported the observation
of very thin graphitic fragments (possibly monolayers) by
transmission electron microscopy. Neither of the earlier
observations was sucient to spark the graphene gold
rush, which awaited macroscopic samples of extracted
atomic planes.
One of the very rst patents pertaining to the production of graphene was led in October 2002 and granted
in 2006 (US Pat. 7071258).[38] Titled, Nano-scaled
Graphene Plates, this patent detailed one of the very rst
large scale graphene production processes. Two years
later, in 2004 Andre Geim and Kostya Novoselov at The
University of Manchester extracted single-atom-thick
crystallites from bulk graphite.[39] They pulled graphene
layers from graphite and transferred them onto thin SiO
2 on a silicon wafer in a process called either micromechanical cleavage or the Scotch tape technique.[40] The
SiO
2 electrically isolated the graphene and weakly interacted
with it, providing nearly charge-neutral graphene layers.
The silicon beneath the SiO
2 could be used as a back gate electrode to vary the
charge density in the graphene over a wide range. They
may not have been the rst to use this technique US
6667100, led in 2002, describes how to process commercially available exible expanded graphite to achieve

Andre Geim and Konstantin Novoselov, 2010

Geim and Novoselov received several awards for their pioneering research on graphene, notably the 2010 Nobel
Prize in Physics.[43]

3 Properties
3.1 Structure
Graphenes stability is due to a tightly packed, periodic
array of carbon atoms and an sp2 orbital hybridization a combination of orbitals p and p that constitute the bond. Graphene has three -bonds and one -bond. The
nal p electron makes up the -bond, and is key to the
half-lled band that permits free-moving electrons.[44]
Graphene sheets in solid form usually show evidence in
diraction for graphites (002) layering. This is true of
some single-walled nanostructures.[45] However, unlayered graphene with only (hk0) rings has been found in the
core of presolar graphite onions.[46] TEM studies show
faceting at defects in at graphene sheets[47] and suggest
a role for two-dimensional crystallization from a melt.
Graphene can self-repair holes in its sheets, when

3 PROPERTIES

exposed to molecules containing carbon, such as


hydrocarbons. Bombarded with pure carbon atoms, the
atoms perfectly align into hexagons, completely lling the
holes.[48][49]
The atomic structure of isolated, single-layer graphene
was studied by transmission electron microscopy (TEM)
on sheets of graphene suspended between bars of a metallic grid.[32] Electron diraction patterns showed the expected honeycomb lattice. Suspended graphene also
showed rippling of the at sheet, with amplitude of
about one nanometer. These ripples may be intrinsic to the material as a result of the instability of twodimensional crystals,[37][50][51] or may originate from the
ubiquitous dirt seen in all TEM images of graphene.
Atomic resolution real-space images of isolated, single- GNR band structure for zig-zag orientation. Tightbinding calculations show that zigzag orientation is always metallic.
layer graphene on SiO
[52][53]
2 substrates are available
via scanning tunneling
microscopy. Photoresist residue, which must be removed to obtain atomic-resolution images, may be the
"adsorbates" observed in TEM images, and may explain
the observed rippling. Rippling on SiO
2 is caused by conformation of graphene to the underlying SiO
2, and is not intrinsic.[52]

3.2

Chemical

Graphene is the only form of carbon (and generally all


solid materials) in which each single atom is in exposure for chemical reaction from two sides (due to the
2D structure). It is known that carbon atoms at the
edge of graphene sheets have special chemical reactivity, and graphene has the highest ratio of edgy carbons (in comparison with similar materials such as carbon nanotubes). In addition, various types of defects
within the sheet, which are very common, increase the
chemical reactivity.[54] The onset temperature of reaction between the basal plane of single-layer graphene
and oxygen gas is below 260 C (530 K) [55] and the
graphene burns at very low temperature (e.g., 350 C
(620 K)).[56] In fact, graphene is chemically the most reactive form of carbon, owing to the lateral availability
of carbon atoms. Graphene is commonly modied with
oxygen- and nitrogen-containing functional groups and
analyzed by infrared spectroscopy and X-ray photoelectron spectroscopy. However, determination of structures
of graphene with oxygen-[57] and nitrogen-[58] containing
functional groups is a dicult task unless the structures
are well controlled.

GNR band structure for armchair orientation. Tightbinding calculations show that armchair orientation can be semiconducting
or metallic depending on width (chirality).

3.3 Electronic
Graphene is a zero-gap semiconductor. Four electronic
properties separate it from other condensed matter systems.
3.3.1 Electronic spectrum
Electrons propagating through graphenes honeycomb lattice eectively lose their mass, producing quasi-particles
that are described by a 2D analogue of the Dirac equation rather than the Schrdinger equation for spin-1 2
particles.[60][61]
Dispersion relation
Using a conventional tightbinding model the dispersion relation produces energy of
the electrons with wave vector k is[62][63]

v (
u
)
In 2013, Stanford University physicists reported that
u
k
a
k
a
k
3a
y
y
x
sheets of graphene one atom thick are a hundred times E = t 2 1 + 4 cos2
+ 4 cos
cos
0
[59]
2
2
2
more chemically reactive than thicker sheets.

3.3

Electronic

with the nearest-neighbor hopping energy 0 2.8 eV


and the lattice constant a 2.46 . The conduction and
valence bands, respectively, correspond to the dierent
signs; they touch each other at six points, the K-values
of the two-dimensional hexagonal Brillouin zone. Two of
these six points are independent, while the rest are equivalent by symmetry. In the vicinity of the K-points the
energy depends linearly on the wave vector, similar to a
relativistic particle.[62][64] Since an elementary cell of the
lattice has a basis of two atoms, the wave function has an
eective 2-spinor structure.

5
ing. Scattering by the acoustic phonons of graphene intrinsically limits room temperature mobility to 200,000
cm2 V1 s1 at a carrier density of 1012 cm2 ,[67][68]
which was later demonstrated and is 10 greater than
copper.[44]

The corresponding resistivity of the graphene sheet would


be 106 cm. This is less than the resistivity of silver,
the lowest known at room temperature.[69] However, for
room temperature graphene on SiO
2 substrates, scattering of electrons by optical phonons
of the substrate is a larger eect than scattering by
As a consequence, at low energies, even neglecting the graphenes own phonons. This limits mobility to 40,000
true spin, the electrons can be described by an equation cm2 V1 s1 .[67]
that is formally equivalent to the massless Dirac equation. Electrical resistance in 40-nanometer-wide nanoribbons
Hence, the electrons and holes are called Dirac fermions of epitaxial graphene changes in discrete steps. The
and the six corners are called the Dirac points.[62] This ribbons conductance exceeds predictions by a factor of
pseudo-relativistic description is restricted to the chiral 10. The ribbons can act more like optical waveguides or
limit, i.e., to vanishing rest mass M 0 , which leads to in- quantum dots, allowing electrons to ow smoothly along
teresting additional features:[62][65]
the ribbon edges. In copper, resistance increases in proportion to length as electrons encounter impurities.[70][71]
vF (r) = E(r).
Here vF ~ 106 m/s (.003 c) is the Fermi velocity in
graphene, which replaces the velocity of light in the Dirac
theory; is the vector of the Pauli matrices, (r) is the
two-component wave function of the electrons, and E is
their energy.[60]

Transport is dominated by two modes. One is ballistic


and temperature independent, while the other is thermally activated. Ballistic electrons resemble those in
cylindrical carbon nanotubes. At room temperature, resistance increases abruptly at a particular lengththe
ballistic mode at 16 micrometres and the other at 160
nanometres (1% of the former length).[70]

The equation describing the electrons linear dispersion The ribbons were grown on the edges of threedimensional structures etched into silicon carbide wafers.
relation is

When the wafers are heated to approximately 1,000 C


E = vF kx2 + ky2 ;
(1,270 K; 1,830 F), silicon is preferentially driven o
where the wavevector k is measured from the Dirac points along the edges, forming nanoribbons whose structure is
(the zero of energy is chosen here to coincide with the determined by the pattern of the three-dimensional surDirac points). The equation uses a pseudospin matrix face. The nanoribbons had perfectly smooth edges, anformula that describes two sublattices of the honeycomb nealed by the fabrication process. Electron mobility measurements surpassing one million correspond to a sheet
lattice.[64]
resistance of one ohm per square two orders of magnitude lower than in two-dimensional graphene.[70]
3.3.2 Single-atom wave propagation
Graphene electrons can cover micrometer distances without scattering, even at room temperature.[60]
Electron waves in graphene propagate within a singleatom layer, making them sensitive to the proxim- Despite zero carrier density near the Dirac points,
exhibits a minimum conductivity on the order
ity of other materials such as high- dielectrics, graphene
2
of
4e
/h
. The origin of this minimum conductivity is
superconductors and ferromagnetics.
still unclear. However, rippling of the graphene sheet or
ionized impurities in the SiO
2 substrate may lead to local puddles of carriers that al3.3.3 Electron transport
low conduction.[61] Several theories suggest that the minExperimental results from transport measurements show imum conductivity should be 4e2 /(h) ; however, most
that graphene has a remarkably high electron mobil- measurements are of order 4e2 /h or greater[37] and deity at room temperature, with reported values in excess pend on impurity concentration.[72]
of 15,000 cm2 V1 s1 .[37] Additionally, the symmetry Near zero carrier density graphene exhibits positive phoof the experimentally measured conductance indicates toconductivity and negative photoconductivity at high
that hole and electron mobilities should be nearly the carrier density. Theis governed by the interplay between
same.[61] The mobility is nearly independent of temper- photoinduced changes of both the Drude weight and the
ature between 10 K and 100 K,[28][66][67] which implies carrier scattering rate.[73]
that the dominant scattering mechanism is defect scatter-

6
Graphene doped with various gaseous species (both acceptors and donors) can be returned to an undoped state
by gentle heating in vacuum.[72][74] Even for dopant concentrations in excess of 1012 cm2 carrier mobility exhibits no observable change.[74] Graphene doped with
potassium in ultra-high vacuum at low temperature can
reduce mobility 20-fold.[72][75] The mobility reduction is
reversible on heating the graphene to remove the potassium.

3 PROPERTIES
clotron mass, despite their zero eective mass.[28]
Graphene samples prepared on nickel lms, and on
both the silicon face and carbon face of silicon carbide, show the anomalous eect directly in electrical
measurements.[79][80][81][82][83][84] Graphitic layers on the
carbon face of silicon carbide show a clear Dirac spectrum in angle-resolved photoemission experiments, and
the eect is observed in cyclotron resonance and tunneling experiments.[85]

Due to graphenes two dimensions, charge fractionalization (where the apparent charge of individual pseudoparticles in low-dimensional systems is less than a single 3.3.5 Strong magnetic elds
quantum[76] ) is thought to occur. It may therefore be a
suitable material for constructing quantum computers[77] In magnetic elds above 10 Teslas or so additional
plateaus of the Hall conductivity at xy = e2 /h with
using anyonic circuits.[78]
= 0, 1, 4 are observed.[86] A plateau at = 3[87] and
the fractional quantum Hall eect at = 1 3 were also
reported.[87][88]
3.3.4 Anomalous quantum Hall eect
The quantum Hall eect is a quantum mechanical version
of the Hall eect, which is the production of transverse
(perpendicular to the main current) conductivity in the
presence of a magnetic eld. The quantization of the Hall
eect xy at integer multiples (the "Landau level") of the
basic quantity e2 /h (where e is the elementary electric
charge and h is Plancks constant) It can usually be observed only in very clean silicon or gallium arsenide solids
at temperatures around 3 K and very high magnetic elds.
Graphene shows the quantum Hall eect with respect
to conductivity-quantization: the eect is anomalous in
that the sequence of steps is shifted by 1/2 with respect to the standard sequence and with an additional
factor of 4. Graphenes Hall conductivity is xy =
4 (N + 1/2) e2 /h , where N is the Landau level and
the double valley and double spin degeneracies give the
factor of 4.[37] These anomalies are present at room temperature, i.e. at roughly 20 C (293 K).[28]
This behavior is a direct result of graphenes massless
Dirac electrons. In a magnetic eld, their spectrum has
a Landau level with energy precisely at the Dirac point.
This level is a consequence of the AtiyahSinger index
theorem and is half-lled in neutral graphene,[62] leading to the "+1/2 in the Hall conductivity.[29] Bilayer
graphene also shows the quantum Hall eect, but with
only one of the two anomalies (i.e. xy = 4 N e2 /h
). In the second anomaly, the rst plateau at N=0 is absent, indicating that bilayer graphene stays metallic at the
neutrality point.[37]

These observations with = 0, 1, 3, 4 indicate that


the four-fold degeneracy (two valley and two spin degrees
of freedom) of the Landau energy levels is partially or
completely lifted.
3.3.6 Casimir eect
The Casimir eect is an interaction between disjoint neutral bodies provoked by the uctuations of the electrodynamical vacuum. Mathematically it can be explained by
considering the normal modes of electromagnetic elds,
which explicitly depend on the boundary (or matching)
conditions on the interacting bodies surfaces. Since
graphene/electromagnetic eld interaction is strong for a
one-atom-thick material, the Casimir eect is of growing
interest.[89][90]
3.3.7 van der Waals force
The van der Waals force (or dispersion force) is also unusual, obeying an inverse cubic, asymptotic power law in
contrast to the usual inverse quartic.[91]

3.4 Massive electrons


Graphenes unit cell has two identical carbon atoms and
two zero-energy states: one in which the electron resides
on atom A, the other in which the electron resides on atom
B. Both states exist at exactly zero energy. However, if
the two atoms in the unit cell are not identical, the situation changes. Hunt et al. show that placing hBN in
contact with graphene can alter the potential felt at atom
A versus atom B enough that the electrons develop a mass
and accompanying band gap of about 30 meV.[92]

Unlike normal metals, graphenes longitudinal resistance


shows maxima rather than minima for integral values
of the Landau lling factor in measurements of the
ShubnikovDe Haas oscillations, whereby the term integral quantum Hall eect. These oscillations show a
phase shift of , known as Berrys phase.[28][61] Berrys
phase arises due to the zero eective carrier mass near The mass can be positive or negative. An arrangement
the Dirac points.[30] The temperature dependence of the that slightly raises the energy of an electron on atom A reloscillations reveals that the carriers have a non-zero cy- ative to atom B gives it a positive mass, while an arrange-

3.5

Optical

ment that raises the energy of atom B produces a negative electron mass. The two versions behave alike and
are indistinguishable via optical spectroscopy. An electron traveling from a positive-mass region to a negativemass region must cross an intermediate region where its
mass once again becomes zero. This region is gapless and
therefore metallic. Metallic modes bounding semiconducting regions of opposite-sign mass is a hallmark of a
topological phase and display much the same physics as
topological insulators.[92]
If the mass in graphene can be controlled, electrons can
be conned to massless regions by surrounding them
with massive regions, allowing the patterning of quantum
dots, wires, and other mesoscopic structures. It also produces one-dimensional conductors along the boundary.
These wires would be protected against backscattering
and could carry currents without dissipation.[92]

3.5

Optical

Photograph of graphene in transmitted light. This one-atomthick crystal can be seen with the naked eye because it absorbs
approximately 2.6% of green light,[93] and 2.3% of red light.[94]

Graphenes unique optical properties produce an unexpectedly high opacity for an atomic monolayer in vacuum, absorbing 2.3% of red light, where is the
ne-structure constant.[95] This is a consequence of the
unusual low-energy electronic structure of monolayer
graphene that features electron and hole conical bands
meeting each other at the Dirac point... [which] is qualitatively dierent from more common quadratic massive
bands".[94] Based on the SlonczewskiWeissMcClure
(SWMcC) band model of graphite, the interatomic distance, hopping value and frequency cancel when optical
conductance is calculated using Fresnel equations in the
thin-lm limit.

7
not precise enough to improve on other techniques for
determining the ne-structure constant.[96]
Graphenes band gap can be tuned from 0 to 0.25 eV
(about 5 micrometre wavelength) by applying voltage to a
dual-gate bilayer graphene eld-eect transistor (FET) at
room temperature.[97] The optical response of graphene
nanoribbons is tunable into the terahertz regime by an
applied magnetic eld.[98] Graphene/graphene oxide systems exhibit electrochromic behavior, allowing tuning of
both linear and ultrafast optical properties.[99]
A graphene-based Bragg grating (one-dimensional
photonic crystal) has been fabricated and demonstrated
its capability for excitation of surface electromagnetic
waves in the periodic structure by using 633 nm HeNe
laser as the light source.[100]

3.5.1 Saturable absorption


Such unique absorption could become saturated when the
input optical intensity is above a threshold value. This
nonlinear optical behavior is termed saturable absorption
and the threshold value is called the saturation uence.
Graphene can be saturated readily under strong excitation
over the visible to near-infrared region, due to the universal optical absorption and zero band gap. This has relevance for the mode locking of ber lasers, where fullband
mode locking has been achieved by graphene-based saturable absorber. Due to this special property, graphene
has wide application in ultrafast photonics. Moreover,
the optical response of graphene/graphene oxide layers
can be tuned electrically.[99][101] Saturable absorption in
graphene could occur at the Microwave and Terahertz
band, owing to its wideband optical absorption property.
The microwave saturable absorption in graphene demonstrates the possibility of graphene microwave and terahertz photonics devices, such as microwave saturable absorber, modulator, polarizer, microwave signal processing and broad-band wireless access networks.[102]

3.5.2 Nonlinear Kerr eect

Under more intensive laser illumination, graphene could


also possess a nonlinear phase shift due to the optical nonlinear Kerr eect. Based on a typical open and close aperture z-scan measurement, graphene possesses a giant nonlinear Kerr coecient of 107 cm2 W1 , almost nine orders of magnitude larger than that of bulk dielectrics.[103]
This suggests that graphene may be a powerful nonlinear
Kerr medium, with the possibility of observing a variety
of nonlinear eects, the most important of which is the
Although conrmed experimentally, the measurement is soliton.[104]

3.6

3 PROPERTIES

Excitonic

much larger than kBT can cause the electronic contribution to increase and dominate over the phonon contribuFirst-principle calculations with quasiparticle corrections tion at low temperatures. The ballistic thermal conducand many-body eects are performed to study the elec- tance of graphene is isotropic.[115][116]
tronic and optical properties of graphene-based materi- Potential for this high conductivity can be seen by conals. The approach is described as three stages.[105] With sidering graphite, a 3D version of graphene that has basal
GW calculation, the properties of graphene-based mate- plane thermal conductivity of over a 1000 Wm1 K1
rials are accurately investigated, including graphene,[106] (comparable to diamond). In graphite, the c-axis (out
graphene nanoribbons,[107] edge and surface functional- of plane) thermal conductivity is over a factor of ~100
ized armchair graphene nanoribbons,[108] hydrogen sat- smaller due to the weak binding forces between basal
urated armchair graphene nanoribbons,[109] Josephson planes as well as the larger lattice spacing.[117] In addition,
eect in graphene SNS junctions with single localized the ballistic thermal conductance of graphene is shown to
defect[110] and scaling properties in armchair graphene give the lower limit of the ballistic thermal conductances,
nanoribbons.[111]
per unit circumference, length of carbon nanotubes.[118]

3.7

Thermal

Graphene is an excellent thermal conductor. Its thermal conductivity was measured recently at room temperature and it is much higher than the value observed in all
the other carbon structures as carbon nanotubes, graphite
and diamond (> 5000 Wm1 K1 ). The ballistic thermal conductance of graphene is isotropic, i.e. same in
all directions. Graphite, the 3 D version of graphene,
shows a thermal conductivity about 5 times smaller (1000
Wm1 K1 ). The phenomenon is governed by the presence of elastic waves propagating in the graphene lattice,
called phonons. The study of thermal conductivity in
graphene may have important implications in graphenebased electronic devices. Even on a substrate, thermal
conductivity reaches 600 Wm1 K1 .[44]
3.7.1

Stability

Despite its 2-D nature, graphene has 3 acoustic phonon


modes. The two in-plane modes (LA, TA) have a linear dispersion relation, whereas the out of plane mode
(ZA) has a quadratic dispersion relation. Due to this,
the T 2 dependent thermal conductivity contribution of
the linear modes is dominated at low temperatures by
the T1.5 contribution of the out of plane mode.[118] Some
graphene phonon bands display negative Grneisen parameters.[119] At low temperatures (where most optical
modes with positive Grneisen parameters are still not
excited) the contribution from the negative Grneisen parameters will be dominant and thermal expansion coefcient (which is directly proportional to Grneisen parameters) negative. The lowest negative Grneisen parameters correspond to the lowest transversal acoustic ZA
modes. Phonon frequencies for such modes increase with
the in-plane lattice parameter since atoms in the layer
upon stretching will be less free to move in the z direction.
This is similar to the behavior of a string, which, when it
is stretched, will have vibrations of smaller amplitude and
higher frequency. This phenomenon, named membrane
eect, was predicted by Lifshitz in 1952.[120]

Ab initio calculations show that a graphene sheet is thermodynamically unstable if its size is less than about 20
nm (graphene is the least stable structure until about
6000 atoms) and becomes the most stable fullerene (as
3.8 Mechanical
within graphite) only for molecules larger than 24,000
atoms.[112]
The carboncarbon bond length in graphene is about
0.142 nanometers.[121] Graphene sheets stack to form
graphite with an interplanar spacing of 0.335 nm.
3.7.2 Conductivity
Graphene is highly impermeable and is highly elastic.[44]
The near-room temperature thermal conductivity of
graphene was measured to be between (4.840.44) Graphene is one of the strongest materials known with
a hypo103 to (5.300.48) 103 Wm1 K1 . These measure- a breaking strength over 100 times greater than[44]
thetical
steel
lm
of
the
same
(thin)
thickness,
with
ments, made by a non-contact optical technique, are in
a
Youngs
modulus
(stiness)
of
1
TPa
(150,000,000
excess of those measured for carbon nanotubes or dia[122]
The Nobel announcement illustrated this by saymonds. The isotopic composition, the ratio of 12 C to psi).
ing
that
a
1 square meter graphene hammock would sup13
C, has a signicant impact on thermal conductivity,
port
a
4
kg
cat but would weigh only as much as one of the
12
where isotopically pure C graphene has higher conduccats
whiskers,
at 0.77 mg (about 0.001% of the weight of
tivity than either a 50:50 isotope ratio or the naturally
[123]
2
1
m
of
paper).
[113]
It can be shown by using the
occurring 99:1 ratio.
WiedemannFranz law, that the thermal conduction is Flat graphene sheets are unstable with respect to scrolling,
phonon-dominated.[114] However, for a gated graphene i.e. bending into a cylindrical shape, which is its lowerstrip, an applied gate bias causing a Fermi energy shift energy state.[124]

9
The spring constant of suspended graphene sheets has
been measured using an atomic force microscope (AFM).
Graphene sheets, held together by van der Waals forces,
were suspended over SiO
2 cavities where an AFM tip was probed to test its mechanical properties. Its spring constant was in the range
15 N/m and the stiness was 0.5 TPa, which diers
from that of bulk graphite. These high values make
graphene very strong and rigid. These intrinsic properties could lead to using graphene for NEMS applications
such as pressure sensors and resonators.[125]
As is true of all materials, regions of graphene are subject to thermal and quantum uctuations in relative displacement. Although the amplitude of these uctuations
is bounded in 3D structures (even in the limit of innite
size), the MerminWagner theorem shows that the amplitude of long-wavelength uctuations grows logarithmically with the scale of a 2D structure, and would therefore
be unbounded in structures of innite size. Local deformation and elastic strain are negligibly aected by this
long-range divergence in relative displacement. It is believed that a suciently large 2D structure, in the absence
of applied lateral tension, will bend and crumple to form a
uctuating 3D structure. Researchers have observed ripples in suspended layers of graphene,[32] and it has been
proposed that the ripples are caused by thermal uctuations in the material. As a consequence of these dynamical deformations, it is debatable whether graphene is truly
a 2D structure.[37][50][51][126]
3.8.1

Cracking

In 2014, researchers from Rice University and the


Georgia Institute of Technology have discovered that although graphene is possibly the strongest material produced today, it is also as brittle as ordinary ceramic.
Graphene cracks like a glass window, unlike steel which
has strong crack resistance. Graphene is 10 times more
prone to cracking than steel.[127]

3.9

Spin transport

Additional plateaus of the Hall conductivity at xy =


e2 /h with = 0, 1, 4 are observed.[86] Also, the
observation of a plateau at = 3 [87] and the fractional
quantum Hall eect at = 1/3 were reported.[87][88]
These observations with = 0, 1, 3, 4 indicate that
the four-fold degeneracy (two valley and two spin degrees
of freedom) of the Landau energy levels is partially or
completely lifted. One hypothesis is that the magnetic
catalysis of symmetry breaking is responsible for lifting
the degeneracy.

4 Forms
4.1 Nanostripes
Graphene nanoribbons (nanostripes in the zig-zag
orientation), at low temperatures, show spin-polarized
metallic edge currents, which also suggests applications
in the new eld of spintronics. (In the armchair orientation, the edges behave like semiconductors.[60] )

4.2 Oxide
Further information: Graphite oxide
Using paper-making techniques on dispersed, oxidized
and chemically processed graphite in water, the monolayer akes form a single sheet and create strong bonds.
These sheets, called graphene oxide paper have a measured tensile modulus of 32 GPa.[131] The chemical property of graphite oxide is related to the functional groups
attached to graphene sheets. These can change the polymerization pathway and similar chemical processes.[132]
Graphene oxide akes in polymers display enhanced
photo-conducting properties.[133] Graphene is normally
hydrophobic and impermeable to all gases and liquids
(vacuum-tight). However when formed into graphene
oxide-based capillary membrane, both liquid water and
water vapor ow through as quickly as if the membrane
was not present.[134]

Graphene is claimed to be an ideal material for


spintronics due to its small spin-orbit interaction and
4.3
the near absence of nuclear magnetic moments in carbon (as well as a weak hyperne interaction). Electrical spin current injection and detection has been demonstrated up to room temperature.[128][129][130] Spin coherence length above 1 micrometre at room temperature was
observed,[128] and control of the spin current polarity with
an electrical gate was observed at low temperature.[129]
3.9.1

Strong magnetic elds

Chemical modication

Photograph of single-layer graphene oxide undergoing high temperature chemical treatment, resulting in sheet folding and loss of
carboxylic functionality, or through room temperature carbodiimide treatment, collapsing into star-like clusters.

Graphenes quantum Hall eect in magnetic elds above


10 Teslas or so reveals additional interesting features. Soluble fragments of graphene can be prepared in

10

FORMS

the laboratory[135] through chemical modication of


graphite. First, microcrystalline graphite is treated with
an acidic mixture of sulfuric acid and nitric acid. A
series of oxidation and exfoliation steps produce small
graphene plates with carboxyl groups at their edges.
These are converted to acid chloride groups by treatment with thionyl chloride; next, they are converted
to the corresponding graphene amide via treatment
with octadecylamine. The resulting material (circular
graphene layers of 5.3 angstrom thickness) is soluble in
tetrahydrofuran, tetrachloromethane and dichloroethane.

Full hydrogenation from both sides of graphene sheet results in graphane, but partial hydrogenation leads to hydrogenated graphene.[138] Similarly, both-side uorination of graphene (or chemical and mechanical exfoliation
of graphite uoride) leads to uorographene (graphene
uoride),[139] while partial uorination (generally halogenation) provides uorinated (halogenated) graphene.

Reuxing single-layer graphene oxide (SLGO) in solvents


leads to size reduction and folding of individual sheets as
well as loss of carboxylic group functionality, by up to
20%, indicating thermal instabilities of SLGO sheets dependent on their preparation methodology. When using
thionyl chloride, acyl chloride groups result, which can
then form aliphatic and aromatic amides with a reactivity
conversion of around 7080%.

Graphene can be a huge ligand to coordinate metals


and metal ions by introducing functional groups. Structures of graphene ligands are similar to e.g. metalporphyrin complex, metal-phthalocyanine complex, and
metal-phenanthroline complex. Copper and nickel ions
has been coordinated with graphene ligands.[140][141]

4.4 Ligand/ Complex

4.5 Bilayer
Main article: Bilayer graphene

Boehm titration results for various chemical reactions of singlelayer graphene oxide, which reveal reactivity of the carboxylic
groups and the resultant stability of the SLGO sheets after treatment.

Bilayer graphene displays the anomalous quantum Hall


eect, a tunable band gap[142] and potential for excitonic
condensation[143] making it a promising candidate for
optoelectronic and nanoelectronic applications. Bilayer
graphene typically can be found either in twisted congurations where the two layers are rotated relative to each
other or graphitic Bernal stacked congurations where
half the atoms in one layer lie atop half the atoms in the
other. Stacking order and orientation govern the optical
and electronic properties of bilayer graphene.

One way to synthesize bilayer graphene is via chemical


vapor deposition, which can produce large bilayer realmost exclusively conform to a Bernal stack
Hydrazine reux is commonly used for reducing SLGO gions that [144]
geometry.
to SLG(R), but titrations show that only around 2030%
of the carboxylic groups are lost, leaving a signicant
number available for chemical attachment. Analysis of
SLG(R) generated by this route reveals that the system 4.6 Fiber
is unstable and using a room temperature stirring with
HCl (< 1.0 M) leads to around 60% loss of COOH In 2011, Xinming Li and Hongwei Zhu from Tsinghua
functionality. Room temperature treatment of SLGO University reported a novel yet simple approach to fabwith carbodiimides leads to the collapse of the individ- ricate graphene bers from chemical vapor deposition
[145]
The method was scalable and
ual sheets into star-like clusters that exhibited poor sub- grown graphene lms.
sequent reactivity with amines (ca. 35% conversion of controllable, delivering tunable morphology and pore
the intermediate to the nal amide).[136] It is apparent that structure by controlling the evaporation of solvents with
conventional chemical treatment of carboxylic groups suitable surface tension. Flexible all-solid-state supercaon SLGO generates morphological changes of individ- pacitors based on this graphene bers were demonstrated
[146]
ual sheets that leads to a reduction in chemical reactivity, in 2013.
which may potentially limit their use in composite synthesis. Therefore, chemical reactions types have been explored. SLGO has also been grafted with polyallylamine, 4.7 3D
cross-linked through epoxy groups. When ltered into
graphene oxide paper, these composites exhibit increased In 2013, a three-dimensional honeycomb of hexagonally
stiness and strength relative to unmodied graphene ox- arranged carbon was termed 3D graphene, although selfide paper.[137]
supporting 3D graphene has not yet been produced.[147]

5.1

4.8

Exfoliation

Reinforced

11
must then be bonded to some substrate to retain its 2d
shape.[15] Other techniques have also been developed.

Graphene reinforced with embedded carbon nanotube reinforcing bars (rebar) is easier to manipulate, while improving the electrical and mechanical qualities of both 5.1 Exfoliation
materials.[148][149]
lowest
Functionalized single- or multiwalled carbon nanotubes As of 2014 exfoliation produced graphene with the
[44]
number
of
defects
and
highest
electron
mobility.
are spin-coated on copper foils and then heated and
cooled, using the nanotubes themselves as the carbon
source. Under heating, the functional carbon groups
decompose into graphene, while the nanotubes partially split and form in-plane covalent bonds with the
graphene, adding strength. stacking domains add
more strength. The nanotubes can overlap, making the
material a better conductor than standard CVD-grown
graphene. The nanotubes eectively bridge the grain
boundaries found in conventional graphene. The technique eliminates the traces of substrate on which laterseparated sheets were deposited using epitaxy.[148]

5.1.1 Adhesive tape


Cleavage is also known as exfoliation. Achieving single
layers typically requires multiple exfoliation steps, each
producing a slice with fewer layers, until only one remains. Geim and Novosolev used adhesive tape to split
their graphene.

After exfoliation the akes are deposited on a silicon


wafer using dry deposition. Crystallites larger than 1
Stacks of a few layers, have been proposed as a mm and visible to the naked eye can be obtained with
cost-eective and physically exible replacement for the technique. It is often referred to as a "scotch tape"
indium tin oxide (ITO) used in displays and photovoltaic or drawing method. The latter name appeared because
the dry deposition resembles drawing with a piece of
cells.[148]
graphite.[150]

Production techniques

Isolated 2D crystals cannot be grown via chemical synthesis beyond small sizes even in principle, because the rapid
growth of phonon density with increasing lateral size
forces 2D crystallites to bend into the third dimension.[15]
However, other routes to 2d materials exist:
Fundamental forces place seemingly insurmountable barriers in the way of creating [2D
crystals]... The nascent 2D crystallites try to
minimize their surface energy and inevitably
morph into one of the rich variety of stable 3D
structures that occur in soot.
But there is a way around the problem.
Interactions with 3D structures stabilize 2D
crystals during growth. So one can make 2D
crystals sandwiched between or placed on top
of the atomic planes of a bulk crystal. In
that respect, graphene already exists within
graphite... One can then hope to fool Nature
and extract single-atom-thick crystallites at a
low enough temperature that they remain in
the quenched state prescribed by the original
higher-temperature 3D growth.[150]
The two basic approaches to producing graphene are to
cleave multi-layer graphite into single layers or to grow it
epitaxially by depositing one layer of carbon onto another
material. The former was developed rst, using adhesive
tape to peel monolayers away. In either case, the graphite

5.1.2 Wedge-based mechanical exfoliation


Another controlled technique to produce few layers of
graphene uses a wedge type of tool[151] to address difculties of the adhesive tape method. In this method, a
sharp single-crystal diamond wedge penetrates onto the
graphite source to exfoliate layers. This method uses
highly ordered pyrolytic graphite (HOPG) as the starting
material. The experiments were supported by molecular
dynamic simulations.[152]

5.1.3 Reduction of graphite oxide


Graphite oxide reduction was probably the rst method
of graphene synthesis. P. Boehm reported producing
monolayer akes of reduced graphene oxide in 1962.[153]
Geim acknowledged Boehms contribution.[154] Rapid
heating of graphite oxide and exfoliation yields highly
dispersed carbon powder with a few percent of graphene
akes. Reduction of graphite oxide monolayer lms, e.g.
by hydrazine with annealing in argon/hydrogen, was reported to yield graphene lms. However, the quality is
lower compared to scotch-tape graphene, due to incomplete removal of functional groups. Furthermore, the
oxidation protocol introduces permanent defects due to
over-oxidation. The oxidation protocol was enhanced to
yield graphene oxide with an almost intact carbon framework that allows ecient removal of functional groups.
The measured charge carrier mobility exceeded 1,000
centimetres (393.70 in)/Vs.[155] Spectroscopic analysis of
reduced graphene oxide has been conducted.[156][157]

12
5.1.4

5 PRODUCTION TECHNIQUES
Shearing

In 2014 defect-free, unoxidized graphene-containing liquids were made from graphite using mixers that produce local shear rates greater than 10. Commercial
graphene products using the output were announced. The
method was claimed to be applicable to boron nitride,
Molybdenum disulde and other layered crystals.[158][159]

of isolated graphene.[165][166] An example of weakly coupled epitaxial graphene is the one grown on SiC.[39]
Graphene monolayers grown on silicon carbide and
iridium are weakly coupled to these substrates (how
weakly remains debated) and the graphenesubstrate interaction can be further passivated.[16]
5.2.1 Silicon carbide

5.1.5

Sonication

Main article: Carbide-derived Carbon

Applying a layer of graphite oxide lm to a DVD and


burning it in a DVD writer produced a thin graphene lm
with high electrical conductivity (1738 siemens per meter) and specic surface area (1520 square meters per
gram) that was highly resistant and malleable.[160]

Heating silicon carbide (SiC) to high temperatures


(>1100 C) under low pressures (~106 torr) reduces it to
graphene.[167] This process produces epitaxial graphene
with dimensions dependent upon the size of the wafer.
The face of the SiC used for graphene formation, siliconor carbon-terminated, highly inuences the thickness,
Solvent-aided Dispersing graphite in a proper liquid mobility and carrier density of the resulting graphene.
medium can produce graphene by sonication. Graphene Graphenes electronic band-structure (so-called
is separated from graphite by centrifugation,[161] produc- Dirac cone structure) was rst visualized in this
ing graphene concentrations initially up to 0.01 mg/ml material.[168][169][170] Weak anti-localization is observed
in N-methylpyrrolidone (NMP) and later to 2.1 mg/ml in this material, but not in exfoliated graphene produced
in NMP,.[162] Using a suitable ionic liquid as the dis- by the drawing method.[171] Large, temperaturepersing liquid medium produced concentrations of 5.33 independent mobilities approach those in exfoliated
mg/ml.[163] Graphene concentration produced by this graphene placed on silicon oxide, but lower than momethod is very low, because nothing prevents the sheets bilities in suspended graphene produced by the drawing
from restacking due to van der Waals forces. The maxi- method. Even without transfer, graphene on SiC exhibits
mum concentrations achieved are the points at which the massless Dirac fermions.[79][80][81][82][83][84][172]
van der Waals forces overcome the interactive forces beThe weak van der Waals force that provides the cotween the graphene sheets and the solvent molecules.
hesion of multilayer graphene stacks does not always
aect the electronic properties of the individual laySolvent/surfactant-aided Adding a surfactant to a sol- ers. That is, while the electronic properties of cergraphenes are identical to that
vent prior to sonication prevents restacking by adsorb- tain multilayered epitaxial
[173]
of
a
single
layer,
in
other
cases the properties are
ing to the graphenes surface. This produces a higher
[168][169]
aected,
as
they
are
in
bulk graphite. This efgraphene concentration, but removing the surfactant refect
is
well
understood
theoretically
and is related to the
quires chemical treatments.
symmetry of the interlayer interactions.[173]
Immiscible liquids Sonicating graphite at the interface
of two immiscible liquids, most notably heptane and water, producing macro-scale graphene lms. The graphene
sheets are adsorbed to the high energy interface between
the heptane and the water, where they are kept from
restacking. The graphene remains at the interface even
when exposed to force in excess of 300,000 g. The solvents may then be evaporated. The sheets are up to ~95%
transparent and conductive.[164]

5.2

Epitaxy

Epitaxial graphene on SiC can be patterned using standard microelectronics methods. A band gap can be created and tuned by laser irradiation.[174]
5.2.2 Metal substrates
The atomic structure of a metal substrate can seed the
growth of graphene.
Ruthenium Graphene grown on ruthenium does not
typically produce uniform layer thickness. Bonding between the bottom graphene layer and the substrate may
aect layer properties.[175]

Epitaxy refers to the deposition of a crystalline overlayer


on a crystalline substrate, where there is registry between
the two. In some cases epitaxial graphene layers are cou- Iridium Graphene grown on iridium is very weakly
pled to surfaces weakly enough (by Van der Waals forces) bonded, uniform in thickness and can be highly ordered.
to retain the two dimensional electronic band structure As on many other substrates, graphene on iridium is

5.3

Nanotube slicing

13

slightly rippled. Due to the long-range order of these gle layer growth is also due to the low concentration of
ripples, minigaps in the electronic band-structure (Dirac carbon in methane. Larger hydrocarbons such as ethane
cone) become visible.[176]
and propane produce bilayer coatings.[184] Atmospheric
pressure CVD growth produces multilayer graphene on
copper (similar to nickel).[185] Ballistic transport has also
Nickel High-quality sheets of few-layer graphene ex- been observed in the graphene grown on copper.[186] The
ceeding 1 cm2 (0.2 sq in) in area have been synthesized process is surface-based rather than relying on absorption
via chemical vapor deposition on thin nickel lms using into the metal and then diusion of carbon into graphene
multiple techniques.
layers on the surface.[187]
The growth of graphene on nickel lms through chemical
vapor deposition occurs in a few steps. First the thin
nickel lm is exposed to Argon gas at 900-1000 degrees
Celsius. Methane is then mixed into the gas, and the carbon from the methane is absorbed into the nickel lm.
The nickel-carbon solution is then cooled down in argon
gas. During the cooling process the carbon diuses out
of the nickel to form graphene lms.[79][177][178][179]
Another used temperatures compatible with conventional
CMOS processing, using a nickel-based alloy with gold as
catalyst.[180] This process dissolves carbon atoms inside
a transition metal melt at a certain temperature and then
precipitates the dissolved carbon at lower temperatures as
single layer graphene (SLG).
The metal is rst melted in contact with a carbon source,
possibly a graphite crucible inside which the melt is carried out or graphite powder/chunks that are placed in the
melt. Keeping the melt in contact with the carbon at a
specic temperature dissolves the carbon atoms, saturating the melt based on the metal-carbon binary phase diagram. Lowering the temperature decreases carbons solubility and the excess carbon precipitates atop the melt.
The oating layer can be either skimmed or frozen for
later removal. Using dierent morphology, including
thick graphite, few layer graphene (FLG) and SLG were
observed on metal substrate. Raman spectroscopy proved
that SLG had grown on nickel substrate. The SLG Raman
spectrum featured no D and D band, indicating its pristine nature. Since nickel is not Raman active, direct Raman spectroscopy of graphene layers on top of the nickel
is achievable.[181]
Another approach covered a sheet of silicon dioxide glass
(the substrate) on one side with a nickel lm. Graphene
deposited via chemical vapor deposition formed into layers on both sides of the lm, one on the exposed top side,
and one on the underside, sandwiched between nickel and
glass. Peeling the nickel and the top layer of graphene left
intervening layer of graphene behind on the glass. While
the top graphene layer could be harvested from the foil as
in earlier methods, the bottom layer was already in place
on the glass. The quality and purity of the attached layer
was not assessed.[182]

Copper An improvement of this technique employs


copper foil; at very low pressure, the growth of graphene
automatically stops after a single graphene layer forms.
Arbitrarily large lms can be created.[178][183] The sin-

5.2.3 Sodium ethoxide pyrolysis


Gram-quantities of graphene were produced by the reduction of ethanol by sodium metal, followed by pyrolysis
of the ethoxide product and washing with water to remove
sodium salts.[188]
5.2.4 Silicon/germanium/hydrogen
A normal silicon wafer coated with a layer of germanium
(Ge) dipped in dilute hydrouoric acid strips the naturally
forming germanium oxide groups, creating hydrogenterminated germanium. Chemical vapor deposition deposits a layer of graphene on top. The graphene can be
peeled from the wafer using a dry process and is then
ready for use. The wafer can be reused. The graphene
is wrinkle-free, high quality and low in defects.[189][190]
5.2.5 Roll-to-roll
In 2014 a two-step roll-to-roll manufacturing process was
announced that allows scalable graphene production. The
rst roll-to-roll step produces the graphene via chemical
vapor deposition. The second step binds the graphene to
a substrate.[191][192]

5.3 Nanotube slicing


Graphene can be created by cutting open carbon nanotubes.[193] In one such method multi-walled carbon nanotubes are cut open in solution by action of potassium
permanganate and sulfuric acid.[194] In another method
graphene nanoribbons were produced by plasma etching
of nanotubes partly embedded in a polymer lm.[195]

5.4 Carbon dioxide reduction


A highly exothermic reaction combusts magnesium in
an oxidation-reduction reaction with carbon dioxide,
producing a variety of carbon nanoparticles including
graphene and fullerenes. The carbon dioxide reactant
may be either solid (dry-ice) or gaseous. The products of
this reaction are carbon and magnesium oxide. US patent
8377408 was issued for this process.[196]

14

5.5

Spin coating

In 2014, carbon nanotube-reinforced graphene was made


via spin coating and annealing functionalized carbon nanotubes. The resulting material was stronger, exible and
more conductive than conventional graphene.[148]

5.6

Supersonic spray

Supersonic acceleration of droplets through a Laval


nozzle was used to deposit small droplets of reduced
graphene-oxide in suspension on a substrate. The droplets
disperse evenly, evaporate rapidly and display reduced
ake aggregations. In addition, the topological defects
(Stone-Wales defect and C
2 vacancies) originally in the akes disappeared. The result was a higher quality graphene layer. The energy of
the impact stretches the graphene and rearranges its carbon atoms into awless hexagonal graphene with no need
for post-treatment.[197][198]

Applications

Main article: Potential applications of graphene


While as of 2014, graphene is not used in commercial
applications, many have been proposed and/or are under
development, in areas including electronics, biological
engineering, ltration, lightweight/strong composite materials, photovoltaics and energy storage.[199] Graphene
is produced as a powder and as a dispersion in a polymer matrix, or adhesive, elastomer, oil and aqueous and
non-aqueous solutions. The dispersion is stated by the
manufacturer to be suitable for advanced composites,[200]
paints and coatings, lubricants, oils and functional uids, capacitors and batteries, thermal management applications, display materials and packaging, inks and 3Dprinters materials, and barriers and lms.[201]

See also
Bismuthide
Borophene
Cadmium arsenide
Exfoliated graphite nano-platelets
Germanene
Graphane
Graphyne
Metal-organic framework

REFERENCES

Molybdenum disulde
Molybdenum diselenide
Nanoribbon
Silicene
Solid-state engine
Stanene
Two-dimensional polymers

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24

10

10

External links

Manchesters Revolutionary 2D Material at The


University of Manchester
Graphene at The Periodic Table of Videos (University of Nottingham)
Graphene portal with daily news and resources
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Graphene: Patent surge reveals global race
(PDF) 'Engineering Controls for Nano-scale
Graphene Platelets During Manufacturing and
Handling Processes

EXTERNAL LINKS

25

11
11.1

Text and image sources, contributors, and licenses


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Graphene Source: http://en.wikipedia.org/wiki/Graphene?oldid=634996410 Contributors: NathanBeach, Bryan Derksen, XJaM, David


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Stepa, Edgar181, Gilliam, Hmains, Chris the speller, TimBentley, JDowning, Thumperward, Rickyjames, Androsyn, OrphanBot, Zirconscot, Cybercobra, Daqu, Rich.lewis, Bezapt, Angela26, Dmh, John, Disavian, JorisvS, Mgiganteus1, NNemec, Pedantic of Purley,
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Wikievil666, The Thing That Should Not Be, Sharkyx, Akiry, Leadwind, Rprpr, Lessogg, Diderots dreams, Alexbot, Jkoepke, Tomeasy,
PixelBot, Sun Creator, Aurelius173, Arjayay, Arkatakor, CowboySpartan, Nuinu, SoxBot III, Wnt, DumZiBoT, XLinkBot, Carbophiliac,
Nepenthes, Jprw, Frood, MystBot, Farthur2, Ryansdowdy, Sfbarot, Addbot, Mortense, Jasperyate, Cheaptubes, DOI bot, Miskaton, Jack
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ChrisGualtieri, YFdyh-bot, Gairderek, Andrewrao8, Dexbot, Mogism, JZNIOSH, Makecat-bot, Graphenebiz, Cerabot, Graphenemaster, TwoTwoHello, Calvinatlan, GuNz 53, Danielj27052705, Marcgc07966, Journals28, MCSortiz, Migueldiascosta, SylvainLi, Reatlas,
TextMech, Clerkerina, Eyesnore, BDyatkin, HCK12345, NavalCrab, Alex M Santos, Kayvanraee, Idjoku, DavidLeighEllis, MaterialsEngineer, CensoredScribe, Dfamos1, Malir84, Kawasakin, Dahankster101, Leoesb1032, Themusicman123456, Tehben1, ( ^ ^), Ibnrasheed,
Citytownhome, Green1jeet, Sam Sailor, Mahan mohammad, Jmmbishop, Olivialopez789, BenPRobinson, Anrnusna, Matsci2, Yshaoya,
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11.2

Images

File:Buckminsterfullerene-perspective-3D-balls.png
Source:
http://upload.wikimedia.org/wikipedia/commons/0/0f/
Buckminsterfullerene-perspective-3D-balls.png License: Public domain Contributors: ? Original artist: ?
File:Cnt_gnrarm_v3.gif Source: http://upload.wikimedia.org/wikipedia/commons/f/fb/Cnt_gnrarm_v3.gif License: CC-BY-3.0 Contributors: CNTBands simulator on www.nanoHUB.org. Link:http://nanohub.org/tools/cntbands-ext/ Original artist: Saumitra R Mehrotra
& Gerhard Klimeck
File:Cnt_zz_v3.gif Source: http://upload.wikimedia.org/wikipedia/commons/3/35/Cnt_zz_v3.gif License: CC-BY-3.0 Contributors:
CNTBands simulator on www.nanoHUB.org. Link:https://nanohub.org/tools/cntbands-ext/ Original artist: Saumitra R Mehrotra & Gerhard Klimeck
File:Commons-logo.svg Source: http://upload.wikimedia.org/wikipedia/en/4/4a/Commons-logo.svg License: ? Contributors: ? Original
artist: ?
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Project. Original artist:

26

11

TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

The people from the Tango! project. And according to the meta-data in the le, specically: Andreas Nilsson, and Jakub Steiner (although
minimally).
File:Ethanol-3D-balls.png Source: http://upload.wikimedia.org/wikipedia/commons/b/b0/Ethanol-3D-balls.png License: Public domain
Contributors: ? Original artist: ?
File:Folder_Hexagonal_Icon.svg Source: http://upload.wikimedia.org/wikipedia/en/4/48/Folder_Hexagonal_Icon.svg License: ? Contributors: ? Original artist: ?
File:Graphen.jpg Source: http://upload.wikimedia.org/wikipedia/commons/9/9e/Graphen.jpg License: CC-BY-SA-3.0 Contributors:
Own work Original artist: AlexanderAlUS
File:Graphene_chemistry.jpg Source: http://upload.wikimedia.org/wikipedia/en/5/5f/Graphene_chemistry.jpg License: CC-BY-SA3.0 Contributors: ? Original artist: ?
File:Graphene_visible.jpg Source: http://upload.wikimedia.org/wikipedia/en/1/19/Graphene_visible.jpg License: PD Contributors: ?
Original artist: ?
File:Nitrous-oxide-3D-balls.png Source: http://upload.wikimedia.org/wikipedia/commons/9/93/Nitrous-oxide-3D-balls.png License:
Public domain Contributors: Own work Original artist: Ben Mills
File:Nobel_Prize_2010-Press_Conference_KVA-DSC_8009.jpg Source:
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Nobel_Prize_2010-Press_Conference_KVA-DSC_8009.jpg License: CC-BY-SA-3.0 Contributors: Own work Original artist: Holger
Motzkau
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File:Portal-puzzle.svg Source: http://upload.wikimedia.org/wikipedia/en/f/fd/Portal-puzzle.svg License: ? Contributors: ? Original artist:
?
File:Slgo.jpg Source: http://upload.wikimedia.org/wikipedia/en/7/70/Slgo.jpg License: CC-BY-SA-3.0 Contributors:
I (Raywhitby (talk)) created this work entirely by myself to be used by Elsevier B.V. Original artist:
Raywhitby (talk)
File:Symbol_book_class2.svg Source: http://upload.wikimedia.org/wikipedia/commons/8/89/Symbol_book_class2.svg License: CCBY-SA-2.5 Contributors: Mad by Lokal_Prol by combining: Original artist: Lokal_Prol
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Original artist: ?

11.3

Content license

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