Graphene (/'grf.i?

n/)[1][2] is an allotrope of carbon in the form of a two-dimens

ional, atomic-scale, hexagonal lattice in which one atom forms each vertex. It i
s the basic structural element of other allotropes, including graphite, charcoal
, carbon nanotubes and fullerenes. It can also be considered as an indefinitely
large aromatic molecule, the ultimate case of the family of flat polycyclic arom
atic hydrocarbons.
File:Graphene and Dirac Cones.ogv
Graphene and its band structure and Dirac Cones, effect of a grid on doping
Graphene has many properties. It is about 100 times stronger than the strongest
steel. It conducts heat and electricity very efficiently and is nearly transpare
nt.[3] Graphene also shows a large and nonlinear diamagnetism,[4] even greater t
han graphite, and can be levitated by Nd-Fe-B magnets. Researchers have identifi
ed the bipolar transistor effect, ballistic transport of charges and large quant
um oscillations in the material.[5]
Scientists have theorized about graphene for years. It has likely been unknowing
ly produced in small quantities for centuries, through the use of pencils and ot
her similar applications of graphite. It was originally observed in electron mic
roscopes in 1962, but only studied while supported on metal surfaces.[6] The mat
erial was later rediscovered, isolated and characterized in 2004 by Andre Geim a
nd Konstantin Novoselov at the University of Manchester.[7][8] Research was info
rmed by existing theoretical descriptions of its composition, structure and prop
erties.[9] High-quality graphene proved to be surprisingly easy to isolate, maki
ng more research possible. This work resulted in the two winning the Nobel Prize
in Physics in 2010 "for groundbreaking experiments regarding the two-dimensiona
l material graphene."[10]
The global market for graphene is reported to have reached $9 million by 2012 wi
th most sales in the semiconductor, electronics, battery energy and composites i
ndustries.
"Graphene" is a combination of "graphite" and the suffix -ene, named by Hanns-Pe
ter Boehm,[12] who described single-layer carbon foils in 1962.[6]
The term graphene first appeared in 1987[13] to describe single sheets of graphi
te as a constituent of graphite intercalation compounds (GICs); conceptually a G
IC is a crystalline salt of the intercalant and graphene. The term was also used
in early descriptions of carbon nanotubes,[14] as well as for epitaxial graphen
e[15] and polycyclic aromatic hydrocarbons.[16] Graphene can be considered an "i
nfinite alternant" (only six-member carbon ring) polycyclic aromatic hydrocarbon
(PAH).[17]
The IUPAC compendium of technology states: "previously, descriptions such as gra
phite layers, carbon layers, or carbon sheets have been used for the term graphe
ne... it is incorrect to use for a single layer a term which includes the term g
raphite, which would imply a three-dimensional structure. The term graphene shou
ld be used only when the reactions, structural relations or other properties of
individual layers are discussed."[18]
Geim defined "isolated or free-standing graphene" as "graphene is a single atomi
c plane of graphite, which
and this is essential
is sufficiently isolated from i
ts environment to be considered free-standing."[19] This definition is narrower
than the IUPAC definition and refers to cloven, transferred, and suspended graph
ene.[citation needed] Other forms of graphene, such as graphene grown on various
metals, can become free-standing if, for example, suspended or transferred to s
ilicon dioxide (SiO
2) or silicon carbide.
In 1859 Benjamin Collins Brodie was aware of the highly lamellar structure of th
ermally reduced graphite oxide.[21][22]

The structure of graphite was solved in 1916[23] by the related method of powder
diffraction.[24] It was studied in detail by V. Kohlschtter and P. Haenni in 191
8, who also described the properties of graphite oxide paper.[25] Its structure
was determined from single-crystal diffraction in 1924.[26]
The theory of graphene was first 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 first pointed out by Gordon Walter Semenoff and Davi
d P. DiVincenzo and Eugene J. Mele.[27] Semenoff emphasized the occurrence in a
magnetic field of an electronic Landau level precisely at the Dirac point. This
level is responsible for the anomalous integer quantum Hall effect.[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 e
lectron microscopy.[32] Before 2004 intercalated graphite compounds were studied
under a transmission electron microscope (TEM). Researchers occasionally observ
ed thin graphitic flakes ("few-layer graphene") and possibly even individual lay
ers. 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. Howe
ver, there is significant charge transfer from the substrate to the epitaxial gr
aphene, and, in some cases, hybridization between the d-orbitals of the substrat
e atoms and p orbitals of graphene, which significantly alters the electronic st
ructure of epitaxial graphene.
Single layers of graphite were also observed by transmission electron microscopy
within bulk materials, in particular inside soot obtained by chemical exfoliati
on. Efforts to make thin films of graphite by mechanical exfoliation started in
1990,[36] but nothing thinner than 50 to 100 layers was produced before 2004.
Initial attempts to make atomically thin graphitic films employed exfoliation te
chniques similar to the drawing method. Multilayer samples down to 10 nm in thic
kness were obtained.[37] Old papers were unearthed[33] in which researchers trie
d to isolate graphene starting with intercalated compounds. These papers reporte
d the observation of very thin graphitic fragments (possibly monolayers) by tran
smission electron microscopy. Neither of the earlier observations was sufficient
to "spark the graphene gold rush," which awaited macroscopic samples of extract
ed atomic planes.
One of the very first patents pertaining to the production of graphene was filed
in October 2002 and granted in 2006 (US Pat. 7071258).[38] Titled, "Nano-scaled
Graphene Plates," this patent detailed one of the very first large scale graphe
ne production processes. Two years later, in 2004 Andre Geim and Kostya Novoselo
v at The University of Manchester extracted single-atom-thick crystallites from
bulk graphite.[7] 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.[39] The SiO
2 electrically isolated the graphene and weakly interacted with it, providing ne
arly 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 gra
phene over a wide range. They may not have been the first to use this technique U
S 6667100, filed in 2002, describes how to process commercially available flexib
le expanded graphite to achieve a graphite thickness of 0.00001" (one hundred-th
ousandth) of an inch. The key to success was high-throughput visual recognition
of graphene on a properly chosen substrate, which provides a small but noticeabl
e optical contrast.

The cleavage technique led directly to the first observation of the anomalous qu
antum Hall effect in graphene,[28][30] which provided direct evidence of graphen
e's theoretically predicted Berry's phase of massless Dirac fermions. The effect
was reported by Geim's group and by Philip Kim and Yuanbo Zhang, whose papers[2
8][30] appeared in the same issue of Nature in 2005. Before these experiments ot
her researchers looked for the quantum Hall effect[40] and Dirac fermions[41] in
bulk graphite.
Even though graphene on nickel and on silicon carbide have both existed in the l
aboratory for decades, graphene mechanically exfoliated on SiO
2 provided the first proof of the Dirac fermion nature of electrons.[citation ne
eded]
Geim and Novoselov received several awards for their pioneering research on grap
hene, notably the 2010 Nobel Prize in Physics.[42]
Recently, several important techniques have been developed to prepare nanostruct
ured graphene, e.g., Graphene Quantum Dots (GQDs); these techniques mainly inclu
de electron beam lithography, chemical synthesis, electrochemical preparation, g
raphene oxide (GO) reduction, C60 catalytic transformation, the microwave assist
ed hydrothermal method (MAH),[43][44] the Soft-Template method,[45] the hydrothe
rmal method,[46][47][48] and the ultrasonic exfoliation method.[49]
In 2014 National Graphene Institute, a 60m Graphene Engineering Innovation Centre
(GEIC), was announced to support applied research and development in partnershi
p with other research organizations and industry.[50]
In North East England two commercial manufacturers, Applied Graphene Materials[5
1] and Thomas Swan Limited[52] (with Trinity College, Dublin researchers),[53] h
ave begun manufacturing. In East Anglia, another manufacturer, FGV Cambridge Nan
osystems,[54][55][56] is operating a large scale graphene powder production faci
lity.
In 2016, Brown University introduced a method for 'crumpling' graphene, adding w
rinkles to the material on a nanoscale. This was achieved by depositing layers o
f graphene oxide onto a shrink film, then shrunken, with the film dissolved befo
re being shrunken again on another sheet of film. The crumpled graphene became s
uperhydrophobic, and, when used as a battery electrode, the material was shown t
o have as much of a 400% increase in electrochemical current density.[57][58]