Graphene

Graphene (/ˈɡræfiːn/)^[1][2] is an allotrope of carbon in the form of a single layer of atoms in a two-dimensional hexagonal lattice in which one atom forms each vertex. It is 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 aromatic hydrocarbons.

Graphene has a special set of properties which set it apart from other allotropes of carbon. In proportion to its thickness, it is about 100 times stronger than the strongest steel, yet its density is dramatically lower than any other steel, with a surfacic mass of 0.763mg per square meter. It conducts heat and electricity very efficiently and is nearly transparent.^[3] Graphene also shows a large and nonlinear diamagnetism,^[4] even greater than graphite, and can be levitated by Nd-Fe-B magnets. Researchers have identified the bipolar transistor effect, ballistic transport of charges and large quantum oscillations in the material.^[5]

Scientists have theorized about graphene for decades, it has likely been unknowingly produced in small quantities for centuries, through the use of pencils and other similar applications of graphite. It was originally observed in electron microscopes in 1962, but only studied while supported on metal surfaces;^[6] the material was later rediscovered, isolated and characterized in 2004 by Andre Geim and Konstantin Novoselov at the University of Manchester.^[7][8] Research was informed by existing theoretical descriptions of its composition, structure and properties.^[9] High-quality graphene proved to be surprisingly easy to isolate, making more research possible; this work resulted in the two winning the Nobel Prize in Physics in 2010 "for groundbreaking experiments regarding the two-dimensional material graphene."^[10]

The global market for graphene is reported to have reached $9 million by 2012, with most of the demand from research and development in semiconductor, electronics, battery energy and composites.^[11]

Definition[edit]

"Graphene" is a combination of "graphite" and the suffix -ene, named by Hanns-Peter Boehm,^[12] who described single-layer carbon foils in 1962.^[6]

The term graphene first appeared in 1987^[13] 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,^[14] as well as for epitaxial graphene^[15] and polycyclic aromatic hydrocarbons.^[16] Graphene can be considered an "infinite alternant" (only six-member carbon ring) polycyclic aromatic hydrocarbon (PAH).^[17]

The IUPAC compendium of technology states: "previously, descriptions such as graphite layers, carbon layers, or carbon sheets have been used for the term graphene... it is incorrect to use for a single layer a term which includes the term graphite, which would imply a three-dimensional structure. The term graphene should 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 atomic plane of graphite, which – and this is essential – is sufficiently isolated from its environment to be considered free-standing."^[19] This definition is narrower than the IUPAC definition and refers to cloven, transferred, and suspended graphene.^{[citation needed]} 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.^[20]

History[edit]

In 1859 Benjamin Collins Brodie was aware of the highly lamellar structure of thermally reduced graphite oxide.^[21][22]

The structure of graphite was determined in 1916^[23] by the related method of powder diffraction,^[24] it was studied in detail by V. Kohlschütter and P. Haenni in 1918, 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 David 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 electron microscopy.^[32] Before 2004 intercalated graphite compounds were studied under a transmission electron microscope (TEM). Researchers occasionally observed thin graphitic flakes ("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 significant charge transfer from the substrate to the epitaxial graphene, and, in some cases, hybridization between the d-orbitals of the substrate atoms and π orbitals of graphene, which significantly alters the electronic structure of epitaxial graphene.

Single layers of graphite were also observed by transmission electron microscopy within bulk materials, in particular inside soot obtained by chemical exfoliation. 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 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 sufficient to "spark the graphene gold rush," which awaited macroscopic samples of extracted 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 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,^[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 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 first to use this technique— US Pat. 6667100,^[40] filed in 2002, describes how to process commercially available flexible expanded graphite to achieve a graphite thickness of 0.00001" (one hundred-thousandth) of an inch. The key to success was high-throughput visual recognition of graphene on a properly chosen substrate, which provides a small but noticeable optical contrast.

The cleavage technique led directly to the first observation of the anomalous quantum Hall effect in graphene,^[28][30] which provided direct evidence of graphene'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^[28][30] appeared in the same issue of Nature in 2005. Before these experiments other researchers looked for the quantum Hall effect^[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 first proof of the Dirac fermion nature of electrons.^{[citation needed]}

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

Recently, several important techniques have been developed to prepare nanostructured graphene, e.g., Graphene Quantum Dots (GQDs); these techniques mainly include electron beam lithography, chemical synthesis, electrochemical preparation, graphene oxide (GO) reduction, C60 catalytic transformation, the microwave assisted hydrothermal method (MAH),^[44][45] the Soft-Template method,^[46] the hydrothermal method,^[47][48][49] and the ultrasonic exfoliation method.^[50]

In 2014 National Graphene Institute, a £60m Graphene Engineering Innovation Centre (GEIC), was announced to support applied research and development in partnership with other research organizations and industry.^[51]

In North East England two commercial manufacturers, Applied Graphene Materials^[52] and Thomas Swan Limited^[53] (with Trinity College, Dublin researchers),^[54] have begun manufacturing. In East Anglia, another manufacturer, FGV Cambridge Nanosystems,^[55][56][57] is operating a large scale graphene powder production facility.

In 2016, Brown University introduced a method for 'crumpling' graphene, adding wrinkles to the material on a nanoscale; this was achieved by depositing layers of graphene oxide onto a shrink film, then shrunken, with the film dissolved before being shrunken again on another sheet of film. The crumpled graphene became superhydrophobic, and, when used as a battery electrode, the material was shown to have as much of a 400% increase in electrochemical current density.^[58][59]

Properties[edit]

Graphene has a theoretical specific surface area (SSA) of 2630 m²/g. This is much larger than that reported to date for carbon black (typically smaller than 900 m²/g) or for carbon nanotubes (CNTs), from ≈100 to 1000 m²/g and is similar to activated carbon.^[60]

Structure[edit]

Graphene is a crystalline allotrope of carbon with 2-dimensional properties, its carbon atoms are densely packed in a regular atomic-scale chicken wire (hexagonal) pattern.^[61]

Each atom has four bonds, one σ bond with each of its three neighbors and one π-bond that is oriented out of plane; the atoms are about 1.42 Å apart.^[61]

Graphene's hexagonal lattice can be regarded as two interleaving triangular lattices; this perspective was successfully used to calculate the band structure for a single graphite layer using a tight-binding approximation.^[61]

Graphene's stability is due to its tightly packed carbon atoms and a sp² orbital hybridization – a combination of orbitals s, p_x and p_y that constitute the σ-bond. The final p_z electron makes up the π-bond. The π-bonds hybridize together to form the π-band and π∗-bands; these bands are responsible for most of graphene's notable electronic properties, via the half-filled band that permits free-moving electrons.^[61] Recent quantitative estimates of aromatic stabilization and limiting size derived from the enthalpies of hydrogenation (ΔH_hydro) agree well with the literature reports.^[62]

Graphene sheets in solid form usually show evidence in diffraction for graphite's (002) layering; this is true of some single-walled nanostructures.^[63] However, unlayered graphene with only (hk0) rings has been found in the core of presolar graphite onions.^[64] TEM studies show faceting at defects in flat graphene sheets^[65] and suggest a role for two-dimensional crystallization from a melt.

Graphene can self-repair holes in its sheets, when exposed to molecules containing carbon, such as hydrocarbons. Bombarded with pure carbon atoms, the atoms perfectly align into hexagons, completely filling the holes.^[66][67]

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 diffraction patterns showed the expected honeycomb lattice. Suspended graphene also showed "rippling" of the flat sheet, with amplitude of about one nanometer; these ripples may be intrinsic to the material as a result of the instability of two-dimensional crystals,^[37][68][69] or may originate from the ubiquitous dirt seen in all TEM images of graphene. Atomic resolution real-space images of isolated, single-layer graphene on SiO
₂ substrates are available^[70] 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.^[70]

Chemical[edit]

Graphene is the only form of carbon (or solid material) in which every atom is available for chemical reaction from two sides (due to the 2D structure). Atoms at the edges of a graphene sheet have special chemical reactivity. Graphene has the highest ratio of edge atoms of any allotrope. Defects within a sheet increase its chemical reactivity;^[71] the onset temperature of reaction between the basal plane of single-layer graphene and oxygen gas is below 260 °C (530 K).^[72] Graphene burns at very low temperature (e.g., 350 °C (620 K)).^[73] Graphene is commonly modified 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-^[74] and nitrogen-^[75] functional groups requires the structures to be well controlled.

In 2013, Stanford University physicists reported that single-layer graphene is a hundred times more chemically reactive than thicker sheets.^[vague][76]

Electronic[edit]

Graphene is a zero-gap semiconductor, because its conduction and valence bands meet at the Dirac points; the Dirac points are six locations in momentum space, on the edge of the Brillouin zone, divided into two non-equivalent sets of three points. The two sets are labeled K and K'; the sets give graphene a valley degeneracy of gv = 2. By contrast, for traditional semiconductors the primary point of interest is generally Γ, where momentum is zero.^[61] Four electronic properties separate it from other condensed matter systems.

However, if the in-plane direction is no longer infinite, but confined, its electronic structure would change, they are referred to as graphene nanoribbons. If it is "zig-zag", the bandgap would still be zero. If it is "armchair", the bandgap would be non-zero (see figure).

Electronic spectrum[edit]

Electrons propagating through graphene's honeycomb lattice effectively lose their mass, producing quasi-particles that are described by a 2D analogue of the Dirac equation rather than the Schrödinger equation for spin-​¹⁄₂ particles.^[77][78]

Dispersion relation [edit]

When the atoms are placed onto the graphene hexagonal lattice, the overlap between the p_z(π) orbitals and the s or the p_x and p_y orbitals is zero by symmetry. The p_z electrons forming the π bands in graphene can therefore be treated independently. Within this π-band approximation, using a conventional tight-binding model, the dispersion relation (restricted to first-nearest-neighbor interactions only) that produces energy of the electrons with wave vector k is^[79][80]

${\displaystyle E=\pm {\sqrt {\gamma _{0}^{2}\left(1+4\cos ^{2}{\frac {k_{y}a}{2}}+4\cos {\frac {k_{y}a}{2}}\cdot \cos {\frac {k_{x}{\sqrt {3}}a}{2}}\right)}}}$

with the nearest-neighbor (π orbitals) hopping energy γ₀ ≈ 2.8 eV and the lattice constant a ≈ 2.46 Å. The conduction and valence bands, respectively, correspond to the different signs. With one p_z electron per atom in this model the valence band is fully occupied, while the conduction band is vacant. The two bands touch at the zone corners (the K point in the Brillouin zone), where there is a zero density of states but no band gap; the graphene sheet thus displays a semimetallic (or zero-gap semiconductor) character, although the same cannot be said of a graphene sheet rolled into a carbon nanotube, due to its curvature. Two of the six Dirac 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.^[79][81] Since an elementary cell of the lattice has a basis of two atoms, the wave function has an effective 2-spinor structure.

As a consequence, at low energies, even neglecting the true spin, the electrons can be described by an equation that is formally equivalent to the massless Dirac equation. Hence, the electrons and holes are called Dirac fermions;^[79] this pseudo-relativistic description is restricted to the chiral limit, i.e., to vanishing rest mass M₀, which leads to interesting additional features:^[79][82]

${\displaystyle v_{F}\,{\vec {\sigma }}\cdot \nabla \psi (\mathbf {r} )\,=\,E\psi (\mathbf {r} ).}$

Here v_F ~ 10⁶ m/s (.003 c) is the Fermi velocity in graphene, which replaces the velocity of light in the Dirac theory; ${\displaystyle {\vec {\sigma }}}$ is the vector of the Pauli matrices, ${\displaystyle \psi (\mathbf {r} )}$ is the two-component wave function of the electrons, and E is their energy.^[77]

The equation describing the electrons' linear dispersion relation is

${\displaystyle E=\hbar v_{F}{\sqrt {k_{x}^{2}+k_{y}^{2}}}}$

where the wavevector k is measured from the Dirac points (the zero of energy is chosen here to coincide with the Dirac points). The equation uses a pseudospin matrix formula that describes two sublattices of the honeycomb lattice.^[81]

Single-atom wave propagation[edit]

Electron waves in graphene propagate within a single-atom layer, making them sensitive to the proximity of other materials such as high-κ dielectrics, superconductors and ferromagnetics.

Electron transport[edit]

Graphene displays remarkable electron mobility at room temperature, with reported values in excess of 15000 cm²⋅V⁻¹⋅s⁻¹.^[37] Hole and electron mobilities were expected to be nearly identical;^[78] the mobility is nearly independent of temperature between 10 K and 100 K,^[28][83][84] which implies that the dominant scattering mechanism is defect scattering. Scattering by graphene's acoustic phonons intrinsically limits room temperature mobility to 200000 cm²⋅V⁻¹⋅s⁻¹ at a carrier density of 10¹² cm⁻²,^[84][85] 10×10⁶ times greater than copper.^[86]

The corresponding resistivity of graphene sheets would be 10⁻⁶ Ω⋅cm. This is less than the resistivity of silver, the lowest otherwise known at room temperature.^[87] However, on SiO
₂ substrates, scattering of electrons by optical phonons of the substrate is a larger effect than scattering by graphene's own phonons. This limits mobility to 40000 cm²⋅V⁻¹⋅s⁻¹.^[84]

Charge transport has major concerns due to adsorption of contaminants such as water and oxygen molecules; this leads to non-repetitive and large hysteresis I-V characteristics. Researchers must carry out electrical measurements in vacuum; the protection of graphene surface by a coating with materials such as SiN, PMMA, h-BN, etc., have been discussed by researchers. In January 2015, the first stable graphene device operation in air over several weeks was reported, for graphene whose surface was protected by aluminum oxide.^[88][89] In 2015 lithium-coated graphene exhibited superconductivity, a first for graphene.^[90]

Electrical resistance in 40-nanometer-wide nanoribbons of epitaxial graphene changes in discrete steps; the ribbons' conductance exceeds predictions by a factor of 10. The ribbons can act more like optical waveguides or quantum dots, allowing electrons to flow smoothly along the ribbon edges. In copper, resistance increases in proportion to length as electrons encounter impurities.^[91][92]

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 length—the ballistic mode at 16 micrometres and the other at 160 nanometres (1% of the former length).^[91]

Graphene electrons can cover micrometer distances without scattering, even at room temperature.^[77]

Despite zero carrier density near the Dirac points, graphene exhibits a minimum conductivity on the order of ${\displaystyle 4e^{2}/h}$. The origin of this minimum conductivity is still unclear. However, rippling of the graphene sheet or ionized impurities in the SiO
₂ substrate may lead to local puddles of carriers that allow conduction.^[78] Several theories suggest that the minimum conductivity should be ${\displaystyle 4e^{2}/{(\pi }h)}$; however, most measurements are of order ${\displaystyle 4e^{2}/h}$ or greater^[37] and depend on impurity concentration.^[93]

Near zero carrier density graphene exhibits positive photoconductivity and negative photoconductivity at high carrier density; this is governed by the interplay between photoinduced changes of both the Drude weight and the carrier scattering rate.^[94]

Graphene doped with various gaseous species (both acceptors and donors) can be returned to an undoped state by gentle heating in vacuum.^[93][95] Even for dopant concentrations in excess of 10¹² cm⁻² carrier mobility exhibits no observable change.^[95] Graphene doped with potassium in ultra-high vacuum at low temperature can reduce mobility 20-fold;^[93][96] the mobility reduction is reversible on heating the graphene to remove the potassium.

Due to graphene's two dimensions, charge fractionalization (where the apparent charge of individual pseudoparticles in low-dimensional systems is less than a single quantum^[97]) is thought to occur, it may therefore be a suitable material for constructing quantum computers^[98] using anyonic circuits.^[99]

Anomalous quantum Hall effect[edit]

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The quantum Hall effect is a quantum mechanical version of the Hall effect, which is the production of transverse (perpendicular to the main current) conductivity in the presence of a magnetic field; the quantization of the Hall effect ${\displaystyle \sigma _{xy}}$ at integer multiples (the "Landau level") of the basic quantity ${\displaystyle e^{2}/h}$ (where e is the elementary electric charge and h is Planck's constant) It can usually be observed only in very clean silicon or gallium arsenide solids at temperatures around 3 K and very high magnetic fields.

Graphene shows the quantum Hall effect with respect to conductivity quantization: the effect 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. Graphene's Hall conductivity is ${\displaystyle \sigma _{xy}=\pm {4\cdot \left(N+1/2\right)e^{2}}/h}$, 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 graphene's massless Dirac electrons. In a magnetic field, their spectrum has a Landau level with energy precisely at the Dirac point; this level is a consequence of the Atiyah–Singer index theorem and is half-filled in neutral graphene,^[79] leading to the "+1/2" in the Hall conductivity.^[29] Bilayer graphene also shows the quantum Hall effect, but with only one of the two anomalies (i.e. ${\displaystyle \sigma _{xy}=\pm {4\cdot N\cdot e^{2}}/h}$). In the second anomaly, the first plateau at N=0 is absent, indicating that bilayer graphene stays metallic at the neutrality point.^[37]

Unlike normal metals, graphene's longitudinal resistance shows maxima rather than minima for integral values of the Landau filling factor in measurements of the Shubnikov–de Haas oscillations, whereby the term integral quantum Hall effect; these oscillations show a phase shift of π, known as Berry's phase.^[28][78] Berry's phase arises due to the zero effective carrier mass near the Dirac points;^[30] the temperature dependence of the oscillations reveals that the carriers have a non-zero cyclotron mass, despite their zero effective mass.^[28]

Graphene samples prepared on nickel films, and on both the silicon face and carbon face of silicon carbide, show the anomalous effect directly in electrical measurements.^{[100][101][102][103][104][105]} Graphitic layers on the carbon face of silicon carbide show a clear Dirac spectrum in angle-resolved photoemission experiments, and the effect is observed in cyclotron resonance and tunneling experiments.^[106]

Strong magnetic fields[edit]

In magnetic fields above 10 tesla or so additional plateaus of the Hall conductivity at σ_xy = νe²/h with ν = 0, ±1, ±4 are observed.^[107] A plateau at ν = 3^[108] and the fractional quantum Hall effect at ν = ​¹⁄₃ were also reported.^[108][109]

These observations with ν = 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.

Casimir effect[edit]

The Casimir effect is an interaction between disjoint neutral bodies provoked by the fluctuations of the electrodynamical vacuum. Mathematically it can be explained by considering the normal modes of electromagnetic fields, which explicitly depend on the boundary (or matching) conditions on the interacting bodies' surfaces. Since graphene/electromagnetic field interaction is strong for a one-atom-thick material, the Casimir effect is of growing interest.^[110][111]

Van der Waals force[edit]

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.^[112]

'Massive' electrons[edit]

Graphene's 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. However, if the two atoms in the unit cell are not identical, the situation changes. Hunt et al. show that placing hexagonal boron nitride (h-BN) 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 [0.03 Electron Volt(eV)].^[113]

The mass can be positive or negative. An arrangement that slightly raises the energy of an electron on atom A relative to atom B gives it a positive mass, while an arrangement 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 negative-mass 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.^[113]

If the mass in graphene can be controlled, electrons can be confined 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.^[113]

Optical[edit]

Graphene's unique optical properties produce an unexpectedly high opacity for an atomic monolayer in vacuum, absorbing πα ≈ 2.3% of red light, where α is the fine-structure constant.^[116] 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 different from more common quadratic massive bands."^[115] Based on the Slonczewski–Weiss–McClure (SWMcC) band model of graphite, the interatomic distance, hopping value and frequency cancel when optical conductance is calculated using Fresnel equations in the thin-film limit.

Although confirmed experimentally, the measurement is not precise enough to improve on other techniques for determining the fine-structure constant.^[117]

Multi-Parametric Surface Plasmon Resonance was used to characterize both thickness and refractive index of chemical-vapor-deposition (CVD)-grown graphene films; the measured refractive index and extinction coefficient values at 670 nm wavelength are 3.135 and 0.897, respectively. The thickness was determined as 3.7Å from a 0.5mm area, which agrees with 3.35Å reported for layer-to-layer carbon atom distance of graphite crystals.^[118] The method can be further used also for real-time label-free interactions of graphene with organic and inorganic substances. Furthermore, the existence of unidirectional surface plasmons in the nonreciprocal graphene-based gyrotropic interfaces has been demonstrated theoretically. By efficiently controlling the chemical potential of graphene, the unidirectional working frequency can be continuously tunable from THz to near-infrared and even visible.^[119] Particularly, the unidirectional frequency bandwidth can be 1– 2 orders of magnitude larger than that in metal under the same magnetic field, which arises from the superiority of extremely small effective electron mass in graphene.

Graphene's band gap can be tuned from 0 to 0.25 eV (about 5 micrometre wavelength) by applying voltage to a dual-gate bilayer graphene field-effect transistor (FET) at room temperature.^[120] The optical response of graphene nanoribbons is tunable into the terahertz regime by an applied magnetic field.^[121] Graphene/graphene oxide systems exhibit electrochromic behavior, allowing tuning of both linear and ultrafast optical properties.^[122]

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 He–Ne laser as the light source.^[123]

Saturable absorption[edit]

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 fluence. 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 fiber 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.^[122][124] 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 a microwave saturable absorber, modulator, polarizer, microwave signal processing and broad-band wireless access networks.^[125]

Nonlinear Kerr effect[edit]

Under more intensive laser illumination, graphene could also possess a nonlinear phase shift due to the optical nonlinear Kerr effect. Based on a typical open and close aperture z-scan measurement, graphene possesses a giant nonlinear Kerr coefficient of 10⁻⁷ cm²⋅W⁻¹, almost nine orders of magnitude larger than that of bulk dielectrics.^[126] This suggests that graphene may be a powerful nonlinear Kerr medium, with the possibility of observing a variety of nonlinear effects, the most important of which is the soliton.^[127]

Excitonic[edit]

First-principle calculations with quasiparticle corrections and many-body effects are performed to study the electronic and optical properties of graphene-based materials; the approach is described as three stages.^[128] With GW calculation, the properties of graphene-based materials are accurately investigated, including bulk graphene,^[129] nanoribbons,^[130] edge and surface functionalized armchair oribbons,^[131] hydrogen saturated armchair ribbons,^[132] Josephson effect in graphene SNS junctions with single localized defect^[133] and armchair ribbon scaling properties.^[134]

Stability[edit]

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 within graphite) only for molecules larger than 24,000 atoms.^[135]

Thermal conductivity[edit]

Thermal transport in graphene is an active area of research, which has attracted attention because of the potential for thermal management applications. Early measurements of the thermal conductivity of suspended graphene reported an exceptionally large thermal conductivity of approximately 5300 W⋅m⁻¹⋅K⁻¹,^[136] compared with the thermal conductivity of pyrolytic graphite of approximately 2000 W⋅m⁻¹⋅K⁻¹ at room temperature.^[137] However, later studies have questioned whether this ultrahigh value had been overestimated, and have instead measured a wide range of thermal conductivities between 1500 – 2500 W⋅m⁻¹⋅K⁻¹ for suspended single layer graphene.^{[138][139][140][141]} The large range in the reported thermal conductivity can be caused by large measurement uncertainties as well as variations in the graphene quality and processing conditions. In addition, it is known that when single-layer graphene is supported on an amorphous material, the thermal conductivity is reduced to about 500 – 600 W⋅m⁻¹⋅K⁻¹ at room temperature as a result of scattering of graphene lattice waves by the substrate,^[142][143] and can be even lower for few layer graphene encased in amorphous oxide.^[144] Likewise, polymeric residue can contribute to a similar decrease in the thermal conductivity of suspended graphene to approximately 500 – 600 W⋅m⁻¹⋅K⁻¹for bilayer graphene.^[145]

It has been suggested that the isotopic composition, the ratio of ¹²C to ¹³C, has a significant impact on the thermal conductivity. For example, isotopically pure ¹²C graphene has higher thermal conductivity than either a 50:50 isotope ratio or the naturally occurring 99:1 ratio,^[146] it can be shown by using the Wiedemann–Franz law, that the thermal conduction is phonon-dominated.^[136] However, for a gated graphene strip, an applied gate bias causing a Fermi energy shift much larger than k_BT can cause the electronic contribution to increase and dominate over the phonon contribution at low temperatures. The ballistic thermal conductance of graphene is isotropic.^[147][148]

Potential for this high conductivity can be seen by considering graphite, a 3D version of graphene that has basal plane thermal conductivity of over a 1000 W⋅m⁻¹⋅K⁻¹ (comparable to diamond). In graphite, the c-axis (out of plane) thermal conductivity is over a factor of ~100 smaller due to the weak binding forces between basal planes as well as the larger lattice spacing.^[149] In addition, the ballistic thermal conductance of graphene is shown to give the lower limit of the ballistic thermal conductances, per unit circumference, length of carbon nanotubes.^[150]

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 T² dependent thermal conductivity contribution of the linear modes is dominated at low temperatures by the T^1.5 contribution of the out of plane mode;^[150] some graphene phonon bands display negative Grüneisen parameters.^[151] At low temperatures (where most optical modes with positive Grüneisen parameters are still not excited) the contribution from the negative Grüneisen parameters will be dominant and thermal expansion coefficient (which is directly proportional to Grüneisen parameters) negative; the lowest negative Grüneisen parameters correspond to the lowest transverse 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 effect," was predicted by Lifshitz in 1952.^[152]

Mechanical[edit]

The carbon–carbon bond length in graphene is about 0.142 nanometers.^[153] Graphene sheets stack to form graphite with an interplanar spacing of 0.335 nm.

Graphene is the strongest material ever tested,^[154] with an intrinsic tensile strength of 130 GPa and a Young's modulus (stiffness) of 1 TPa (150000000 psi).^[155] The Nobel announcement illustrated this by saying that a 1 square meter graphene hammock would support a 4 kg cat but would weigh only as much as one of the cat's whiskers, at 0.77 mg (about 0.001% of the weight of 1 m² of paper).^[156]

Large-angle-bent graphene monolayer has been achieved with negligible strain, showing mechanical robustness of the two-dimensional carbon nanostructure. Even with extreme deformation, excellent carrier mobility in monolayer graphene can be preserved.^[157]

The spring constant of suspended graphene sheets has been measured using an atomic force microscope (AFM). Graphene sheets were suspended over SiO
₂ cavities where an AFM tip was used to apply a stress to the sheet to test its mechanical properties. Its spring constant was in the range 1–5 N/m and the stiffness was 0.5 TPa, which differs from that of bulk graphite. These intrinsic properties could lead to applications such as NEMS as pressure sensors and resonators.^[158] Due to its large surface energy and out of plane ductility, flat graphene sheets are unstable with respect to scrolling, i.e. bending into a cylindrical shape, which is its lower-energy state.^[159]

As is true of all materials, regions of graphene are subject to thermal and quantum fluctuations in relative displacement. Although the amplitude of these fluctuations is bounded in 3D structures (even in the limit of infinite size), the Mermin–Wagner theorem shows that the amplitude of long-wavelength fluctuations grows logarithmically with the scale of a 2D structure, and would therefore be unbounded in structures of infinite size. Local deformation and elastic strain are negligibly affected by this long-range divergence in relative displacement, it is believed that a sufficiently large 2D structure, in the absence of applied lateral tension, will bend and crumple to form a fluctuating 3D structure. Researchers have observed ripples in suspended layers of graphene,^[32] and it has been proposed that the ripples are caused by thermal fluctuations in the material; as a consequence of these dynamical deformations, it is debatable whether graphene is truly a 2D structure.^{[37][68][69][160]} It has recently been shown that these ripples, if amplified through the introduction of vacancy defects, can impart a negative Poisson's ratio into graphene, resulting in the thinnest auxetic material known so far.^[161]

Graphene nanosheets have been incorporated into a Ni matrix through a plating process to form Ni-graphene composites on a target substrate; the enhancement in mechanical properties of the composites is attributed to the high interaction between Ni and graphene and the prevention of the dislocation sliding in the Ni matrix by the graphene.^[162]

Fracture toughness[edit]

In 2014, researchers from Rice University and the Georgia Institute of Technology have indicated that despite its strength, graphene is also relatively brittle, with a fracture toughness of about 4 MPa√m;^[163] this indicates that imperfect graphene is likely to crack in a brittle manner like ceramic materials, as opposed to many metallic materials which tend to have fracture toughnesses in the range of 15–50 MPa√m. Later in 2014, the Rice team announced that graphene showed a greater ability to distribute force from an impact than any known material, ten times that of steel per unit weight;^[164] the force was transmitted at 22.2 kilometres per second (13.8 mi/s).^[165]

Mechanical Properties of Polycrystalline Graphene[edit]

Various methods – most notably, chemical vapor deposition (CVD), as discussed in the section below - have been developed to produce large-scale graphene needed for device applications; such methods often synthesize polycrystalline graphene.^[166] The mechanical properties of polycrystalline graphene is affected by the nature of the defects, such as grain-boundaries (GB) and vacancies, present in the system and the average grain-size. How the mechanical properties change with such defects have been investigated by researchers, theoretically and experimentally.^{[167][166][168][169]}

Graphene grain boundaries typically contain heptagon-pentagon pairs; the arrangement of such defects depends on whether the GB is in zig-zag or armchair direction. It further depends on the tilt-angle of the GB.^[170] In 2010, researchers from Brown University computationally predicted that as the tilt-angle increases, the grain boundary strength also increases.They showed that the weakest link in the grain boundary is at the critical bonds of the heptagon rings; as the grain boundary angle increases, the strain in these heptagon rings decreases, causing the grain-boundary to be stronger than lower-angle GBs. They proposed that, in fact, for sufficiently large angle GB, the strength of the GB is similar to pristine graphene.^[171] In 2012, it was further shown that the strength can increase or decrease, depending on the detailed arrangements of the defects;^[172] these predictions have since been supported by experimental evidences. In a 2013 study led by James Hone's group, researchers probed the elastic stiffness and strength of CVD-grown graphene by combining nano-indentation and high-resolution TEM, they found that the elastic stiffness is identical and strength is only slightly lower than those in pristine graphene.^[173] In the same year, researchers from UC Berkeley and UCLA probed bi-crystalline graphene with TEM and AFM, they found that the strength of grain-boundaries indeed tend to increase with the tilt angle.^[174]

While the presence of vacancies is not only prevalent in polycrystalline graphene, vacancies can have significant effects on the strength of graphene; the general consensus is that the strength decreases along with increasing densities of vacancies. In fact, various studies have shown that for graphene with for sufficiently low density of vacancies, the strength does not vary significantly from that of pristine graphene. On the other hand, high density of vacancies can severely reduce the strength of graphene.^[168]

Compared to the fairly well-understood nature of the effect that grain boundary and vacancies have on the mechanical properties of graphene, there is no clear consensus on the general effect that the average grain size has on the strength of polycrystalline graphene.^{[167][168][169]} In fact, three notable theoretical/computational studies on this topic have led to three different conclusions.^{[175][176][177]} First, in 2012, Kotakoski and Myer studied the mechanical properties of polycrystalline graphene with “realistic atomistic model”, using molecular-dynamics (MD) simulation. To emulate the growth mechanism of CVD, they first randomly selected nucleation sites that are at least 5A (arbitrarily chosen) apart from other sites. Polycrystalline graphene was generated from these nucleation sites and was subsequently annealed at 3000K, then quenched. Based on this model, they found that cracks are initiated at grain-boundary junctions, but the grain size does not significantly affect the strength.^[175] Second, in 2013, Z. Song et al. used MD simulations to study the mechanical properties of polycrystalline graphene with uniform-sized hexagon-shaped grains. The hexagon grains were oriented in various lattice directions and the GBs consisted of only heptagon, pentagon, and hexagonal carbon rings; the motivation behind such model was that similar systems had been experimentally observed in graphene flakes grown on the surface of liquid copper. While they also noted that crack is typically initiated at the triple junctions, they found that as the grain size decreases, the yield strength of graphene increases. Based on this finding, they proposed that polycrystalline follows pseudo Hall-Petch relationship.^[176] Third, in 2013, Z. D. Sha et al. studied the effect of grain size on the properties of polycrystalline graphene, by modelling the grain patches using Voronoi construction. The GBs in this model consisted of heptagon, pentagon, and hexagon, as well as squares, octagons, and vacancies. Through MD simulation, contrary to the fore-mentioned study, they found inverse Hall-Petch relationship, where the strength of graphene increases as the grain size increases.^[177] Experimental observations and other theoretical predictions also gave differing conclusions, similar to the three given above;^[169] such discrepancies show the complexity of the effects that grain size, arrangements of defects, and the nature of defects have on the mechanical properties of polycrystalline graphene.

Spin transport[edit]

Graphene is claimed to be an ideal material for spintronics due to its small spin-orbit interaction and the near absence of nuclear magnetic moments in carbon (as well as a weak hyperfine interaction). Electrical spin current injection and detection has been demonstrated up to room temperature.^{[178][179][180]} Spin coherence length above 1 micrometre at room temperature was observed,^[178] and control of the spin current polarity with an electrical gate was observed at low temperature.^[179]

Strong magnetic fields[edit]

Graphene's quantum Hall effect in magnetic fields above 10 Teslas or so reveals additional interesting features. Additional plateaus of the Hall conductivity at ${\displaystyle \sigma _{xy}=\nu e^{2}/h}$ with ${\displaystyle \nu =0,\pm {1},\pm {4}}$ are observed.^[107] Also, the observation of a plateau at ${\displaystyle \nu =3}$^[108] and the fractional quantum Hall effect at ${\displaystyle \nu =1/3}$ were reported.^[108][109]

These observations with ${\displaystyle \nu =0,\pm 1,\pm 3,\pm 4}$ 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.^{[citation needed]}

Spintronic and magnetic properties can be present in graphene simultaneously.^[181] Low-defect graphene nanomeshes manufactured by using a non-lithographic method exhibit large-amplitude ferromagnetism even at room temperature. Additionally a spin pumping effect is found for fields applied in parallel with the planes of few-layer ferromagnetic nanomeshes, while a magnetoresistance hysteresis loop is observed under perpendicular fields.

Magnetic[edit]

In 2014 researchers magnetized graphene by placing it on an atomically smooth layer of magnetic yttrium iron garnet; the graphene's electronic properties were unaffected. Prior approaches involved doping graphene with other substances;^[182] the dopant's presence negatively affected its electronic properties.^[183]

Biological[edit]

Researchers at the Graphene Research Centre at the National University of Singapore (NUS) discovered in 2011 the amazing ability of graphene to accelerate the osteogenic differentiation of human Mesenchymal Stem Cells without the use of biochemical inducers.^[184]

In 2015 researchers used graphene to create sensitive biosensors by using epitaxial graphene on silicon carbide; the sensors bind to the 8-hydroxydeoxyguanosine (8-OHdG) and is capable of selective binding with antibodies. The presence of 8-OHdG in blood, urine and saliva is commonly associated with DNA damage. Elevated levels of 8-OHdG have been linked to increased risk of developing several cancers.^[185]

The Cambridge Graphene Centre and the University of Trieste in Italy conducted a collaborative research on use of Graphene as electrodes to interact with brain neurons; the research was recently published in the journal of ACS Nano.

The research revealed that uncoated Graphene can be used as neuro-interface electrode without altering or damaging the neural functions such as signal loss or formation of scar tissue. Graphene electrodes in body stay significantly more stable than modern day electrodes (of tungsten or silicon) because of its unique properties such as flexibility, bio-compatibility, and conductivity, it could possibly help in restoring sensory function or motor disorders in paralysis or Parkinson patients.^[186]

Support Substrate[edit]

The electronics property of graphene can be significantly influenced by the supporting substrate. Studies of graphene monolayers on clean and hydrogen(H)-passivated silicon (100) (Si(100)/H) surfaces have been performed;^[187] the Si(100)/H surface does not perturb the electronic properties of graphene, whereas the interaction between the clean Si(100) surface and graphene changes the electronic states of graphene significantly. This effect results from the covalent bonding between C and surface Si atoms, modifying the π-orbital network of the graphene layer; the local density of states shows that the bonded C and Si surface states are highly disturbed near the Fermi energy.

Forms[edit]

Monolayer sheets[edit]

In 2013 a group of Polish scientists presented a production unit that allows the manufacture of continuous monolayer sheets;^[188] the process is based on graphene growth on a liquid metal matrix.^[189] The product of this process was called HSMG.

Bilayer graphene[edit]

Bilayer graphene displays the anomalous quantum Hall effect, a tunable band gap^[190] and potential for excitonic condensation^[191] –making it a promising candidate for optoelectronic and nanoelectronic applications. Bilayer graphene typically can be found either in twisted configurations where the two layers are rotated relative to each other or graphitic Bernal stacked configurations where half the atoms in one layer lie atop half the atoms in the other.^[192] 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 regions that almost exclusively conform to a Bernal stack geometry.^[192]

Graphene superlattices[edit]

Periodically stacked graphene and its insulating isomorph provide a fascinating structural element in implementing highly functional superlattices at the atomic scale, which offers possibilities in designing nanoelectronic and photonic devices. Various types of superlattices can be obtained by stacking graphene and its related forms;^[193] the energy band in layer-stacked superlattices is found to be more sensitive to the barrier width than that in conventional III–V semiconductor superlattices. When adding more than one atomic layer to the barrier in each period, the coupling of electronic wavefunctions in neighboring potential wells can be significantly reduced, which leads to the degeneration of continuous subbands into quantized energy levels; when varying the well width, the energy levels in the potential wells along the L-M direction behave distinctly from those along the K-H direction.

Graphene nanoribbons[edit]

Graphene nanoribbons ("nanostripes" in the "zig-zag" orientation), at low temperatures, show spin-polarized metallic edge currents, which also suggests applications in the new field of spintronics. (In the "armchair" orientation, the edges behave like semiconductors.^[77])

Graphene quantum dots[edit]

Graphene quantum dots (GQDs) have mainly been fabricated by the microwave assisted hydrothermal method (MAH),^[44][45] the Soft-Template method,^[46] the hydrothermal method,^[47][48][49] the ultrasonic exfoliation method,^[50] the electron beam lithography method, the chemical synthesis method, the electrochemical preparation method, the graphene oxide (GO) reduction method, and the C60 catalytic transformation method, etc.

Graphene oxide[edit]

Using paper-making techniques on dispersed, oxidized and chemically processed graphite in water, the monolayer flakes form a single sheet and create strong bonds; these sheets, called graphene oxide paper, have a measured tensile modulus of 32 GPa.^[194] 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.^[195] Graphene oxide flakes in polymers display enhanced photo-conducting properties.^[196] 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 flow through as quickly as if the membrane was not present.^[197]

Chemical modification[edit]

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Soluble fragments of graphene can be prepared in the laboratory^[198] through chemical modification 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.

Refluxing 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 70–80%.

Hydrazine reflux is commonly used for reducing SLGO to SLG(R), but titrations show that only around 20–30% of the carboxylic groups are lost, leaving a significant number available for chemical attachment. Analysis of SLG(R) generated by this route reveals that the system is unstable and using a room temperature stirring with HCl (< 1.0 M) leads to around 60% loss of COOH functionality. Room temperature treatment of SLGO with carbodiimides leads to the collapse of the individual sheets into star-like clusters that exhibited poor subsequent reactivity with amines (c. 3–5% conversion of the intermediate to the final amide).^[199] It is apparent that conventional chemical treatment of carboxylic groups on SLGO generates morphological changes of individual sheets that leads to a reduction in chemical reactivity, which may potentially limit their use in composite synthesis. Therefore, chemical reactions types have been explored. SLGO has also been grafted with polyallylamine, cross-linked through epoxy groups; when filtered into graphene oxide paper, these composites exhibit increased stiffness and strength relative to unmodified graphene oxide paper.^[200]

Full hydrogenation from both sides of graphene sheet results in graphane, but partial hydrogenation leads to hydrogenated graphene.^[201] Similarly, both-side fluorination of graphene (or chemical and mechanical exfoliation of graphite fluoride) leads to fluorographene (graphene fluoride),^[202] while partial fluorination (generally halogenation) provides fluorinated (halogenated) graphene.

Graphene ligand/complex[edit]

Graphene can be a ligand to coordinate metals and metal ions by introducing functional groups. Structures of graphene ligands are similar to e.g. metal-porphyrin complex, metal-phthalocyanine complex, and metal-phenanthroline complex. Copper and nickel ions can be coordinated with graphene ligands.^[203][204]

Graphene fiber[edit]

In 2011, researchers reported a novel yet simple approach to fabricate graphene fibers from chemical vapor deposition grown graphene films;^[205] the method was scalable and controllable, delivering tunable morphology and pore structure by controlling the evaporation of solvents with suitable surface tension. Flexible all-solid-state supercapacitors based on this graphene fibers were demonstrated in 2013.^[206]

In 2015 intercalating small graphene fragments into the gaps formed by larger, coiled graphene sheets, after annealing provided pathways for conduction, while the fragments helped reinforce the fibers.^{[sentence fragment]} The resulting fibers offered better thermal and electrical conductivity and mechanical strength. Thermal conductivity reached 1290 watts per meter per kelvin, while tensile strength reached 1080 megapascals.^[207]

In 2016, Kilometer-scale continuous graphene fibers with outstanding mechanical properties and excellent electrical conductivity are produced by high-throughput wet-spinning of graphene oxide liquid crystals followed by graphitization through a full-scale synergetic defect-engineering strategy;^[208] the graphene fibers with superior performances promise wide applications in functional textiles, lightweight motors, microelectronic devices, etc.

Tsinghua University in Beijing, led by Wei Fei of the Department of Chemical Engineering, claims to be able to create a carbon nanotube fibre which has a tensile strength of 80 gigapascals.^[209]

3D graphene[edit]

In 2013, a three-dimensional honeycomb of hexagonally arranged carbon was termed 3D graphene. Recently, self-supporting 3D graphene has also been produced.^[210] 3D structures of graphene can be fabricated by using either CVD or solution based methods. A recent review by Khurram and Xu et al., have provided the summary of the state-of-the-art techniques for fabrication of the 3D structure of graphene and other related two-dimensional materials.^[211] Recently, researchers at Stony Brook University have reported a novel radical-initiated crosslinking method to fabricate porous 3D free-standing architectures of graphene and carbon nanotubes using nanomaterials as building blocks without any polymer matrix as support;^[212] these 3D graphene (all-carbon) scaffolds/foams have applications in several fields such as energy storage, filtration, thermal management and biomedical devices and implants.^[211][213]

Box-shaped graphene (BSG) nanostructure appeared after mechanical cleavage of pyrolytic graphite has been reported recently;^[214] the discovered nanostructure is a multilayer system of parallel hollow nanochannels located along the surface and having quadrangular cross-section. The thickness of the channel walls is approximately equal to 1 nm. Potential fields of BSG application include: ultra-sensitive detectors, high-performance catalytic cells, nanochannels for DNA sequencing and manipulation, high-performance heat sinking surfaces, rechargeable batteries of enhanced performance, nanomechanical resonators, electron multiplication channels in emission nanoelectronic devices, high-capacity sorbents for safe hydrogen storage.

Three dimensional bilayer graphene has also been reported.^[215][216]

Pillared graphene[edit]

Pillared graphene is a hybrid carbon, structure consisting of an oriented array of carbon nanotubes connected at each end to a sheet of graphene, it was first described theoretically by George Froudakis and colleagues of the University of Crete in Greece in 2008. Pillared graphene has not yet been synthesised in the laboratory, but it has been suggested that it may have useful electronic properties, or as a hydrogen storage material.

Reinforced graphene[edit]

Graphene reinforced with embedded carbon nanotube reinforcing bars ("rebar") is easier to manipulate, while improving the electrical and mechanical qualities of both materials.^[217][218]

Functionalized single- or multiwalled carbon nanotubes 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. π–π stacking domains add more strength. The nanotubes can overlap, making the material a better conductor than standard CVD-grown graphene; the nanotubes effectively bridge the grain boundaries found in conventional graphene. The technique eliminates the traces of substrate on which later-separated sheets were deposited using epitaxy.^[217]

Stacks of a few layers have been proposed as a cost-effective and physically flexible replacement for indium tin oxide (ITO) used in displays and photovoltaic cells.^[217]

Molded graphene[edit]

A film of graphene that had been soaked in solvent to make it swell and become malleable was overlaid on an underlying substrate "former"; the solvent evaporated over time, leaving behind a layer of graphene that had taken on the shape of the underlying structure. In this way the team^[who?] was able to produce a range of relatively intricate micro-structured shapes.^[219] Features vary from 3.5 to 50 μm. Pure graphene and gold-decorated graphene were each successfully integrated with the substrate.^[220]

Graphene aerogel[edit]

An aerogel made of graphene layers separated by carbon nanotubes was measured at 0.16 milligrams per cubic centimeter. A solution of graphene and carbon nanotubes in a mold is freeze dried to dehydrate the solution, leaving the aerogel; the material has superior elasticity and absorption. It can recover completely after more than 90% compression, and absorb up to 900 times its weight in oil, at a rate of 68.8 grams per second.^[221]

Graphene nanocoil[edit]

In 2015 a coiled form of graphene was discovered in graphitic carbon (coal); the spiraling effect is produced by defects in the material's hexagonal grid that causes it to spiral along its edge, mimicking a Riemann surface, with the graphene surface approximately perpendicular to the axis. When voltage is applied to such a coil, current flows around the spiral, producing a magnetic field; the phenomenon applies to spirals with either zigzag or armchair patterns, although with different current distributions. Computer simulations indicated that a conventional spiral inductor of 205 microns in diameter could be matched by a nanocoil just 70 nanometers wide, with a field strength reaching as much as 1 tesla.^[222]

The nano-solenoids analyzed through computer models at Rice should be capable of producing powerful magnetic fields of about 1 tesla, about the same as the coils found in typical loudspeakers, according to Yakobson and his team – and about the same field strength as some MRI machines, they found the magnetic field would be strongest in the hollow, nanometer-wide cavity at the spiral's center.^[222]

A solenoid made with such a coil behaves as a quantum conductor whose current distribution between the core and exterior varies with applied voltage, resulting in nonlinear inductance.^[223]

Production[edit]

A rapidly increasing list of production techniques have been developed to enable graphene's use in commercial applications.

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.^[19]

In all cases, graphene must bond to a substrate to retain its two-dimensional shape.^[19]

Exfoliation[edit]

As of 2014, exfoliation produced graphene with the lowest number of defects and highest electron mobility.^[86]

Geim and Novoselov initially used adhesive tape to pull graphene sheets away from graphite. Achieving single layers typically requires multiple exfoliation steps. After exfoliation the flakes are deposited on a silicon wafer. Crystallites larger than 1 mm and visible to the naked eye can be obtained.^[224]

Alternatively a sharp single-crystal diamond wedge penetrates onto the graphite source to cleave layers.^[225]

P. Boehm reported producing monolayer flakes of reduced graphene oxide in 1962.^[226][227] Rapid heating of graphite oxide and exfoliation yields highly dispersed carbon powder with a few percent of graphene flakes.

Another method is reduction of graphite oxide monolayer films, e.g. by hydrazine with annealing in argon/hydrogen with an almost intact carbon framework that allows efficient removal of functional groups. Measured charge carrier mobility exceeded 1,000 centimetres (393.70 in)/Vs.^[228]

In 2014 defect-free, unoxidized graphene-containing liquids were made from graphite using mixers that produce local shear rates greater than 10×10⁴.^[229][230]

Burning a graphite oxide coated DVD produced a conductive graphene film (1738 siemens per meter) and specific surface area (1520 square meters per gram) that was highly resistant and malleable.^[231]

Dispersing graphite in a liquid medium can produce graphene by sonication followed by centrifugation,^[232] producing concentrations 2.1 mg/ml in N-methylpyrrolidone.^[233] Using a suitable ionic liquid as the dispersing liquid medium produced concentrations of 5.33 mg/ml.^[234] Restacking is an issue with this technique.

Adding a surfactant to a solvent prior to sonication prevents restacking by adsorbing to the graphene's surface; this produces a higher graphene concentration, but removing the surfactant requires chemical treatments.^{[citation needed]}

Sonicating graphite at the interface of two immiscible liquids, most notably heptane and water, produced macro-scale graphene films; the graphene sheets are adsorbed to the high energy interface between the materials and are kept from restacking. The sheets are up to about 95% transparent and conductive.^[235]

With definite cleavage parameters, the box-shaped graphene (BSG) nanostructure can be prepared on graphite crystal.^[214]

Molten salts[edit]

Graphite particles can be corroded in molten salts to form a variety of carbon nanostructures including graphene.^[236] Hydrogen cations, dissolved in molten lithium chloride, can be discharged on cathodically polarized graphite rods, which then intercalate, peeling graphene sheets; the graphene nanosheets produced displayed a single-crystalline structure with a lateral size of several hundred nanometers and a high degree of crystallinity and thermal stability.^[237]

Electrochemical synthesis[edit]

Electrochemical synthesis can exfoliate graphene. Varying a pulsed voltage controls thickness, flake area, number of defects and affects its properties; the process begins by bathing the graphite in a solvent for intercalation. The process can be tracked by monitoring the solution's transparency with an LED and photodiode. ^[238][239]

Hydrothermal self-assembly[edit]

Graphene has been prepared by using a sugar (e.g. glucose, sugar, fructose, etc.) This substrate-free "bottom-up" synthesis is safer, simpler and more environmentally friendly than exfoliation. The method can control thickness, ranging from monolayer to multilayers, which is known as "Tang-Lau Method".^[240]

Hydrothermal reduction of graphene oxide[edit]

A dispersed reduced graphene oxide suspension was synthesized in water by a hydrothermal dehydration method without using any surfactant; the approach is facile, industrially applicable, environmentally friendly and cost effective. Viscosity measurements confirmed that the graphene colloidal suspension (Graphene nanofluid) exhibit Newtonian behavior, with the viscosity showing close resemblance to that of water.^[241]

Chemical vapor deposition[edit]

Epitaxy[edit]

Epitaxial graphene may be coupled to surfaces weakly enough (by Van der Waals forces) to retain the two dimensional electronic band structure of isolated graphene.^[242]

Heating silicon carbide (SiC) to high temperatures (1100 °C) under low pressures (c. 10⁻⁶ torr) reduces it to graphene.^{[101][102][103][104][105][243]}

A normal silicon wafer coated with a layer of germanium (Ge) dipped in dilute hydrofluoric acid strips the naturally forming germanium oxide groups, creating hydrogen-terminated germanium. CVD can coat that with graphene.^[244][245]

The direct synthesis of graphene on insulator TiO₂ with high-dielectric-constant (high-κ). A two-step CVD process is shown to grow graphene directly on TiO₂ crystals or exfoliated TiO₂ nanosheets without using any metal catalyst.^[246]

Metal substrates[edit]

The atomic structure of metal substrates including ruthenium,^[247] iridium,^[248] nickel^[249] and copper^[250]

Sodium ethoxide pyrolysis[edit]

Gram-quantities were produced by the reduction of ethanol by sodium metal, followed by pyrolysis and washing with water.^[251]

Roll-to-roll[edit]

In 2014 a two-step roll-to-roll manufacturing process was announced; the first roll-to-roll step produces the graphene via chemical vapor deposition. The second step binds the graphene to a substrate.^[252][253]

Cold wall[edit]

Growing graphene in an industrial resistive-heating cold wall CVD system was claimed to produce graphene 100 times faster than conventional CVD systems, cut costs by 99% and produce material with enhanced electronic qualities.^[254][255]

Wafer scale CVD graphene[edit]

CVD graphene is scalable and has been integrated with ubiquitous CMOS technology via growth on deposited Cu thin film catalyst on 100 to 300 mm standard Si/SiO2 wafers^{[256][257][258]} on an Axitron Black Magic system. Monolayer graphene coverage of >95% is achieved on 100 to 300 mm wafer substrates with negligible defects, confirmed by extensive Raman mapping.^[257][258]

Nanotube slicing[edit]

Graphene can be created by opening carbon nanotubes by cutting or etching.^[259] In one such method multi-walled carbon nanotubes are cut open in solution by action of potassium permanganate and sulfuric acid.^[260][261]

Carbon dioxide reduction[edit]

A highly exothermic reaction combusts magnesium in an oxidation–reduction reaction with carbon dioxide, producing carbon nanoparticles including graphene and fullerenes.^[262]

Spin coating[edit]

In 2014, carbon nanotube-reinforced graphene was made via spin coating and annealing functionalized carbon nanotubes.^[217]

Supersonic spray[edit]

Supersonic acceleration of droplets through a Laval nozzle was used to deposit reduced graphene-oxide on a substrate; the energy of the impact rearranges that carbon atoms into flawless graphene.^[263][264]

Another approach sprays buckyballs at supersonic speeds onto a substrate; the balls cracked open upon impact, and the resulting unzipped cages then bond together to form a graphene film.^[265]

Laser[edit]

In 2014 a CO
₂ infrared laser produced and patterned porous three-dimensional graphene film networks from commercial polymer films. The result exhibits high electrical conductivity. Laser-induced production appeared to allow roll-to-roll manufacturing processes.^[266]

Microwave-assisted oxidation[edit]

In 2012, microwave energy was reported to directly synthesize graphene in one step;^[267] this approach avoids use of potassium permanganate in the reaction mixture. It was also reported that by microwave radiation assistance, graphene oxide with or without holes can be synthesized by controlling microwave time.^[268] Microwave heating can dramatically shorten the reaction time from days to seconds.

Ion implantation[edit]

Accelerating carbon ions inside an electrical field into a semiconductor made of thin nickel films on a substrate of SiO2/Si, creates a wafer-scale (4 inches (100 mm)) wrinkle/tear/residue-free graphene layer at a relatively low temperature of 500 °C.^[269][270]

Graphene analogs[edit]

Graphene analogs^[271] (also referred to as "artificial graphene") are two-dimensional systems which exhibit similar properties to graphene. Graphene analogs are studied intensively since the discovery of graphene in 2004. People try to develop systems in which the physics is easier to observe and to manipulate than in graphene. In those systems, electrons are not always the particles which are used, they might be optical photons,^[272] microwave photons,^[273] plasmons,^[274] microcavity polaritons,^[275] or even atoms.^[276] Also, the honeycomb structure in which those particles evolve can be of a different nature than carbon atoms in graphene, it can be, respectively, a photonic crystal, an array of metallic rods, metallic nanoparticles, a lattice of coupled microcavities, or an optical lattice.

Applications[edit]

Graphene is a transparent and flexible conductor that holds great promise for various material/device applications, including solar cells,^[277] light-emitting diodes (LED), touch panels, and smart windows or phones.^[278] According to information from Changzhou, China-based 2D Carbon Graphene Material Co.,Ltd, graphene-based touch panel modules have been sold in volume to cell phone, wearable device, and home appliance manufacturers.^{[citation needed]} For instance, smartphone products with graphene touch screens are already on the market.

In 2013, Head announced their new range of graphene tennis racquets.^[279]

As of 2015, there is one product available for commercial use: a graphene-infused printer powder.^[280] Many other uses for graphene have been proposed or are under development, in areas including electronics, biological engineering, filtration, lightweight/strong composite materials, photovoltaics and energy storage.^[211][281] Graphene is often produced as a powder and as a dispersion in a polymer matrix; this dispersion is supposedly suitable for advanced composites,^[282][283] paints and coatings, lubricants, oils and functional fluids, capacitors and batteries, thermal management applications, display materials and packaging, solar cells, inks and 3D-printers’ materials, and barriers and films.^[284]

In 2016, researchers have been able to make a graphene film that can absorb 95% of light incident on it,^[285] it is also getting cheaper; recently scientists at the University of Glasgow have produced graphene at a cost that is 100 times less than the previous methods.^[286]

In August 2, 2016, BAC's new Mono model is said to be made out of graphene as a first of both a street-legal track car and a production car.^[287]

Health risks[edit]

The toxicity of graphene has been extensively debated in the literature; the most comprehensive review on graphene toxicity published by Lalwani et al. exclusively summarizes the in vitro, in vivo, antimicrobial and environmental effects and highlights the various mechanisms of graphene toxicity.^[288] Results show that the toxicity of graphene is dependent on several factors such as shape, size, purity, post-production processing steps, oxidative state, functional groups, dispersion state, synthesis methods, route and dose of administration, and exposure times.

Research at Stony Brook University showed that graphene nanoribbons, graphene nanoplatelets and graphene nano–onions are non-toxic at concentrations up to 50 µg/ml; these nanoparticles do not alter the differentiation of human bone marrow stem cells towards osteoblasts (bone) or adipocytes (fat) suggesting that at low doses graphene nanoparticles are safe for biomedical applications.^[289] Research at Brown university found that 10 µm few-layered graphene flakes are able to pierce cell membranes in solution, they were observed to enter initially via sharp and jagged points, allowing graphene to be internalized in the cell. The physiological effects of this remain uncertain, and this remains a relatively unexplored field.^[290][291]

See also[edit]

References[edit]

Sources[edit]

• Geim, A. K.; Novoselov, K. S. (2007). "The rise of graphene". Nature Materials. 6 (3): 183–91. Bibcode:2007NatMa...6..183G. doi:10.1038/nmat1849. PMID 17330084.

External links[edit]

Wikimedia Commons has media related to Graphene.

• Manchester's Revolutionary 2D Material at The University of Manchester
• Graphene at The Periodic Table of Videos (University of Nottingham)
• Peres, N M R; Ribeiro, R M (2009). "Focus on Graphene". New Journal of Physics. 11 (9): 095002. Bibcode:2009NJPh...11i5002P. doi:10.1088/1367-2630/11/9/095002.
• Graphene: Patent surge reveals global race
• 'Engineering Controls for Nano-scale Graphene Platelets During Manufacturing and Handling Processes' (PDF)
• Band structure of graphene (PDF).