Graphene (/ˈɡræfiːn/)[1] is a variety of theelementcarbon which occurs naturally in small amounts. In graphene, the carbon forms a sheet of interlockedatoms as hexagons one carbon atom thick. The result resembles the face of ahoneycomb. When many hundreds of graphene layers build up, they are called graphite.
Commonly known types of carbon arediamond andgraphite. In 1947, the Canadian physicist P. R. Wallace suggested carbon could also exist in sheets. The German chemist Hanns-Peter Boehm and coworkers isolated single sheets from graphite, giving them the name graphene in 1986. In 2004, the material was characterized by Andre Geim and Konstantin Novoselov at theUniversity of Manchester, England. They received the 2010 Nobel Prize in Physics for their experiments.
In technical terms, graphene is acarbon allotrope consisting of asingle layer of atoms arranged in ahoneycomb planarnanostructure.[2][3] The name "graphene" is derived from "graphite" and the suffix-ene, indicating the presence of double bonds within the carbon structure.
Graphene is known for its exceptionally hightensile strength,electrical conductivity,transparency, and being the thinnest two-dimensional material in the world.[4] Despite the nearly transparent nature of a single graphene sheet, graphite (formed from stacked layers of graphene) appears black because it absorbs all visible light wavelengths.[5][6] On a microscopic scale, graphene is the strongest material ever measured.[7][8]
Photograph of a suspended graphene membrane in transmitted light. This one-atom-thick material can be seen with the naked eye because it absorbs approximately 2.3% of light.[5][6]
The existence of graphene was first theorized in 1947 byPhilip R. Wallace during his research on graphite's electronic properties, while the termgraphene was first defined byHanns-Peter Boehm in 1987.[9] In 2004, the material was isolated and characterized byAndre Geim andKonstantin Novoselov at theUniversity of Manchester[10][11] using a piece of graphite andadhesive tape.[12] In 2010, Geim and Novoselov were awarded theNobel Prize in Physics for their "groundbreaking experiments regarding the two-dimensional material graphene".[13] While small amounts of graphene are easy to produce using the method by which it was originally isolated, attempts to scale and automate the manufacturing process for mass production have had limited success out of concern for cost-effectiveness and quality control.[14][15] The global graphene market was $9 million in 2012,[16] with most of the demand from research and development insemiconductors, electronics,electric batteries,[17] andcomposites.
TheIUPAC (International Union of Pure and Applied Chemistry) advises using the term "graphite" for the three-dimensional material and reserving "graphene" for discussions about the properties or reactions of single-atom layers.[18] A narrower definition, of "isolated or free-standing graphene", requires that the layer be sufficiently isolated from its environment,[19] but would include layers suspended or transferred tosilicon dioxide orsilicon carbide.[20]
The theory of graphene was first explored byP. R. Wallace in 1947 as a starting point for understanding the electronic properties of 3D graphite. The emergent masslessDirac equation was separately pointed out in 1984 byGordon Walter Semenoff,[30] and by David P. Vincenzo and Eugene J. Mele.[31] Semenoff emphasized the occurrence in a magnetic field of an electronicLandau level precisely at theDirac point. This level is responsible for the anomalous integerQuantum Hall effect.[32][33][34]
Observations of thin graphite layers and related structures
Transmission electron microscopy (TEM) images of thingraphite samples consisting of a few graphene layers were published by G. Ruess and F. Vogt in 1948.[35] Eventually, single layers were also observed directly.[36] Single layers of graphite were also observed bytransmission electron microscopy within bulk materials, particularly inside soot obtained by chemicalexfoliation.[37]
From 1961 to 1962,Hanns-Peter Boehm published a study of extremely thin flakes of graphite.[38] The study measured flakes as small as ~0.4nm, which is around 3 atomic layers of amorphous carbon. This was the best possible resolution for TEMs in the 1960s. However, it is impossible to distinguish between suspended monolayer and multilayer graphene by their TEM contrasts, and the only known method is to analyze the relative intensities of various diffraction spots.[36] The first reliable TEM observations of monolayers are likely given in references 24 and 26 of Geim and Novoselov's 2007 review.[2]
In 1975, van Bommel et al.epitaxially grew a single layer of graphite on top of silicon carbide.[39] Others grew single layers of carbon atoms on other materials.[40][41] 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 between the two materials and, in some cases, hybridization between thed-orbitals of the substrate atoms and π orbitals of graphene, which significantly alter the electronic structure compared to that of free-standing graphene.
Boehm et al. coined the term "graphene" for the hypothetical single-layer structure in 1986.[42] The term was used again in 1987 to describe single sheets of graphite as a constituent ofgraphite intercalation compounds,[43] which can be seen as crystalline salts of the intercalant and graphene. It was also used in the descriptions ofcarbon nanotubes by R. Saito andMildred andGene Dresselhaus in 1992,[44] and in the description ofpolycyclic aromatic hydrocarbons in 2000 by S. Wang and others.[45]
Efforts to make thin films of graphite by mechanical exfoliation started in 1990.[46]Initial attempts employed exfoliation techniques similar to the drawing method. Multilayer samples down to 10 nm in thickness were obtained.[2]
In 2002, Robert B. Rutherford and Richard L. Dudman filed for a patent in the US on a method to produce graphene by repeatedly peeling off layers from a graphite flake adhered to a substrate, achieving a graphite thickness of 0.00001inches (0.00025millimetres). The key to success was the ability to quickly and efficiently identify graphene flakes on the substrate using optical microscopy, which provided a small but visible contrast between the graphene and the substrate.[47]
Another U.S. patent was filed in the same year by Bor Z. Jang and Wen C. Huang for a method to produce graphene-based on exfoliation followed by attrition.[48]
In 2014, inventorLarry Fullerton patented a process for producing single-layer graphene sheets by graphene's strongdiamagnetic properties.[49]
Graphene was properly isolated and characterized in 2004 byAndre Geim andKonstantin Novoselov at theUniversity of Manchester.[10][11] They pulled graphene layers from graphite with a commonadhesive tape in a process called micro-mechanical cleavage, colloquially referred to as the Scotch tape technique.[50] The graphene flakes were then transferred onto a thinsilicon dioxide layer on asilicon plate ("wafer"). The silica electrically isolated the graphene and weakly interacted with it, providing nearly charge-neutral graphene layers. The silicon beneath theSiO 2 could be used as a "back gate" electrode to vary the charge density in the graphene over a wide range.
This work resulted in the two winning the Nobel Prize in Physics in 2010 for their groundbreaking experiments with graphene.[50][51][52] Their publication and the surprisingly easy preparation method that they described, sparked a "graphene gold rush". Research expanded and split off into many different subfields, exploring different exceptional properties of the material—quantum mechanical, electrical, chemical, mechanical, optical, magnetic, etc.
Since the early 2000s, several companies and research laboratories have been working to develop commercial applications of graphene. In 2014, aNational Graphene Institute was established with that purpose at the University of Manchester, with a £60 million initial funding.[53] InNorth East England two commercial manufacturers, Applied Graphene Materials[54] and Thomas Swan Limited[55][56] have begun manufacturing.Cambridge Nanosystems[57] is a large-scale graphene powder production facility inEast Anglia.
Graphene is a single layer of carbon atoms tightly bound in a hexagonal honeycomb lattice. It is an allotrope of carbon in the form of a plane of sp2-bonded atoms with a molecular bond length = 0.142 nm (1.42 Å).
The area of ahexagon of side being, one hexagonal unit of graphene has an area of nm2. There are two carbon atoms per unit, together having a mass of mg. The (two-dimensional) density of graphene is therefore mg per square meter. A kilogram of graphene therefore has an area of m2 or 131.2hectares.
In a graphene sheet, each atom is connected to its three nearest carbon neighbors byσ-bonds, and a delocalizedπ-bond, which contributes to avalence band that extends over the whole sheet. This type ofbonding is also seen inpolycyclic aromatic hydrocarbons.[58][37] The valence band is touched by aconduction band, making graphene asemimetal with unusualelectronic properties that are best described by theories for massless relativistic particles.[2] Charge carriers in graphene show linear, rather than quadratic, dependence of energy on momentum, and field-effect transistors with graphene can be made that show bipolar conduction. Charge transport isballistic over long distances; the material exhibits largequantum oscillations and large nonlineardiamagnetism.[59]
Carbon orbitals 2s, 2px, 2py form the hybrid orbital sp2 with three major lobes at 120°. The remaining orbital, pz, extends out of the graphene's plane.Sigma and pi bonds in graphene. Sigma bonds result from an overlap of sp2 hybrid orbitals, whereas pi bonds emerge from tunneling between the protruding pz orbitals.
Three of the four outer-shellelectrons of each atom in a graphene sheet occupy three sp2hybrid orbitals – a combination of orbitals s, px and py — that are shared with the three nearest atoms, forming σ-bonds. The length of thesebonds is about 0.142 nanometers.[60][61]
The remaining outer-shell electron occupies a pz orbital that is oriented perpendicularly to the plane. These orbitals hybridize together to form two half-filled bands of free-moving electrons, π, and π∗, which are responsible for most of graphene's notable electronic properties.[60] Recent quantitative estimates of aromatic stabilization and limiting size derived from the enthalpies ofhydrogenation (ΔHhydro) agree well with the literature reports.[62]
Graphene sheets stack to form graphite with an interplanar spacing of 0.335 nm (3.35 Å).[63]
Graphene sheets in solid form usually show evidence in diffraction for graphite's (002) layering. This is true of some single-walled nanostructures.[64] However, unlayered graphene displaying only (hk0) rings have been observed in the core ofpresolar graphite onions.[65] TEM studies show faceting at defects in flat graphene sheets[66] and suggest a role for two-dimensional crystallization from a melt.
Thehexagonal lattice structure of isolated, single-layer graphene can be directly seen with transmission electron microscopy (TEM) of sheets of graphene suspended between bars of a metallic grid.[36] Some of these images showed a "rippling" of the flat sheet, with an amplitude of about one nanometer. These ripples may be intrinsic to the material as a result of the instability of two-dimensional crystals,[2][67][68] or may originate from the ubiquitous dirt seen in all TEM images of graphene.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.[69]
The hexagonal structure is also seen inscanning tunneling microscope (STM) images of graphene supported on silicon dioxide substrates[70] The rippling seen in these images is caused by the conformation of graphene to the substrates' lattice and is not intrinsic.[70]
Ab initio calculations show that a graphene sheet is thermodynamically unstable if its size is less than about 20 nm and becomes the most stablefullerene (as within graphite) only for molecules larger than 24,000 atoms.[71]
Electronic band structure of graphene. Valence and conduction bands meet at the six vertices of the hexagonal Brillouin zone and form linearly dispersing Dirac cones.
Graphene is a zero-gapsemiconductor because its conduction andvalence bands meet at theDirac points. The Dirac points are six locations inmomentum space on the edge of theBrillouin zone, divided into two non-equivalent sets of three points. These sets are labeled K and K'. These sets give graphene avalley degeneracy of. In contrast, for traditional semiconductors, the primary point of interest is generally Γ, where momentum is zero.[60]
If the in-plane direction is confined rather than infinite, its electronic structure changes. These confined structures are referred to asgraphene nanoribbons. If the nanoribbon has a "zig-zag" edge, the bandgap remains zero. If it has an "armchair" edge, the bandgap is non-zero.
Graphene's honeycomb structure can be viewed as two interleaving triangular lattices. This perspective has been used to calculate the band structure for a single graphite layer using a tight-binding approximation.[60]
Electrons propagating through the graphene honeycomb lattice effectively lose their mass, producingquasi-particles described by a 2D analogue of theDirac equation rather than theSchrödinger equation for spin-1/2 particles.[72][73]
The cleavage technique led directly to the first observation of the anomalous quantum Hall effect in graphene in 2005 by Geim's group and byPhilip Kim andYuanbo Zhang. This effect provided direct evidence of graphene's theoretically predictedBerry's phase of masslessDirac fermions and proof of the Dirac fermion nature of electrons.[32][34] These effects were previously observed in bulk graphite by Yakov Kopelevich, Igor A. Luk'yanchuk, and others, in 2003–2004.[74][75]
When atoms are placed onto the graphene hexagonal lattice, the overlap between thepz(π) orbitals and thes or thepx andpy orbitals is zero by symmetry. Therefore,pz electrons forming the π bands in graphene can be treated independently. Within this π-band approximation, using a conventionaltight-binding model, thedispersion relation (restricted to first-nearest-neighbor interactions only) that produces the energy of the electrons with wave vectork is:[30][76]
with the nearest-neighbor (π orbitals) hopping energyγ0 ≈2.8 eV and thelattice constanta ≈2.46 Å. The conduction and valence bands correspond to the different signs. With onepz 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 (theK point in the Brillouin zone), where there is a zero density of states but no band gap. Thus, graphene exhibits a semi-metallic (or zero-gap semiconductor) character, although this is not true for a graphene sheet rolled into acarbon nanotube due to its curvature. Two of the six Dirac points are independent, while the rest are equivalent by symmetry. Near theK-points, the energy dependslinearly on the wave vector, similar to a relativistic particle.[30][77] Since an elementary cell of the lattice has a basis of two atoms, thewave function has an effective2-spinor structure.
Consequently, at low energies even neglecting the true spin, electrons can be described by an equation formally equivalent to the masslessDirac equation. Hence, the electrons and holes are called Diracfermions.[30] This pseudo-relativistic description is restricted to thechiral limit, i.e., to vanishing rest massM0, leading to interesting additional features:[30][78]
HerevF ~106 m/s (.003 c) is theFermi velocity in graphene, which replaces the velocity of light in the Dirac theory; is the vector of thePauli matrices, is the two-component wave function of the electrons, andE is their energy.[72]
The equation describing the electrons' linear dispersion relation is:
where thewavevectorq is measured from the Brillouin zone vertex K,, and the zero of energy is set to coincide with the Dirac point. The equation uses a pseudospin matrix formula that describes two sublattices of the honeycomb lattice.[77]
Electron waves in graphene propagate within a single-atom layer, making them sensitive to the proximity of other materials such ashigh-κ dielectrics,superconductors, andferromagnets.
When the gate voltage in a field effect graphene device is changed from positive to negative, conduction switches from electrons to holes. The charge carrier concentration is proportional to the applied voltage. Graphene is neutral at zero gate voltage and resistivity is at its maximum because of the dearth of charge carriers. The rapid fall of resistivity when carriers are injected shows their high mobility, here of the order of 5000 cm2/Vs. n-Si/SiO2 substrate, T=1K.[2]
Graphene exhibits highelectron mobility at room temperature, with values reported in excess of15000 cm2⋅V−1⋅s−1.[2] Hole and electron mobilities are nearly identical.[73] The mobility is independent of temperature between10 K and100 K,[32][79][80] showing minimal change even at room temperature (300 K),[2] suggesting that the dominant scattering mechanism isdefect scattering. Scattering by graphene's acousticphonons intrinsically limits room temperature mobility in freestanding graphene to200000 cm2⋅V−1⋅s−1 at a carrier density of1012 cm−2.[80][81]
The correspondingresistivity of graphene sheets is10−8 Ω⋅m, lower than the resistivity ofsilver, which is the lowest known at room temperature.[82] However, onSiO 2 substrates, electron scattering by optical phonons of the substrate has a more significant effect than scattering by graphene's phonons, limiting mobility to40000 cm2⋅V−1⋅s−1.[80]
Charge transport can be affected by the adsorption of contaminants such aswater andoxygen molecules, leading to non-repetitive and large hysteresis I-V characteristics. Researchers need to conduct electrical measurements in a vacuum. Coating the graphene surface with materials such as SiN,PMMA or h-BN has been proposed for protection. In January 2015, the first stable graphene device operation in the air over several weeks was reported for graphene whose surface was protected byaluminum oxide.[83][84] In 2015,lithium-coated graphene exhibitedsuperconductivity, a first for graphene.[85]
Electrical resistance in 40-nanometer-widenanoribbons of epitaxial graphene changes in discrete steps. The ribbons' conductance exceeds predictions by a factor of 10. The ribbons can function more likeoptical waveguides orquantum dots, allowing electrons to flow smoothly along the ribbon edges. In copper, resistance increases proportionally with length as electrons encounter impurities.[86][87]
Transport is dominated by two modes: one ballistic and temperature-independent, and the other thermally activated. Ballistic electrons resemble those in cylindrical carbon nanotubes. At room temperature, resistance increases abruptly at a specific length—the ballistic mode at 16 micrometers and the thermally activated mode at 160 nanometers (1% of the former length).[86]
Graphene electrons can traverse micrometer distances without scattering, even at room temperature.[72]
Despite zero carrier density near the Dirac points, graphene exhibits a minimum conductivity on the order of. The origin of this minimum conductivity is still unclear. However, rippling of the graphene sheet or ionized impurities in theSiO 2 substrate may lead to local puddles of carriers that allow conduction.[73] Several theories suggest that the minimum conductivity should be; however, most measurements are of the order of or greater[2] and depend on impurity concentration.[88]
Near zero carrier density, graphene exhibits positive photoconductivity and negative photoconductivity at high carrier density, governed by the interplay between photoinduced changes of both theDrude weight and the carrier scattering rate.[89]
Graphene doped with various gaseous species (both acceptors and donors) can be returned to an undoped state by gentle heating in a vacuum.[88][90] Even fordopant concentrations in excess of 1012 cm−2, carrier mobility exhibits no observable change.[90] Graphene doped withpotassium inultra-high vacuum at low temperature can reduce mobility 20-fold.[88][91] 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)[92] is thought to occur. It may therefore be a suitable material for constructingquantum computers[93] usinganyonic circuits.[94]
Thequantum Hall effect is a quantum mechanical version of theHall effect, which is the production of transverse (perpendicular to the main current) conductivity in the presence of amagnetic field. The quantization of theHall effect at integer multiples (the "Landau level") of the basic quantitye2/h (wheree is the elementary electric charge andh is thePlanck constant). It can usually be observed only in very cleansilicon orgallium arsenide solids at temperatures around3 K and very high magnetic fields.
Graphene shows the quantum Hall effect: the conductivity quantization is unusual 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, whereN is the Landau level and the double valley and double spin degeneracies give the factor of 4.[2] These anomalies are present not only at extremely low temperatures but also at room temperature, i.e. at roughly 20 °C (293 K).[32]
This behavior is a direct result of graphene's chiral, massless Dirac electrons.[2][95] In a magnetic field, their spectrum has a Landau level with energy precisely at the Dirac point. This level is a consequence of theAtiyah–Singer index theorem and is half-filled in neutral graphene,[30] leading to the "+1/2" in the Hall conductivity.[33]Bilayer graphene also shows the quantum Hall effect, but with only one of the two anomalies (i.e.). In the second anomaly, the first plateau atN = 0 is absent, indicating that bilayer graphene stays metallic at the neutrality point.[2]
Chiral half-integer quantum Hall effect in graphene. Plateaux in transverse conductivity appear at half-integer multiples of 4e2/h.[2]
Unlike normal metals, graphene's longitudinal resistance shows maxima rather than minima for integral values of the Landau filling factor in measurements of theShubnikov–de Haas oscillations, thus the term "integral quantum Hall effect". These oscillations show a phase shift of π, known asBerry's phase.[32][73] Berry's phase arises due to chirality or dependence (locking) of the pseudospin quantum number on the momentum of low-energy electrons near the Dirac points.[34] The temperature dependence of the oscillations reveals that the carriers have a non-zero cyclotron mass, despite their zero effective mass in the Dirac-fermion formalism.[32]
Graphene samples prepared on nickel films, and on both the silicon face and carbon face ofsilicon carbide, show the anomalous effect directly in electrical measurements.[96][97][98][99][100][101] Graphitic layers on the carbon face of silicon carbide show a clearDirac spectrum inangle-resolved photoemission experiments, and the effect is observed in cyclotron resonance and tunneling experiments.[102]
Graphene's unit cell has two identical carbon atoms and two zero-energy states: one where the electron resides on atom A, and the other on atom B. However, if the unit cell's two atoms are not identical, the situation changes. Research shows that placinghexagonal boron nitride (h-BN) in contact with graphene can alter the potential felt at atoms A and B sufficiently for the electrons to develop a mass and an accompanying band gap of about 30 meV.[103]
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 viaoptical 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 atopological phase and displays much the same physics as topological insulators.[103]
If the mass in graphene can be controlled, electrons can be confined to massless regions by surrounding them with massive regions, allowing the patterning ofquantum dots, wires, and other mesoscopic structures. It also produces one-dimensional conductors along the boundary. These wires would be protected againstbackscattering and could carry currents without dissipation.[103]
While a single electron exhibits zero effective mass in graphene, as the entire set of electrons is moved with an electric field, the Fermi disk shifts, with both the total kinetic energy and the magnitude of the total momentum being increased. Since is minimum when, to the first order, must hold.[104] The proportional constant must be given by where is the collective mass (inertia) of graphene electrons. Another view of this is to associate the total kinetic energy with the current. Because the total momentum is proportional to the current, must hold. The proportional constant must be given by, where is a quantity of inductance unit, but its origin is not the Faraday induction but the inertial effect. is the graphene kinetic inductance,[104] and is given by per unit length for a graphene strip with a width ( is the Fermi energy). The kinetic inductance, representing the collective inertial effect, is intimately linked to graphene plasmonics, and was directly measured via microwave network analysis in 2014.[104]
In magnetic fields above 10tesla, additional plateaus of the Hall conductivity atσxy =νe2/h withν = 0, ±1, ±4 are observed.[105] A plateau atν = 3[106] and thefractional quantum Hall effect atν =1/3 were also reported.[106][107]
These observations withν = 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.
TheCasimir effect is an interaction between disjoint neutral bodies provoked by the fluctuations of the electromagnetic vacuum. Mathematically, it can be explained by considering the normal modes of electromagnetic fields, which explicitly depend on the boundary conditions on the interacting bodies' surfaces. Due to graphene's strong interaction with the electromagnetic field as a one-atom-thick material, the Casimir effect has garnered significant interest.[108][109]
TheVan der Waals force (or dispersion force) is also unusual, obeying an inverse cubic asymptoticpower law in contrast to the usual inverse quartic law.[110]
Graphene'spermittivity varies with frequency. Over a range from microwave to millimeter wave frequencies, it is approximately 3.3.[111] This permittivity, combined with its ability to function as both a conductor and as an insulator, theoretically allows compactcapacitors made of graphene to store large amounts of electrical energy.
Graphene exhibits unique optical properties, showing unexpectedly highopacity for an atomic monolayer in vacuum, absorbing approximatelyπα ≈ 2.3% oflight from visible to infrared wavelengths,[5][6][112] whereα is thefine-structure constant. This is due to the unusual low-energy electronic structure of monolayer graphene, characterized by electron and holeconical bands meeting at theDirac point, which is qualitatively different from more common quadratic massive bands.[5] Based on the Slonczewski–Weiss–McClure (SWMcC) band model of graphite, calculations usingFresnel equations in the thin-film limit account for interatomic distance, hopping values, and frequency, thus assessing optical conductance.
Experimental verification, though confirmed, lacks the precision required to improve upon existing techniques for determining thefine-structure constant.[113]
Multi-parametric surface plasmon resonance has been utilized to characterize both the thickness and refractive index of chemical-vapor-deposition (CVD)-grown graphene films. At a wavelength of 670 nm (6.7×10−7m), measured refractive index and extinction coefficient values are 3.135 and 0.897, respectively. Thickness determination yielded 3.7 Å across a 0.5mm area, consistent with the 3.35 Å reported for layer-to-layer carbon atom distance of graphite crystals.[114] This method is applicable for real-time label-free interactions of graphene with organic and inorganic substances. The existence of unidirectional surface plasmons in nonreciprocal graphene-based gyrotropic interfaces has been theoretically demonstrated, offering tunability from THz to near-infrared and visible frequencies by controlling graphene's chemical potential.[115] Particularly, the unidirectional frequency bandwidth can be 1– 2 orders of magnitude larger than that achievable with metal under similar magnetic field conditions, stemming from graphene's extremely small effective electron mass.
Graphene'sband gap can be tuned from 0 to0.25 eV (about 5-micrometer wavelength) by applying a voltage to a dual-gatebilayer graphenefield-effect transistor (FET) at room temperature.[116] The optical response ofgraphene nanoribbons is tunable into theterahertz regime by an applied magnetic fields.[117] Graphene/graphene oxide systems exhibitelectrochromic behavior, enabling tuning of both linear and ultrafast optical properties.[118]
A graphene-basedBragg grating (one-dimensionalphotonic crystal) has been fabricated, demonstrating its capability to excite surface electromagnetic waves in periodic structure using a 633 nm (6.33×10−7m) He–Ne laser as the light source.[119]
Graphene exhibits unique saturable absorption, which saturates when the input optical intensity exceeds a threshold value. This nonlinear optical behavior, termedsaturable absorption, occurs across the visible tonear-infrared spectrum, due to graphene's universal optical absorption and zero band gap. This property has enabled full-band mode-locking infiber lasers using graphene-based saturable absorbers, contributing significantly to ultrafastphotonics. Additionally, the optical response of graphene/graphene oxide layers can be electrically tuned.[118][120][121][122][123][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 microwaves and terahertz photonics devices, such as a microwave-saturable absorber, modulator, polarizer, microwave signal processing, and broadband wireless access networks.[125]
Under intense laser illumination, graphene exhibits a nonlinear phase shift due to the optical nonlinearKerr effect. Graphene demonstrates a large nonlinear Kerr coefficient of10−7 cm2⋅W−1, nearly nine orders of magnitude larger than that of bulk dielectrics,[126] suggesting its potential as a powerful nonlinear Kerr medium capable of supporting various nonlinear effects, includingsolitons.[127]
First-principle calculations incorporating quasiparticle corrections and many-body effects have been employed to study the electronic and optical properties of graphene-based materials. The approach was described as three stages.[128] With GW calculation, the properties of graphene-based materials were accurately investigated, including bulk graphene,[129]nanoribbons,[130] edge and surface functionalized armchair ribbons,[131] hydrogen saturated armchair ribbons,[132]Josephson effect in graphene SNS junctions with single localized defect[133] and armchair ribbon scaling properties.[134]
Graphene is considered an ideal material forspintronics due to its minimalspin–orbit interaction, the near absence ofnuclear magnetic moments in carbon, and weakhyperfine interaction. Electrical injection and detection ofspin current have been demonstrated up to room temperature,[135][136][137] with spin coherence length exceeding 1 micrometer observed at this temperature.[135] Control of spin current polarity via electrical gating has been achieved at low temperatures.[136]
Graphene's quantum Hall effect in magnetic fields above approximately 10tesla reveals additional interesting features. Additional plateaus in Hall conductivity at with have been observed,[105] along with plateau at[106] and a fractional quantum Hall effect at.[106][107]
These observations with 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 proposes thatmagnetic catalysis ofsymmetry breaking is responsible for this degeneracy lift.[citation needed]
Graphene exhibitsspintronic and magnetic properties concurrently.[138] Low-defect graphene Nano-meshes, fabricated using a non-lithographic approach, exhibit significant ferromagnetism even at room temperature. Additionally, a spin pumping effect has been observed with fields applied in parallel to the planes of few-layer ferromagnetic nano-meshes, while amagnetoresistance hysteresis loop is evident under perpendicular fields. Charge-neutral graphene has demonstrated magnetoresistance exceeding 100% in magnetic fields generated by standard permanent magnets (approximately 0.1 tesla), marking a record magneto resistivityat room temperature among known materials.[139]
In 2010, researchers magnetized graphene by producing it via CVD on the Ni(111) substrate[140] and then in 2014 by placing it on an atomically smooth layer of magneticyttrium iron garnet, maintaining graphene's electronic properties unaffected. Previous methods involved doping graphene with other substances.[141] The dopant's presence negatively affected its electronic properties.[142]
As notedabove, the (two-dimensional) density of graphene is 0.762 mg per square meter.
Graphene is the strongest material ever tested,[7][8] with an intrinsictensile strength of 130 GPa (19,000,000 psi) (with representative engineering tensile strength ~50-60 GPa for stretching large-area freestanding graphene) and aYoung's modulus (stiffness) close to 1 TPa (150,000,000 psi). The Nobel announcement illustrated this by saying that a 1 square meter graphene hammock would support a4 kg cat but would weigh only as much as one of the cat's whiskers, at0.77 mg (about 0.001% of the weight of1 m2 of paper).[143]
Large-angle bending of graphene monolayers with minimal strain demonstrates its mechanical robustness. Even under extreme deformation, monolayer graphene maintains excellent carrier mobility.[144]
Thespring constant of suspended graphene sheets has been measured using anatomic force microscope (AFM). Graphene sheets were suspended overSiO 2 cavities where an AFM tip was used to apply stress to the sheet to test its mechanical properties. Its spring constant was in the range 1–5 N/m and the stiffness was0.5 TPa, which differs from that of bulk graphite. These intrinsic properties could lead to applications such asNEMS as pressure sensors and resonators.[145] 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.[146]
In two-dimensional structures like graphene, thermal and quantum fluctuations cause relative displacement, with fluctuations growing logarithmically with structure size as per theMermin–Wagner theorem. This 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,[36] 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.[2][67][68][147][148] These ripples, when amplified by vacancy defects, induce a negativePoisson's ratio into graphene, resulting in the thinnestauxetic material known so far.[149]
Graphene-nickel (Ni) composites, created through plating processes, exhibit enhanced mechanical properties due to strong Ni-graphene interactions inhibiting dislocation sliding in the Ni matrix.[150]
In 2014, researchers fromRice University and theGeorgia Institute of Technology have indicated that despite its strength, graphene is also relativelybrittle, with afracture toughness of about 4 MPa√m.[151] This indicates that imperfect graphene is likely to crack in a brittle manner likeceramic materials, as opposed to manymetallic materials which tend to have fracture toughness 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.[152] The force was transmitted at 22.2 kilometres per second (13.8 mi/s).[153]
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.[154] The mechanical properties of polycrystalline graphene are affected by the nature of the defects, such asgrain-boundaries (GB) andvacancies, present in the system and the average grain-size.
Graphene grain boundaries typically contain heptagon-pentagon pairs. The arrangement of such defects depends on whether the GB is in a zig-zag or armchair direction. It further depends on the tilt-angle of the GB.[155] In 2010, researchers fromBrown 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.[156] In 2012, it was further shown that the strength can increase or decrease, depending on the detailed arrangements of the defects.[157] These predictions have since been supported by experimental evidence. In a 2013 study led by James Hone's group, researchers probed the elasticstiffness andstrength of CVD-grown graphene by combining nano-indentation and high-resolutionTEM. They found that the elastic stiffness is identical and strength is only slightly lower than those in pristine graphene.[158] In the same year, researchers fromUniversity of California, Berkeley andUniversity of California, Los Angeles probed bi-crystalline graphene withTEM andAFM. They found that the strength of grain boundaries indeed tends to increase with the tilt angle.[159]
While the presence of vacancies is not only prevalent in polycrystalline graphene, vacancies can have significant effects on the strength of graphene. The consensus is that the strength decreases along with increasing densities of vacancies. Various studies have shown that for graphene with a sufficiently low density of vacancies, the strength does not vary significantly from that of pristine graphene. On the other hand, a high density of vacancies can severely reduce the strength of graphene.[160]
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.[161][160][162] In fact, three notable theoretical or computational studies on this topic have led to three different conclusions.[163][164][165] First, in 2012, Kolakowski and Myer studied the mechanical properties of polycrystalline graphene with "realistic atomistic model", usingmolecular-dynamics (MD) simulation. To emulate the growth mechanism of CVD, they first randomly selectednucleation 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, and 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.[163] 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 a 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 pseudoHall-Petch relationship.[164] Third, in 2013, Z. D. Sha et al. studied the effect of grain size on the properties of polycrystalline graphene, by modeling the grain patches usingVoronoi construction. The GBs in this model consisted of heptagons, pentagons, and hexagons, as well as squares, octagons, and vacancies. Through MD simulation, contrary to the aforementioned study, they found an inverse Hall-Petch relationship, where the strength of graphene increases as the grain size increases.[165] Experimental observations and other theoretical predictions also gave differing conclusions, similar to the three given above.[162] 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.
Thermal transport in graphene is a burgeoning area of research, particularly for its potential applications in thermal management. Most experimental measurements have posted large uncertainties in the results of thermal conductivity due to the limitations of the instruments used. Following predictions for graphene and relatedcarbon nanotubes,[166] early measurements of thethermal conductivity of suspended graphene reported an exceptionally large thermal conductivity up to5300 W⋅m−1⋅K−1,[167] compared with the thermal conductivity of pyrolyticgraphite of approximately2000 W⋅m−1⋅K−1 at room temperature.[168] However, later studies primarily on more scalable but more defected graphene derived by Chemical Vapor Deposition have been unable to reproduce such high thermal conductivity measurements, producing a wide range of thermal conductivities between1500 –2500 W⋅m−1⋅K−1 for suspended single-layer graphene.[169][170][171][172] 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 about500 –600 W⋅m−1⋅K−1 at room temperature as a result of scattering of graphene lattice waves by the substrate,[173][174] and can be even lower for few-layer graphene encased in amorphous oxide.[175] Likewise, polymeric residue can contribute to a similar decrease in the thermal conductivity of suspended graphene to approximately500 –600 W⋅m−1⋅K−1 for bilayer graphene.[176]
Isotopic composition, specifically the ratio of12C to13C, significantly affects graphene's thermal conductivity. Isotopically pure12C graphene exhibits higher thermal conductivity than either a 50:50 isotope ratio or the naturally occurring 99:1 ratio.[177] It can be shown by using theWiedemann–Franz law, that the thermal conduction isphonon-dominated.[167] However, for a gated graphene strip, an applied gate bias causing aFermi energy shift much larger thankBT can cause the electronic contribution to increase and dominate over thephonon contribution at low temperatures. The ballistic thermal conductance of graphene is isotropic.[178][179]
Graphite, a 3D counterpart to graphene, exhibits abasal planethermal conductivity exceeding1000 W⋅m−1⋅K−1 (similar todiamond), 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 largerlattice spacing.[180] In addition, the ballistic thermal conductance of graphene is shown to give the lower limit of the ballistic thermal conductance, per unit circumference, length of carbon nanotubes.[181]
Graphene's thermal conductivity is influenced by its threeacoustic phonon modes: two lineardispersion relation dispersion relation in-plane modes (LA, TA) and one quadratic dispersion relation out-of-plane mode (ZA). At low temperatures, the dominance of the T1.5 thermal conductivity contribution of the out-of-plane mode supersedes theT2 dependence of the linear modes.[181] Some graphene phonon bands exhibit negativeGrüneisen parameters,[182] resulting in negativethermal expansion coefficient at low temperatures. The lowest negative Grüneisen parameters correspond to the lowest transverse acoustic ZA modes, whose frequencies increase with in-planelattice parameter, akin to a stretched string with higher frequency vibrations.[183]
Graphene has a theoreticalspecific surface area (SSA) of2630 m2/g. This is much larger than that reported to date for carbon black (typically smaller than900 m2/g) or for carbon nanotubes (CNTs), from ≈100 to1000 m2/g and is similar toactivated carbon.[184]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 anyallotrope. Defects within a sheet increase its chemical reactivity.[185] The onset temperature of reaction between the basal plane of single-layer graphene and oxygen gas is below 260 °C (530 K).[186] Graphene burns at very low temperatures (e.g., 350 °C (620 K)).[187] Graphene is commonly modified with oxygen- and nitrogen-containingfunctional groups and analyzed byinfrared spectroscopy andX-ray photoelectron spectroscopy. However, the determination of structures of graphene with oxygen-[188] and nitrogen-[189] functional groups require 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 multilayer sheets.[190]
Graphene can self-repair holes in its sheets, when exposed to molecules containing carbon, such ashydrocarbons. Bombarded with pure carbon atoms, the atoms perfectly align intohexagons, filling the holes.[191][192]
Despite the promising results in different cell studies and proof of concept studies, there is still incomplete understanding of the full biocompatibility of graphene-based materials.[193] Different cell lines react differently when exposed to graphene, and it has been shown that the lateral size of the graphene flakes, the form and surface chemistry can elicit different biological responses on the same cell line.[194]
There are indications that graphene has promise as a useful material for interacting with neural cells; studies on cultured neural cells show limited success.[195][196]
Graphene also has some utility inosteogenesis. Researchers at the Graphene Research Centre at theNational University of Singapore (NUS) discovered in 2011 the ability of graphene to accelerate the osteogenic differentiation of humanmesenchymal stem cells without the use of biochemical inducers.[197]
Graphene can be used in biosensors; in 2015, researchers demonstrated that a graphene-based sensor can be used to detect a cancer risk biomarker. In particular, by using epitaxial graphene on silicon carbide, they were repeatedly able to detect 8-hydroxydeoxyguanosine (8-OHdG), a DNA damage biomarker.[198]
The electronic 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.[199] 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.
In 2013 a group of Polish scientists presented a production unit that allows the manufacture of continuous monolayer sheets.[200] The process is based on graphene growth on a liquid metal matrix.[201] The product of this process was calledHigh Strength Metallurgical Graphene. In a new study published in Nature, the researchers have used a single-layer graphene electrode and a novel surface-sensitive non-linear spectroscopy technique to investigate the top-most water layer at the electrochemically charged surface. They found that the interfacial water response to the applied electric field is asymmetric concerning the nature of the applied field.[202]
Bilayer graphene displays theanomalous quantum Hall effect, a tunableband gap[203] and potential forexcitonic condensation[204] –making it a promising candidate foroptoelectronic andnanoelectronic applications. Bilayer graphene typically can be found either intwisted 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.[205] Stacking order and orientation govern the optical and electronic properties of bilayer graphene.
One way to synthesize bilayer graphene is viachemical vapor deposition, which can produce large bilayer regions that almost exclusively conform to a Bernal stack geometry.[205]
It has been shown that the two graphene layers can withstand important strain or doping mismatch[206] which ultimately should lead to their exfoliation.
Turbostratic graphene exhibits weak interlayer coupling, and the spacing is increased with respect to Bernal-stacked multilayer graphene. Rotational misalignment preserves the 2D electronic structure, as confirmed byRaman spectroscopy.[207] The D peak is very weak, whereas the 2D and G peaks remain prominent.[207]
A rather peculiar feature is that the I2D/IG ratio can exceed 10. However, most importantly, the M peak, which originates from AB stacking, is absent, whereas the TS1 and TS2 modes are visible in theRaman spectrum.[208][209] The material is formed through conversion of non-graphenic carbon into graphenic carbon without providing sufficient energy to allow for the reorganization through annealing of adjacent graphene layers into crystalline graphitic structures.
Periodically stacked graphene and its insulating isomorph provide a fascinating structural element in implementing highly functional superlattices at the atomic scale, which offers possibilities for designing nanoelectronic and photonic devices. Various types of superlattices can be obtained by stacking graphene and its related forms.[210] 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.
A superlattice corresponds to a periodic or quasi-periodic arrangement of different materials and can be described by a superlattice period which confers a new translational symmetry to the system, impacting their phonon dispersions and subsequently their thermal transport properties. Recently, uniform monolayer graphene-hBN structures have been successfully synthesized via lithography patterning coupled with chemical vapor deposition (CVD).[211] Furthermore, superlattices of graphene-HBN are ideal model systems for the realization and understanding of coherent (wave-like) and incoherent (particle-like) phonon thermal transport.[212][213][214][215][216]
Names for graphene edge topologiesGNR Electronic band structure of graphene strips of varying widths in zig-zag orientation. Tight-binding calculations show that they are all metallic.GNR Electronic band structure of graphene strips of various widths in the armchair orientation. Tight-binding calculations show that they are semiconducting or metallic depending on width (chirality).
Graphene nanoribbons ("nanostripes" in the "zig-zag"/"zigzag" orientation), at low temperatures, show spin-polarized metallic edge currents, which also suggests applications in the new field ofspintronics. (In the "armchair" orientation, the edges behave like semiconductors.[72])
Agraphene quantum dot (GQD) is a graphene fragment with a size lesser than 100 nm. The properties of GQDs are different from bulk graphene due to the quantum confinement effects which only become apparent when the size is smaller than 100 nm.[217][218][219]
Graphene oxide is usually produced through chemical exfoliation of graphite. A particularly popular technique is the improvedHummers' method.[220] 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, calledgraphene oxide paper, have a measuredtensile modulus of 32GPa.[221] The chemical property of graphite oxide is related to the functional groups attached to graphene sheets. These can change thepolymerization pathway and similar chemical processes.[222] Graphene oxide flakes inpolymerss display enhanced photo-conducting properties.[223] Graphene is normallyhydrophobic and impermeable to all gases and liquids (vacuum-tight). However, when formed into a graphene oxide-based capillary membrane, both liquid water and water vapor flow through as quickly as if the membrane were not present.[224]
In 2022, researchers evaluated the biological effects of low doses on graphene oxide on larvae and imago ofDrosophila melanogaster. Results show that oral administration of graphene oxide at concentrations of 0.02-1% has a beneficial effect on the developmental rate and hatching ability of larvae. Long-term administration of a low dose of graphene oxide extends the lifespan of Drosophila and significantly enhances resistance to environmental stresses. These suggest that graphene oxide affects carbohydrate and lipid metabolism in adult Drosophila. These findings might provide a useful reference to assess the biological effects of graphene oxide, which could play an important role in a variety of graphene-based biomedical applications.[225]
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.
Soluble fragments of graphene can be prepared in the laboratory through chemical modification of graphite.[226] First, microcrystalline graphite is treated with an acidic mixture of sulfuric acid andnitric acid. A series of oxidation and exfoliation steps produce small graphene plates withcarboxyl groups at their edges. These are converted toacid chloride groups by treatment withthionyl chloride; next, they are converted to the corresponding grapheneamide via treatment with octadecyl amine. The resulting material (circular graphene layers of 5.3 Å or 5.3×10−10m thickness) is soluble intetrahydrofuran,tetrachloromethane anddichloroethane.
Refluxing single-layer graphene oxide (SLGO) insolvents 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%.
Boehm titration results for various chemical reactions of single-layer graphene oxide, which reveal reactivity of the carboxylic groups and the resultant stability of the SLGO sheets after treatment.
Hydrazine reflux is commonly used for reducing SLGO to SLG(R), buttitrations 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 withhydrochloric acid (< 1.0 M) leads to around 60% loss of COOH functionality. Room temperature treatment of SLGO withcarbodiimides 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).[227] 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 reaction types have been explored. SLGO has also been grafted withpolyallylamine, cross-linked throughepoxy groups. When filtered into graphene oxide paper, these composites exhibit increased stiffness and strength relative to unmodified graphene oxide paper.[228]
Fullhydrogenation from both sides of the graphene sheet results inGraphane, but partial hydrogenation leads to hydrogenated graphene.[229] Similarly, both-side fluorination of graphene (or chemical and mechanical exfoliation of graphite fluoride) leads tofluorographene (graphene fluoride),[230] while partial fluorination (generallyhalogenation) provides fluorinated (halogenated) graphene.
Graphene can be aligand tocoordinate 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.[231][232]
In 2011, researchers reported a novel yet simple approach to fabricating graphene fibers from chemical vapor deposition-grown graphene films.[233] The method was scalable and controllable, delivering tunable morphology and pore structure by controlling the evaporation of solvents with suitablesurface tension. Flexible all-solid-state supercapacitors based on these graphene fibers were demonstrated in 2013.[234]
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 1,290 W/m/K (1,290 watts per metre per kelvin), while tensile strength reached 1,080 MPa (157,000 psi).[235]
In 2016, kilometer-scale continuous graphene fibers with outstanding mechanical properties and excellent electrical conductivity were produced by high-throughput wet-spinning of graphene oxide liquid crystals followed bygraphitization through a full-scale synergetic defect-engineering strategy.[236] 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 fiber that has a tensile strength of 80 GPa (12,000,000 psi).[237]
In 2013, a three-dimensionalhoneycomb of hexagonally arranged carbon was termed 3D graphene, and self-supporting 3D graphene was also produced.[238] 3D structures of graphene can be fabricated by using either CVD or solution-based methods. A 2016 review by Khurram and Xu et al. provided a summary of then-state-of-the-art techniques for fabrication of the 3D structure of graphene and other related two-dimensional materials.[239] In 2013, researchers atStony Brook University 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.[240] These 3D graphenes (all-carbon) scaffolds/foams have applications in several fields such as energy storage, filtration, thermal management, and biomedical devices and implants.[239][241]
Box-shaped graphene (BSG)nanostructure appearing after mechanical cleavage ofpyrolytic graphite was reported in 2016.[242] 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-sensitivedetectors, high-performance catalytic cells, nanochannels forDNAsequencing and manipulation, high-performance heat sinking surfaces,rechargeable batteries of enhanced performance,nanomechanical resonators, electron multiplication channels in emissionNano-electronic devices, high-capacitysorbents for safehydrogen storage.
Three dimensional bilayer graphene has also been reported.[243][244]
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 at theUniversity of Crete in Greece in 2008. Pillared graphene has not yet been synthesized in the laboratory, but it has been suggested that it may have useful electronic properties, or as a hydrogen storage material.
Graphene reinforced with embeddedcarbon nanotube reinforcing bars ("rebar") is easier to manipulate, while improving the electrical and mechanical qualities of both materials.[245][246]
Functionalized single- or multi-walled carbon nanotubes are spin-coated on copper foils and then heated and cooled, using the nanotubes themselves as the carbon source. Under heating, the functionalcarbon groups decompose into graphene, while the nanotubes partially split and form in-planecovalent 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 thegrain boundaries found in conventional graphene. The technique eliminates the traces of substrate on which later-separated sheets were deposited using epitaxy.[245]
Stacks of a few layers have been proposed as a cost-effective and physically flexible replacement forindium tin oxide (ITO) used in displays andphotovoltaic cells.[245]
In 2015, researchers from theUniversity of Illinois at Urbana–Champaign (UIUC) developed a new approach for forming 3D shapes from flat, 2D sheets of graphene.[247] 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, they were able to produce a range of relatively intricate micro-structured shapes.[248] Features vary from 3.5 to 50 μm. Pure graphene and gold-decorated graphene were each successfully integrated with the substrate.[249]
Anaerogel 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.[250]
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 aRiemann 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 1tesla.[251]
The nano-solenoids analyzed through computer models atRice University 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.[251]
Asolenoid made with such a coil behaves as a quantum conductor whose current distribution between the core and exterior varies with applied voltage, resulting in nonlinearinductance.[252]
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 becamesuperhydrophobic, and when used as a battery electrode, the material was shown to have as much as a 400% increase inelectrochemicalcurrent density.[253][254]
A rapidly increasing list of production techniques have been developed to enable graphene's use in commercial applications.[255]
Isolated 2D crystals cannot be grown via chemical synthesis beyond small sizes even in principle, because the rapid growth ofphonon density with increasing lateral size forces 2D crystallites to bend into the third dimension. In all cases, graphene must bond to a substrate to retain its two-dimensional shape.[19]
Small graphene structures, such as graphene quantum dots and nanoribbons, can be produced by "bottom-up" methods that assemble the lattice from organic molecule monomers (e. g. citric acid, glucose). "Top-down" methods, on the other hand, cut bulk graphite and graphene materials with strong chemicals (e. g. mixed acids).[256]
The most famous, clean and rather straightforward method of isolating graphene sheets, called micro-mechanical cleavage or more colloquially called the scotch tape method, was introduced by Novoselov et al. in 2004, which usesadhesive tape to mechanically cleave high-qualitygraphitecrystals into successively thinner platelets. Other methods do exist like exfoliation.[256]
Geim and Novoselov initially usedadhesive 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.[257]
As of 2014, exfoliation produced graphene with the lowest number of defects and highest electron mobility. One specific exfoliation technique involved using asharp single-crystal diamond wedge to penetrate the graphite source and precisely cleave individual layers. That same year, researchers also developed liquid-phase methods, creating defect-free, unoxidized graphene-containing liquids from graphite using mixers that generate extremely high local shear rates greater than10×104.[258][259]
A 2014 study published inNature Materials demonstrated that scalable production of defect-free graphene is possible through shear exfoliation using ahigh-shear mixer. This technique can produce large quantities of few-layer graphene in solution while preserving structural integrity.[260] As turbulence is not necessary for mechanical exfoliation, resonant acoustic mixing or low-speedball milling can also be effective in the production of high-yield and water-soluble graphene.[261][262]
Liquid phase exfoliation (LPE) is a relatively simple method that involves dispersing graphite in a liquid medium to produce graphene bysonication or high shear mixing, followed bycentrifugation. Restacking is an issue with this technique unless solvents with appropriate surface energy are used (e.g. NMP). Adding asurfactant 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.[263][264]
LPE results in nanosheets with a broad size distribution and thicknesses roughly in the range of 1-10 monolayers. However, liquid cascade centrifugation can be used to size-select the suspensions and achieve monolayer enrichment.[265]
Sonicating graphite at the interface of twoimmiscible liquids, most notablyheptane 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.[266]
With definite cleavage parameters, the box-shaped graphene (BSG)nanostructure can be prepared ongraphitecrystal.[242] A major advantage of LPE is that it can be used to exfoliate many inorganic 2D materials beyond graphene, e.g. BN, MoS2, WS2.[267]
Liquid-phase exfoliation can also be done by a less-known process of intercalatingsupercritical carbon dioxide (scCO2) into the interstitial spaces in the graphite lattice, followed by rapid depressurization. The scCO2 intercalates easily inside the graphite lattice at a pressure of roughly 100atm. Carbon dioxide turns gaseous as soon as the vessel is depressurized and makes the graphite explode into few-layered graphene.[256]
This method may have multiple advantages: being non-toxic, the graphite does not have to be chemically treated in any way before the process, and the whole process can be completed in a single step as opposed to other exfoliation methods.[256]
Another approach spraysbuckyballs 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.[271]
P. Boehm reported producing monolayer flakes of reduced graphene oxide in 1962.[272][273] Rapid heating of graphite oxide and exfoliation yields highly dispersed carbon powder with a few percent of graphene flakes.
Another method is the reduction of graphite oxide monolayer films, e.g. byhydrazine withannealing inargon/hydrogen with an almost intact carbon framework that allows efficient removal of functional groups. Measuredcharge carrier mobility exceeded 1,000 cm/Vs (10 m/Vs).[274]
Burning a graphite oxide coatedDVD produced a conductive graphene film (1,738 siemens per meter) and specific surface area (1,520 square meters per gram) that was highly resistant and malleable.[275]
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) exhibits Newtonian behavior, with the viscosity showing a close resemblance to that of water.[276]
Graphite particles can be corroded in molten salts to form a variety of carbon nanostructures including graphene.[277] 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.[278]
Electrochemical synthesis can exfoliate graphene. Varying a pulsed voltage controls thickness, flake area, and 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.[279][280]
Graphene has been prepared by using a sugar likeglucose,fructose, etc. This substrate-free "bottom-up" synthesis is safer, simpler and more environmentally friendly than exfoliation. The method can control the thickness, ranging from monolayer to multilayer, which is known as the "Tang-Lau Method".[281][282][283][284]
In 2012, microwave energy was reported to directly synthesize graphene in one step.[286] 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.[287] Microwave heating can dramatically shorten the reaction time from days to seconds.
Graphene can also be made bymicrowave assisted hydrothermal pyrolysis.[217][218]
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.[292]
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.[298][299]
Large-area Raman mapping of CVD graphene on deposited Cu thin film on 150 mm SiO2/Si wafers reveals >95% monolayer continuity and an average value of ~2.62 forI2D/IG. The scale bar is 200 μm.
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.[300][301]
CVD graphene is scalable and has been grown on deposited Cu thin film catalyst on 100 to 300 mm standard Si/SiO2 wafers[302][303][304] 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.[303][304]
As reported by a group led by D. H. Adamson, graphene can be produced from natural graphite while preserving the integrity of the sheets using the solvent interface trapping method (SITM). SITM uses a high-energy interface, such as oil and water, to exfoliate graphite to graphene. Stacked graphite delaminates, or spreads, at the oil/water interface to produce few-layer graphene in a thermodynamically favorable process in much the same way as small molecule surfactants spread to minimize the interfacial energy. In this way, graphene behaves like a 2D surfactant.[305][306][307] SITM has been reported for a variety of applications such conductive polymer-graphene foams,[308][309][310][311] conductive polymer-graphene microspheres,[312] conductive thin films[313] and conductive inks.[314]
A highly exothermic reaction combustsmagnesium in an oxidation-reduction reaction with carbon dioxide, producing carbon nanoparticles including graphene andfullerenes.[315]
Supersonic acceleration of droplets through aLaval nozzle was used to deposit reduced graphene oxide on a substrate. The energy of the impact rearranges those carbon atoms into flawless graphene.[316][317]
In 2014, aCO 2infrared laser was used to produce patterned porous three-dimensional laser-induced graphene (LIG) film networks from commercial polymer films. The resulting material exhibits high electrical conductivity and surface area. The laser induction process is compatible with roll-to-roll manufacturing processes.[318] A similar material, laser-induced graphene fibers (LIGF), was reported in 2018.[319]
In 2019, flash Joule heating (transient high-temperature electrothermal heating) was discovered to be a method to synthesize turbostratic graphene in bulk powder form. The method involves electrothermally converting various carbon sources, such as carbon black, coal, and food waste into micron-scale flakes of graphene.[208][320] More recent works demonstrated the use of mixedplastic waste, waste rubber tires, and pyrolysis ash as carbon feedstocks.[321][322][323] The graphenization process is kinetically controlled, and the energy dose is chosen to preserve the carbon in its graphenic state (excessive energy input leads to subsequent graphitization through annealing).
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.[324][325]
Integration of graphene in the widely employedCMOS fabrication process demands its transfer-free direct synthesis ondielectric substrates at temperatures below 500 °C. At theIEDM 2018, researchers fromUniversity of California, Santa Barbara, demonstrated a novel CMOS-compatible graphene synthesis process at 300 °C suitable for back-end-of-line (BEOL) applications.[326][327][328] The process involves pressure-assisted solid-statediffusion ofcarbon through athin-film of metal catalyst. The synthesized large-area graphene films were shown to exhibit high quality (viaRaman characterization) and similarresistivity values when compared with high-temperature CVD synthesized graphene films of the same cross-section down to widths of 20nm.
In addition to experimental investigation of graphene and graphene-based devices, numerical modeling and simulation of graphene has also been an important research topic. TheKubo formula provides an analytic expression for the graphene's conductivity and shows that it is a function of several physical parameters including wavelength, temperature, and chemical potential.[329] Moreover, a surface conductivity model, which describes graphene as an infinitesimally thin (two-sided) sheet with a local and isotropic conductivity, has been proposed. This model permits the derivation of analytical expressions for the electromagnetic field in the presence of a graphene sheet in terms of a dyadic Green function (represented using Sommerfeld integrals) and exciting electric current.[330]
Even though these analytical models and methods can provide results for several canonical problems for benchmarking purposes, many practical problems involving graphene, such as the design of arbitrarily shaped electromagnetic devices, are analytically intractable. With the recent advances in the field ofcomputational electromagnetics (CEM), various accurate and efficient numerical methods have become available for analysis of electromagnetic field/wave interactions on graphene sheets and/or graphene-based devices. A comprehensive summary of computational tools developed for analyzing graphene-based devices/systems is proposed.[331]
Graphene analogs[332] (also referred to as "artificial graphene") are two-dimensional systems which exhibit similar properties to graphene. Graphene analogs have been studied intensively since the discovery of graphene in 2004. People try to develop systems in which the physics is easier to observe and manipulate than in graphene. In those systems, electrons are not always the particles that are used. They might be optical photons,[333] microwave photons,[334] plasmons,[335] microcavity polaritons,[336] or even atoms.[337] Also, the honeycomb structure in which those particles evolve can be of a different nature than carbon atoms in graphene. It can be, respectively, aphotonic crystal, an array of metallic rods, metallicnanoparticles, a lattice of coupled microcavities, or anoptical lattice.
Graphene is a transparent and flexible conductor that holds great promise for various material/device applications, including solar cells,[338] light-emitting diodes (LED), integrated photonic circuit devices,[339][340] touch panels, and smart windows or phones.[341] Smartphone products with graphene touch screens are already on the market.[342]
In 2013, Head announced their new range of graphene tennis racquets.[343]
As of 2015, there is one product available for commercial use: a graphene-infused printer powder.[344] Many other uses for graphene have been proposed or are under development, in areas including electronics,biological engineering,filtration, lightweight/strongcomposite materials,photovoltaics andenergy storage.[239][345] Graphene is often produced as a powder and as a dispersion in a polymer matrix. This dispersion is supposedly suitable for advanced composites,[346][347] paints and coatings, lubricants, oils and functional fluids, capacitors and batteries, thermal management applications, display materials and packaging, solar cells, inks and 3D-printer materials, and barriers and films.[348]
On 2 August 2016,Briggs Automative Company's new Mono model is said to be made out of graphene as the first of both a street-legal track car and a production car.[349]
The potential of epitaxial graphene onSiC formetrology has been shown since 2010, displaying quantum Hall resistance quantization accuracy of three parts per billion in monolayer epitaxial graphene. Over the years precisions of parts-per-trillion in the Hall resistance quantization and giant quantum Hall plateaus have been demonstrated. Developments in the encapsulation and doping of epitaxial graphene have led to the commercialization of epitaxial graphene quantum resistance standards.[353]
Novel uses for graphene continue to be researched and explored. One such use is in combination with water-based epoxy resins to produce anticorrosive coatings.[354] The van der Waals nature of graphene and other two-dimensional (2D) materials also permits van der Waals heterostructures[355] and integrated circuits based onVan der Waals integration of 2D materials.[356][357]
Graphene is utilized in detecting gasses and chemicals in environmental monitoring, developing highly sensitive biosensors for medical diagnostics, and creating flexible, wearable sensors for health monitoring.[358][359] Graphene's transparency also enhances optical sensors, making them more effective in imaging and spectroscopy.[360]
One review on graphene toxicity published in 2016 by Lalwani et al. summarizes thein vitro,in vivo, antimicrobial and environmental effects and highlights the various mechanisms of graphene toxicity.[361] Another review published in 2016 by Ou et al. focused on graphene-family nanomaterials (GFNs) and revealed several typical mechanisms such as physical destruction,oxidative stress,DNA damage, inflammatory response,apoptosis,autophagy, andnecrosis.[362]
A 2020 study showed 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.[363]
In 2014, research atStony Brook University showed thatgraphene 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 marrowstem cells towardsosteoblasts (bone) oradipocytes (fat), suggesting that at low doses, graphene nanoparticles are safe for biomedical applications.[364] In 2013, research atBrown University found that 10 μm few-layered graphene flakes can piercecell 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 unknown, and this remains a relatively unexplored field.[365][366]
^"Graphene: A Complete Chemical History".ACS Material. 20 September 2019. Retrieved1 October 2024.In 1947, the existence of graphene was theorized by Philip R Wallace as an attempt to understand electronic properties of 3D graphite. He did not use the term "graphene", but instead referred to it as a "single hexagonal layer."
^Howe, J. Y.; Rawn, C. J.; Jones, L. E.; Ow, H. (June 2003). "Improved crystallographic data for graphite".Powder Diffraction.18 (2):150–154.Bibcode:2003PDiff..18..150H.doi:10.1154/1.1536926.
^DiVincenzo, D. P.; Mele, E. J. (1984). "Self-Consistent Effective Mass Theory for Intralayer Screening in Graphite Intercalation Compounds".Physical Review B.295 (4):1685–1694.Bibcode:1984PhRvB..29.1685D.doi:10.1103/PhysRevB.29.1685.
^Forbeaux, I.; Themlin, J.-M.; Debever, J.-M. (1998). "Heteroepitaxial graphite on 6H-SiC(0001): Interface formation through conduction-band electronic structure".Physical Review B.58 (24):16396–16406.Bibcode:1998PhRvB..5816396F.doi:10.1103/PhysRevB.58.16396.
^Boehm, H. P.; Setton, R.; Stumpp, E. (1986). "Nomenclature and terminology of graphite intercalation compounds".Carbon.24 (2):241–245.Bibcode:1986Carbo..24..241B.doi:10.1016/0008-6223(86)90126-0.A single carbon layer of the graphitic structure would be the final member of infinite size of this series. The termgraphene layer should be used for such a single carbon layer.
^Wang, S.; Yata, S.; Nagano, J.; Okano, Y.; Kinoshita, H.; Kikuta, H.; Yamabe, T. (2000). "A new carbonaceous material with large capacity and high efficiency for rechargeable Li-ion batteries".Journal of the Electrochemical Society.147 (7): 2498.Bibcode:2000JElS..147.2498W.doi:10.1149/1.1393559.
^Bor Z. Jang and Wen C. Huang (2002): "Nano-scaled graphene platesArchived 22 October 2020 at theWayback Machine". US Patent 7071258. Filed on 2002-10-21, granted on 2006-07-04, assigned to Global Graphene Group Inc; to expire on 6 January 2024.
^ab"The Story of Graphene".www.graphene.manchester.ac.uk. The University of Manchester. 10 September 2014. Retrieved9 October 2014.Following discussions with colleagues, Andre and Kostya adopted a method that researchers in surface science were using – using simple Sellotape to peel away layers of graphite to expose a clean surface for study under the microscope.
^Zdetsis, Aristides D.; Economou, E. N. (23 July 2015). "A Pedestrian Approach to the Aromaticity of Graphene and Nanographene: Significance of Huckel's (4 n +2)π Electron Rule".The Journal of Physical Chemistry C.119 (29):16991–17003.doi:10.1021/acs.jpcc.5b04311.
^Li, Zhilin; Chen, Lianlian; Meng, Sheng; Guo, Liwei; Huang, Jiao; Liu, Yu; Wang, Wenjun; Chen, Xiaolong (2015). "Field and temperature dependence of intrinsic diamagnetism in graphene: Theory and experiment".Phys. Rev. B.91 (9) 094429.Bibcode:2015PhRvB..91i4429L.doi:10.1103/PhysRevB.91.094429.S2CID55246344.
^Dixit, Vaibhav A.; Singh, Yashita Y. (June 2019). "How much aromatic are naphthalene and graphene?".Computational and Theoretical Chemistry.1162 112504.doi:10.1016/j.comptc.2019.112504.S2CID196975315.
^Kasuya, D.; Yudasaka, M.; Takahashi, K.; Kokai, F.; Iijima, S. (2002). "Selective Production of Single-Wall Carbon Nanohorn Aggregates and Their Formation Mechanism".J. Phys. Chem. B.106 (19):4947–4951.doi:10.1021/jp020387n.
^abcChen, J. H.; Jang, Chaun; Xiao, Shudong; Ishigami, Masa; Fuhrer, Michael S. (2008). "Intrinsic and Extrinsic Performance Limits of Graphene Devices onSiO 2".Nature Nanotechnology.3 (4):206–9.arXiv:0711.3646.doi:10.1038/nnano.2008.58.PMID18654504.S2CID12221376.
^Akturk, A.; Goldsman, N. (2008). "Electron transport and full-band electron-phonon interactions in graphene".Journal of Applied Physics.103 (5): 053702–053702–8.Bibcode:2008JAP...103e3702A.doi:10.1063/1.2890147.
^Baringhaus, J.; Ruan, M.; Edler, F.; Tejeda, A.; Sicot, M.; Taleb-Ibrahimi, A.; Li, A. P.; Jiang, Z.; Conrad, E. H.; Berger, C.; Tegenkamp, C.; De Heer, W. A. (2014). "Exceptional ballistic transport in epitaxial graphene nanoribbons".Nature.506 (7488):349–354.arXiv:1301.5354.Bibcode:2014Natur.506..349B.doi:10.1038/nature12952.PMID24499819.S2CID4445858.
^Kim, Kuen Soo; Zhao, Yue; Jang, Houk; Lee, Sang Yoon; Kim, Jong Min; Kim, Kwang S.; Ahn, Jong-Hyun; Kim, Philip; Choi, Jae-Young; Hong, Byung Hee (2009). "Large-scale pattern growth of graphene films for stretchable transparent electrodes".Nature.457 (7230):706–10.Bibcode:2009Natur.457..706K.doi:10.1038/nature07719.PMID19145232.S2CID4349731.
^abJobst, Johannes; Waldmann, Daniel; Speck, Florian; Hirner, Roland; Maude, Duncan K.; Seyller, Thomas; Weber, Heiko B. (2009). "How Graphene-like is Epitaxial Graphene? Quantum Oscillations and Quantum Hall Effect".Physical Review B.81 (19) 195434.arXiv:0908.1900.Bibcode:2010PhRvB..81s5434J.doi:10.1103/PhysRevB.81.195434.S2CID118710923.
^abShen, T.; Gu, J. J.; Xu, M.; Wu, Y. Q.; Bolen, M. L.; Capano, M. A.; Engel, L. W.; Ye, P. D. (2009). "Observation of quantum-Hall effect in gated epitaxial graphene grown on SiC (0001)".Applied Physics Letters.95 (17): 172105.arXiv:0908.3822.Bibcode:2009ApPhL..95q2105S.doi:10.1063/1.3254329.S2CID9546283.
^abWu, Xiaosong; Hu, Yike; Ruan, Ming; Madiomanana, Nerasoa K.; Hankinson, John; Sprinkle, Mike; Berger, Claire; de Heer, Walt A. (2009). "Half integer quantum Hall effect in high mobility single layer epitaxial graphene".Applied Physics Letters.95 (22): 223108.arXiv:0909.2903.Bibcode:2009ApPhL..95v3108W.doi:10.1063/1.3266524.S2CID118422866.
^abLara-Avila, Samuel; Kalaboukhov, Alexei; Paolillo, Sara; Syväjärvi, Mikael; Yakimova, Rositza; Fal'ko, Vladimir; Tzalenchuk, Alexander; Kubatkin, Sergey (7 July 2009). "SiC Graphene Suitable For Quantum Hall Resistance Metrology".Science Brevia.arXiv:0909.1193.Bibcode:2009arXiv0909.1193L.
^abAlexander-Webber, J. A.; Baker, A. M. R.; Janssen, T. J. B. M.; Tzalenchuk, A.; Lara-Avila, S.; Kubatkin, S.; Yakimova, R.; Piot, B. A.; Maude, D. K.; Nicholas, R. J. (2013). "Phase Space for the Breakdown of the Quantum Hall Effect in Epitaxial Graphene".Physical Review Letters.111 (9) 096601.arXiv:1304.4897.Bibcode:2013PhRvL.111i6601A.doi:10.1103/PhysRevLett.111.096601.PMID24033057.S2CID118388086.
^Braga, S.; Coluci, V. R.; Legoas, S. B.; Giro, R.; Galvão, D. S.; Baughman, R. H. (2004). "Structure and Dynamics of Carbon Nanoscrolls".Nano Letters.4 (5):881–884.Bibcode:2004NanoL...4..881B.doi:10.1021/nl0497272.
^Lee, G.-H.; Cooper, R. C.; An, S. J.; Lee, S.; van der Zande, A.; Petrone, N.; Hammerberg, A. G.; Lee, C.; Crawford, B.; Oliver, W.; Kysar, J. W.; Hone, J. (31 May 2013). "High-Strength Chemical-Vapor-Deposited Graphene and Grain Boundaries".Science.340 (6136):1073–1076.Bibcode:2013Sci...340.1073L.doi:10.1126/science.1235126.PMID23723231.S2CID35277622.
^abZhang, Teng; Li, Xiaoyan; Gao, Huajian (November 2015). "Fracture of graphene: a review".International Journal of Fracture.196 (1–2):1–31.doi:10.1007/s10704-015-0039-9.S2CID135899138.
^Akinwande, Deji; Brennan, Christopher J.; Bunch, J. Scott; Egberts, Philip; Felts, Jonathan R.; Gao, Huajian; Huang, Rui; Kim, Joon-Seok; Li, Teng; Li, Yao; Liechti, Kenneth M.; Lu, Nanshu; Park, Harold S.; Reed, Evan J.; Wang, Peng; Yakobson, Boris I.; Zhang, Teng; Zhang, Yong-Wei; Zhou, Yao; Zhu, Yong (May 2017). "A review on mechanics and mechanical properties of 2D materials—Graphene and beyond".Extreme Mechanics Letters.13:42–77.arXiv:1611.01555.Bibcode:2017ExML...13...42A.doi:10.1016/j.eml.2017.01.008.S2CID286118.
^abIsacsson, Andreas; Cummings, Aron W.; Colombo, Luciano; Colombo, Luigi; Kinaret, Jari M.; Roche, Stephan (19 December 2016). "Scaling properties of polycrystalline graphene: A review".2D Materials.4 (1): 012002.arXiv:1612.01727.doi:10.1088/2053-1583/aa5147.S2CID118840850.
^Klemens, P. G. (2001). "Theory of Thermal Conduction in Thin Ceramic Films".International Journal of Thermophysics.22 (1):265–275.doi:10.1023/A:1006776107140.S2CID115849714.
^Pettes, Michael Thompson; Jo, Insun; Yao, Zhen; Shi, Li (2011). "Influence of Polymeric Residue on the Thermal Conductivity of Suspended Bilayer Graphene".Nano Letters.11 (3):1195–1200.Bibcode:2011NanoL..11.1195P.doi:10.1021/nl104156y.PMID21314164.
^Lifshitz, I. M. (1952).Journal of Experimental and Theoretical Physics (in Russian). Vol. 22. p. 475.
^Bonaccorso, F.; Colombo, L.; Yu, G.; Stoller, M.; Tozzini, V.; Ferrari, A. C.; Ruoff, R. S.; Pellegrini, V. (2015). "Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage".Science.347 (6217) 1246501.Bibcode:2015Sci...347...41B.doi:10.1126/science.1246501.PMID25554791.S2CID6655234.
^Denis, P. A.; Iribarne, F. (2013). "Comparative Study of Defect Reactivity in Graphene".Journal of Physical Chemistry C.117 (37):19048–19055.doi:10.1021/jp4061945.
^Eftekhari, A.; Jafarkhani, P. (2013). "Curly Graphene with Specious Interlayers Displaying Superior Capacity for Hydrogen Storage".Journal of Physical Chemistry C.117 (48):25845–25851.doi:10.1021/jp410044v.
^Yamada, Y.; Yasuda, H.; Murota, K.; Nakamura, M.; Sodesawa, T.; Sato, S. (2013). "Analysis of heat-treated graphite oxide by X-ray photoelectron spectroscopy".Journal of Materials Science.48 (23):8171–8198.Bibcode:2013JMatS..48.8171Y.doi:10.1007/s10853-013-7630-0.S2CID96586004.
^Bonaccorso, Francesco; Colombo, Luigi; Yu, Guihua; Stoller, Meryl; Tozzini, Valentina; Ferrari, Andrea C.; Ruoff, Rodney S.; Pellegrini, Vittorio (2 January 2015). "Graphene, related two-dimensional crystals, and hybrid systems for energy conversion and storage".Science.347 (6217) 1246501.Bibcode:2015Sci...347...41B.doi:10.1126/science.1246501.PMID25554791.S2CID6655234.
^Liao, Ken-Hsuan; Lin, Yu-Shen; Macosko, Christopher W.; Haynes, Christy L. (27 July 2011). "Cytotoxicity of Graphene Oxide and Graphene in Human Erythrocytes and Skin Fibroblasts".ACS Applied Materials & Interfaces.3 (7):2607–2615.Bibcode:2011AAMI....3.2607L.doi:10.1021/am200428v.PMID21650218.
^Fabbro, Alessandra; Scaini, Denis; León, Verónica; Vázquez, Ester; Cellot, Giada; Privitera, Giulia; Lombardi, Lucia; Torrisi, Felice; Tomarchio, Flavia; Bonaccorso, Francesco; Bosi, Susanna; Ferrari, Andrea C.; Ballerini, Laura; Prato, Maurizio (26 January 2016). "Graphene-Based Interfaces Do Not Alter Target Nerve Cells".ACS Nano.10 (1):615–623.Bibcode:2016ACSNa..10..615F.doi:10.1021/acsnano.5b05647.hdl:11368/2860012.PMID26700626.
^Xu, Yang; He, K. T.; Schmucker, S. W.; Guo, Z.; Koepke, J. C.; Wood, J. D.; Lyding, J. W.; Aluru, N. R. (2011). "Inducing Electronic Changes in Graphene through Silicon (100) Substrate Modification".Nano Letters.11 (7):2735–2742.Bibcode:2011NanoL..11.2735X.doi:10.1021/nl201022t.PMID21661740.S2CID207573621.
^Kula, Piotr; Pietrasik, Robert; Dybowski, Konrad; Atraszkiewicz, Radomir; Szymanski, Witold; Kolodziejczyk, Lukasz; Niedzielski, Piotr; Nowak, Dorota (2014). "Single and Multilayer Growth of Graphene from the Liquid Phase".Applied Mechanics and Materials.510:8–12.doi:10.4028/www.scientific.net/AMM.510.8.S2CID93345920.
^Montenegro, Angelo; Dutta, Chayan; Mammetkuliev, Muhammet; Shi, Haotian; Hou, Bingya; Bhattacharyya, Dhritiman; Zhao, Bofan; Cronin, Stephen B.; Benderskii, Alexander V. (3 June 2021). "Asymmetric response of interfacial water to applied electric fields".Nature.594 (7861):62–65.Bibcode:2021Natur.594...62M.doi:10.1038/s41586-021-03504-4.PMID34079138.S2CID235321882.
^abLenski, Daniel R.; Fuhrer, Michael S. (2011). "Raman and optical characterization of multilayer turbostratic graphene grown via chemical vapor deposition".Journal of Applied Physics.110 (1): 013720–013720–4.arXiv:1011.1683.Bibcode:2011JAP...110a3720L.doi:10.1063/1.3605545.
^Tang, Libin; Ji, Rongbin; Li, Xueming; Teng, Kar Seng; Lau, Shu Ping (2013). "Size-Dependent Structural and Optical Characteristics of Glucose-Derived Graphene Quantum Dots".Particle & Particle Systems Characterization.30 (6):523–531.doi:10.1002/ppsc.201200131.hdl:10397/32222.S2CID96410135.
^Marcano, Daniela C.; Kosynkin, Dmitry V.; Berlin, Jacob M.; Sinitskii, Alexander; Sun, Zhengzong; Slesarev, Alexander; Alemany, Lawrence B.; Lu, Wei; Tour, James M. (24 August 2010). "Improved Synthesis of Graphene Oxide".ACS Nano.4 (8):4806–4814.Bibcode:2010ACSNa...4.4806M.doi:10.1021/nn1006368.ISSN1936-0851.PMID20731455.
^Whitby, Raymond L. D.; Korobeinyk, Alina; Glevatska, Katya V. (2011). "Morphological changes and covalent reactivity assessment of single-layer graphene oxides under carboxylic group-targeted chemistry".Carbon.49 (2):722–725.Bibcode:2011Carbo..49..722W.doi:10.1016/j.carbon.2010.09.049.
^Elias, D. C.; Nair, R. R.; Mohiuddin, T. M. G.; Morozov, S. V.; Blake, P.; Halsall, M. P.; Ferrari, A. C.; Boukhvalov, D. W.; Katsnelson, M. I.; Geim, A. K.; Novoselov, K. S. (2009). "Control of Graphene's Properties by Reversible Hydrogenation: Evidence for Graphane".Science.323 (5914):610–3.arXiv:0810.4706.Bibcode:2009Sci...323..610E.doi:10.1126/science.1167130.PMID19179524.S2CID3536592.
^Garcia, J. C.; de Lima, D. B.; Assali, L. V. C.; Justo, J. F. (2011). "Group IV graphene- and graphane-like nanosheets".Journal of Materials Chemistry C.115 (27):13242–13246.arXiv:1204.2875.doi:10.1021/jp203657w.S2CID98682200.
^Chen, Po-Yen; Sodhi, Jaskiranjeet; Qiu, Yang; Valentin, Thomas M.; Steinberg, Ruben Spitz; Wang, Zhongying; Hurt, Robert H.; Wong, Ian Y. (6 May 2016). "Multiscale Graphene Topographies Programmed by Sequential Mechanical Deformation".Advanced Materials.28 (18). John Wiley & Sons, Inc.:3564–3571.Bibcode:2016AdM....28.3564C.doi:10.1002/adma.201506194.PMID26996525.S2CID19544549.
^Kusmartsev, F. V.; Wu, W. M.; Pierpoint, M. P.; Yung, K. C. (2014). "Application of Graphene within Optoelectronic Devices and Transistors".arXiv:1406.0809 [cond-mat.mtrl-sci].
^Paton, Keith R.; Varrla, Eswaraiah; Backes, Claudia; Smith, Ronan J.; Khan, Umar; O'Neill, Arlene; Boland, Conor; Lotya, Mustafa; Istrate, Oana M.; King, Paul; Higgins, Tom; Barwich, Sebastian; May, Peter; Puczkarski, Pawel; Ahmed, Iftikhar; Moebius, Matthias; Pettersson, Henrik; Long, Edmund; Coelho, João; O'Brien, Sean E.; McGuire, Eva K.; Sanchez, Beatriz Mendoza; Duesberg, Georg S.; McEvoy, Niall; Pennycook, Timothy J.; Downing, Clive; Crossley, Alison; Nicolosi, Valeria; Coleman, Jonathan N. (2014)."Scalable production of large quantities of defect-free few-layer graphene by shear exfoliation in liquids"(PDF).Nature Materials.13 (6):624–630.Bibcode:2014NatMa..13..624P.doi:10.1038/nmat3944.PMID24747780.S2CID43256835.
^ROUZAFZAY, F.; SHIDPOUR, R. (2020). "Graphene@ZnO nanocompound for short-time water treatment under sun-simulated irradiation: Effect of shear exfoliation of graphene using kitchen blender on photocatalytic degradation".Alloys and Compounds.829 154614.doi:10.1016/J.JALLCOM.2020.154614.S2CID216233251.
^USA US11038172B2, Bor Z. Jang, "Environmentally benign process for producing graphene-protected anode particles for lithium batteries", published 10 September 2020, issued 15 June 2021, assigned to Nanotek Instruments, Inc and Global Graphene Group, Inc
^Lotya, Mustafa; Hernandez, Yenny; King, Paul J.; Smith, Ronan J.; Nicolosi, Valeria; Karlsson, Lisa S.; Blighe, Fiona M.; De, Sukanta; Wang, Zhiming; McGovern, I. T.; Duesberg, Georg S.; Coleman, Jonathan N. (18 March 2009). "Liquid Phase Production of Graphene by Exfoliation of Graphite in Surfactant/Water Solutions".Journal of the American Chemical Society.131 (10):3611–3620.arXiv:0809.2690.Bibcode:2009JAChS.131.3611L.doi:10.1021/ja807449u.PMID19227978.S2CID16624132.
^Backes, Claudia; Campi, Davide; Szydlowska, Beata M.; Synnatschke, Kevin; Ojala, Ezgi; Rashvand, Farnia; Harvey, Andrew; Griffin, Aideen; Sofer, Zdenek; Marzari, Nicola; Coleman, Jonathan N.; O'Regan, David D. (25 June 2019). "Equipartition of Energy Defines the Size–Thickness Relationship in Liquid-Exfoliated Nanosheets".ACS Nano.13 (6):7050–7061.arXiv:2006.14909.Bibcode:2019ACSNa..13.7050B.doi:10.1021/acsnano.9b02234.PMID31199123.S2CID189813507.
^Coleman, Jonathan N.; Lotya, Mustafa; O'Neill, Arlene; Bergin, Shane D.; King, Paul J.; Khan, Umar; Young, Karen; Gaucher, Alexandre; De, Sukanta; Smith, Ronan J.; Shvets, Igor V.; Arora, Sunil K.; Stanton, George; Kim, Hye-Young; Lee, Kangho; Kim, Gyu Tae; Duesberg, Georg S.; Hallam, Toby; Boland, John J.; Wang, Jing Jing; Donegan, John F.; Grunlan, Jaime C.; Moriarty, Gregory; Shmeliov, Aleksey; Nicholls, Rebecca J.; Perkins, James M.; Grieveson, Eleanor M.; Theuwissen, Koenraad; McComb, David W.; Nellist, Peter D.; Nicolosi, Valeria (4 February 2011). "Two-Dimensional Nanosheets Produced by Liquid Exfoliation of Layered Materials".Science.331 (6017):568–571.Bibcode:2011Sci...331..568C.doi:10.1126/science.1194975.hdl:2262/66458.PMID21292974.S2CID23576676.
^Brumfiel, G. (2009). "Nanotubes cut to ribbons New techniques open up carbon tubes to create ribbons".Nature.doi:10.1038/news.2009.367.
^Geim, Andre (January 2010)."Many Pioneers in Graphene Discovery".Letters to the Editor. American Physical Society.Archived from the original on 2 November 2021. Retrieved10 November 2019.
^Eigler, S.; Enzelberger-Heim, M.; Grimm, S.; Hofmann, P.; Kroener, W.; Geworski, A.; Dotzer, C.; Röckert, M.; Xiao, J.; Papp, C.; Lytken, O.; Steinrück, H.-P.; Müller, P.; Hirsch, A. (2013). "Wet Chemical Synthesis of Graphene".Advanced Materials.25 (26):3583–3587.Bibcode:2013AdM....25.3583E.doi:10.1002/adma.201300155.PMID23703794.S2CID26172029.
^Sadri, R. (15 February 2017). "Experimental study on thermo-physical and rheological properties of stable and green reduced graphene oxide nanofluids: Hydrothermal assisted technique".Journal of Dispersion Science and Technology.38 (9):1302–1310.doi:10.1080/01932691.2016.1234387.S2CID53349683.
^Tang, L.; Li, X.; Ji, R.; Teng, K. S.; Tai, G.; Ye, J.; Wei, C.; Lau, S. P. (2012). "Bottom-up synthesis of large-scale graphene oxide nanosheets".Journal of Materials Chemistry.22 (12): 5676.doi:10.1039/C2JM15944A.hdl:10397/15682.
^Li, Xueming; Lau, Shu Ping; Tang, Libin; Ji, Rongbin; Yang, Peizhi (2013). "Multicolour Light emission from chlorine-doped graphene quantum dots".Journal of Materials Chemistry C.1 (44):7308–7313.doi:10.1039/C3TC31473A.hdl:10397/34810.S2CID137213724.
^Chiu, Pui Lam; Mastrogiovanni, Daniel D. T.; Wei, Dongguang; Louis, Cassandre; Jeong, Min; Yu, Guo; Saad, Peter; Flach, Carol R.; Mendelsohn, Richard; Garfunkel, Eric; He, Huixin (4 April 2012). "Microwave- and Nitronium Ion-Enabled Rapid and Direct Production of Highly Conductive Low-Oxygen Graphene".Journal of the American Chemical Society.134 (13):5850–5856.Bibcode:2012JAChS.134.5850C.doi:10.1021/ja210725p.PMID22385480.S2CID11991071.
^Patel, Mehulkumar; Feng, Wenchun; Savaram, Keerthi; Khoshi, M. Reza; Huang, Ruiming; Sun, Jing; Rabie, Emann; Flach, Carol; Mendelsohn, Richard; Garfunkel, Eric; He, Huixin (2015). "Microwave Enabled One-Pot, One-Step Fabrication and Nitrogen Doping of Holey Graphene Oxide for Catalytic Applications".Small.11 (27):3358–68.doi:10.1002/smll.201403402.hdl:2027.42/112245.PMID25683019.S2CID14567874.
^Lee, J.-H.; Lee, E. K.; Joo, W.-J.; Jang, Y.; Kim, B.-S.; Lim, J. Y.; Choi, S.-H.; Ahn, S. J.; Ahn, J. R.; Park, M.-H.; Yang, C.-W.; Choi, B. L.; Hwang, S.-W.; Whang, D. (2014). "Wafer-Scale Growth of Single-Crystal Monolayer Graphene on Reusable Hydrogen-Terminated Germanium".Science.344 (6181):286–9.Bibcode:2014Sci...344..286L.doi:10.1126/science.1252268.PMID24700471.S2CID206556123.
^Bansal, Tanesh; Durcan, Christopher A.; Jain, Nikhil; Jacobs-Gedrim, Robin B.; Xu, Yang; Yu, Bin (2013). "Synthesis of few-to-monolayer graphene on rutile titanium dioxide".Carbon.55:168–175.Bibcode:2013Carbo..55..168B.doi:10.1016/j.carbon.2012.12.023.
^Mattevi, Cecilia; Kim, Hokwon; Chhowalla, Manish (2011). "A review of chemical vapour deposition of graphene on copper".Journal of Materials Chemistry.21 (10):3324–3334.doi:10.1039/C0JM02126A.S2CID213144.
^Tao, Li; Lee, Jongho; Chou, Harry; Holt, Milo; Ruoff, Rodney S.; Akinwande, Deji (27 March 2012). "Synthesis of High Quality Monolayer Graphene at Reduced Temperature on Hydrogen-Enriched Evaporated Copper (111) Films".ACS Nano.6 (3):2319–2325.Bibcode:2012ACSNa...6.2319T.doi:10.1021/nn205068n.PMID22314052.S2CID30130350.
^abTao, Li; Lee, Jongho; Holt, Milo; Chou, Harry; McDonnell, Stephen J.; Ferrer, Domingo A.; Babenco, Matías G.; Wallace, Robert M.; Banerjee, Sanjay K. (15 November 2012). "Uniform Wafer-Scale Chemical Vapor Deposition of Graphene on Evaporated Cu (111) Film with Quality Comparable to Exfoliated Monolayer".The Journal of Physical Chemistry C.116 (45):24068–24074.doi:10.1021/jp3068848.S2CID55726071.
^abRahimi, Somayyeh; Tao, Li; Chowdhury, Sk. Fahad; Park, Saungeun; Jouvray, Alex; Buttress, Simon; Rupesinghe, Nalin; Teo, Ken; Akinwande, Deji (28 October 2014). "Toward 300 mm Wafer-Scalable High-Performance Polycrystalline Chemical Vapor Deposited Graphene Transistors".ACS Nano.8 (10):10471–10479.Bibcode:2014ACSNa...810471R.doi:10.1021/nn5038493.PMID25198884.S2CID5077855.
^Chakrabarti, A.; Lu, J.; Skrabutenas, J. C.; Xu, T.; Xiao, Z.; Maguire, J. A.; Hosmane, N. S. (2011). "Conversion of carbon dioxide to few-layer graphene".Journal of Materials Chemistry.21 (26): 9491.doi:10.1039/C1JM11227A.S2CID96850993.
^Kim, D. Y.; Sinha-Ray, S.; Park, J. J.; Lee, J. G.; Cha, Y. H.; Bae, S. H.; Ahn, J. H.; Jung, Y. C.; Kim, S. M.; Yarin, A. L.; Yoon, S. S. (2014). "Self-Healing Reduced Graphene Oxide Films by Supersonic Kinetic Spraying".Advanced Functional Materials.24 (31):4986–4995.doi:10.1002/adfm.201400732.S2CID96283118.
^Kim, Do-Yeon; Sinha-Ray, Suman; Park, Jung-Jae; Lee, Jong-Gun; Cha, You-Hong; Bae, Sang-Hoon; Ahn, Jong-Hyun; Jung, Yong Chae; Kim, Soo Min; Yarin, Alexander L.; Yoon, Sam S. (2014)."Supersonic spray creates high-quality graphene layer".Advanced Functional Materials.24 (31). KurzweilAI:4986–4995.doi:10.1002/adfm.201400732.S2CID96283118.Archived from the original on 4 June 2014. Retrieved14 June 2014.
^Kim, Janghyuk; Lee, Geonyeop; Kim, Jihyun (20 July 2015). "Wafer-scale synthesis of multi-layer graphene by high-temperature carbon ion implantation".Applied Physics Letters.107 (3): 033104.Bibcode:2015ApPhL.107c3104K.doi:10.1063/1.4926605.
^Monetta, T.; Acquesta, A.; Carangelo, A.; Bellucci, F. (1 September 2018). "Considering the effect of graphene loading in water-based epoxy coatings".Journal of Coatings Technology and Research.15 (5):923–931.doi:10.1007/s11998-018-0045-8.ISSN1935-3804.S2CID139956928.
