Boehm et al. coined the term "graphene" for the hypothetical single-layer structure in 1986. The term was used again in 1987 to describe single sheets of graphite as a constituent of graphite intercalation compounds, which can be seen as crystalline salts of the intercalant and graphene. It was also used in the descriptions of carbon nanotubes by R. Saito and Mildred and Gene Dresselhaus in 1992, and in the description of polycyclic aromatic hydrocarbons in 2000 by S. Wang and others.
Efforts to make thin films of graphite by mechanical exfoliation started in 1990.
Initial attempts employed exfoliation techniques similar to the drawing method. Multilayer samples down to 10 nm in thickness were obtained.
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 0.00001 inches (0.00025 millimetres). 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.
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.
This work resulted in the two winning the Nobel Prize in Physics in 2010 for their groundbreaking experiments with graphene. 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, a National Graphene Institute was established with that purpose at the University of Manchester, with a £60 million initial funding. In North East England two commercial manufacturers, Applied Graphene Materials and Thomas Swan Limited have begun manufacturing. Cambridge Nanosystems is a large-scale graphene powder production facility in East 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 of 0.142 nm (1.42 Å). In a graphene sheet, each atom is connected to its three nearest carbon neighbors by σ-bonds, and a delocalized π-bond, which contributes to a valence band that extends over the whole sheet. This type of bonding is also seen in polycyclic aromatic hydrocarbons. The valence band is touched by a conduction band, making graphene a semimetal with unusual electronic properties that are best described by theories for massless relativistic particles. 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 is ballistic over long distances; the material exhibits large quantum oscillations and large nonlinear diamagnetism.
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. Recent quantitative estimates of aromatic stabilization and limiting size derived from the enthalpies of hydrogenation (ΔHhydro) agree well with the literature reports.
Graphene sheets in solid form usually show evidence in diffraction for graphite's (002) layering. This is true of some single-walled nanostructures. However, unlayered graphene displaying only (hk0) rings have been observed in the core of presolar graphite onions. TEM studies show faceting at defects in flat graphene sheets and suggest a role for two-dimensional crystallization from a melt.
If the in-plane direction is confined rather than infinite, its electronic structure changes. These confined structures are referred to as graphene 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.
Electrons propagating through the graphene honeycomb lattice effectively lose their mass, producing quasi-particles described by a 2D analogue of the Dirac equation rather than the Schrödinger equation for spin-1/2 particles.
The cleavage technique led directly to the first observation of the anomalous quantum Hall effect in graphene in 2005 by Geim's group and by Philip Kim and Yuanbo Zhang. This effect provided direct evidence of graphene's theoretically predicted Berry's phase of massless Dirac fermions and proof of the Dirac fermion nature of electrons. These effects were previously observed in bulk graphite by Yakov Kopelevich, Igor A. Luk'yanchuk, and others, in 2003–2004.
When atoms are placed onto the graphene hexagonal lattice, the overlap between the pz(π) orbitals and the s or the px and py 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 conventional tight-binding model, the dispersion relation (restricted to first-nearest-neighbor interactions only) that produces the energy of the electrons with wave vector k is:
E
(
k
x
,
k
y
)
=
±
γ
0
1
+
4
cos
2
1
2
a
k
x
+
4
cos
1
2
a
k
x
⋅
cos
3
2
a
k
y
{\displaystyle E(k_{x},k_{y})=\pm \,\gamma _{0}{\sqrt {1+4\cos ^{2}{{\tfrac {1}{2}}ak_{x}}+4\cos {{\tfrac {1}{2}}ak_{x}}\cdot \cos {{\tfrac {\sqrt {3}}{2}}ak_{y}}}}}
Consequently, at low energies even neglecting the true spin, electrons can be described by an equation formally equivalent to the massless Dirac equation. Hence, the electrons and holes are called Dirac fermions. This pseudo-relativistic description is restricted to the chiral limit, i.e., to vanishing rest mass M0, leading to interesting additional features:
v
F
σ
→
⋅
∇
ψ
(
r
)
=
E
ψ
(
r
)
.
{\displaystyle v_{F}\,{\vec {\sigma }}\cdot \nabla \psi (\mathbf {r} )\,=\,E\psi (\mathbf {r} ).}
Electron waves in graphene propagate within a single-atom layer, making them sensitive to the proximity of other materials such as high-κ dielectrics, superconductors, and ferromagnets.
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).
Graphene electrons can traverse micrometer distances without scattering, even at room temperature.
Despite zero carrier density near the Dirac points, graphene exhibits a minimum conductivity on the order of
4
e
2
/
h
{\displaystyle 4e^{2}/h}
. The origin of this minimum conductivity is still unclear. However, rippling of the graphene sheet or ionized impurities in the SiO2 substrate may lead to local puddles of carriers that allow conduction. Several theories suggest that the minimum conductivity should be
4
e
2
/
(
π
h
)
{\displaystyle 4e^{2}/{(\pi }h)}
; however, most measurements are of the order of
4
e
2
/
h
{\displaystyle 4e^{2}/h}
or greater and depend on impurity concentration.
Near zero carrier density, graphene exhibits positive photoconductivity and negative photoconductivity at high carrier density, governed by the interplay between photoinduced changes of both the Drude weight and the carrier scattering rate.
Graphene doped with various gaseous species (both acceptors and donors) can be returned to an undoped state by gentle heating in a vacuum. Even for dopant concentrations in excess of 1012 cm−2, carrier mobility exhibits no observable change. Graphene doped with potassium in ultra-high vacuum at low temperature can reduce mobility 20-fold. 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) is thought to occur. It may therefore be a suitable material for constructing quantum computers using anyonic circuits.
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
σ
x
y
=
±
4
⋅
(
N
+
1
/
2
)
e
2
/
h
{\displaystyle \sigma _{xy}=\pm {4\cdot \left(N+1/2\right)e^{2}}/h}
, where N is the Landau level and the double valley and double spin degeneracies give the factor of 4. These anomalies are present not only at extremely low temperatures but also at room temperature, i.e. at roughly 20 °C (293 K).
This behavior is a direct result of graphene's chiral, massless Dirac electrons. In a magnetic field, their spectrum has a Landau level with energy precisely at the Dirac point. This level is a consequence of the Atiyah–Singer index theorem and is half-filled in neutral graphene, leading to the "+1/2" in the Hall conductivity. Bilayer graphene also shows the quantum Hall effect, but with only one of the two anomalies (i.e.
σ
x
y
=
±
4
⋅
N
⋅
e
2
/
h
{\displaystyle \sigma _{xy}=\pm {4\cdot N\cdot e^{2}}/h}
). In the second anomaly, the first plateau at N = 0 is absent, indicating that bilayer graphene stays metallic at the neutrality point.
Unlike normal metals, graphene's longitudinal resistance shows maxima rather than minima for integral values of the Landau filling factor in measurements of the Shubnikov–de Haas oscillations, thus the term "integral quantum Hall effect". These oscillations show a phase shift of π, known as Berry's phase. 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. 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.
Graphene samples prepared on nickel films, and on both the silicon face and carbon face of silicon carbide, show the anomalous effect directly in electrical measurements. Graphitic layers on the carbon face of silicon carbide show a clear Dirac spectrum in angle-resolved photoemission experiments, and the effect is observed in cyclotron resonance and tunneling experiments.
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 placing hexagonal 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.
The mass can be positive or negative. An arrangement that slightly raises the energy of an electron on atom A relative to atom B gives it a positive mass, while an arrangement that raises the energy of atom B produces a negative electron mass. The two versions behave alike and are indistinguishable via optical spectroscopy. An electron traveling from a positive-mass region to a negative-mass region must cross an intermediate region where its mass once again becomes zero. This region is gapless and therefore metallic. Metallic modes bounding semiconducting regions of opposite-sign mass is a hallmark of a topological phase and displays much the same physics as topological insulators.
If the mass in graphene can be controlled, electrons can be confined to massless regions by surrounding them with massive regions, allowing the patterning of quantum dots, wires, and other mesoscopic structures. It also produces one-dimensional conductors along the boundary. These wires would be protected against backscattering and could carry currents without dissipation.
Experimental verification, though confirmed, lacks the precision required to improve upon existing techniques for determining the fine-structure constant.
Graphene exhibits unique saturable absorption, which saturates when the input optical intensity exceeds a threshold value. This nonlinear optical behavior, termed saturable absorption, occurs across the visible to near-infrared spectrum, due to graphene's universal optical absorption and zero band gap. This property has enabled full-band mode-locking in fiber lasers using graphene-based saturable absorbers, contributing significantly to ultrafast photonics. Additionally, the optical response of graphene/graphene oxide layers can be electrically tuned.
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.
Under intense laser illumination, graphene exhibits a nonlinear phase shift due to the optical nonlinear Kerr effect. Graphene demonstrates a large nonlinear Kerr coefficient of 10−7 cm2⋅W−1, nearly nine orders of magnitude larger than that of bulk dielectrics, suggesting its potential as a powerful nonlinear Kerr medium capable of supporting various nonlinear effects, including solitons.
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. With GW calculation, the properties of graphene-based materials were accurately investigated, including bulk graphene, nanoribbons, edge and surface functionalized armchair ribbons, hydrogen saturated armchair ribbons, Josephson effect in graphene SNS junctions with single localized defect and armchair ribbon scaling properties.
These observations with
ν
=
0
,
±
1
,
±
3
,
±
4
{\displaystyle \nu =0,\pm 1,\pm 3,\pm 4}
indicate that the four-fold degeneracy (two valley and two spin degrees of freedom) of the Landau energy levels is partially or completely lifted. One hypothesis proposes that magnetic catalysis of symmetry breaking is responsible for this degeneracy lift.
In 2010 researchers magnetized graphene by producing it via CVD on the Ni(111) substrate and then in 2014 by placing it on an atomically smooth layer of magnetic yttrium iron garnet, maintaining graphene's electronic properties unaffected. Previous methods involved doping graphene with other substances. The dopant's presence negatively affected its electronic properties.
The (two-dimensional) density of graphene is 0.763 mg per square meter.
Large-angle bending of graphene monolayers with minimal strain demonstrates its mechanical robustness. Even under extreme deformation, monolayer graphene maintains excellent carrier mobility.
In two-dimensional structures like graphene, thermal and quantum fluctuations cause relative displacement, with fluctuations growing logarithmically with structure size as per the Mermin–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, 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. These ripples, when amplified by vacancy defects, induce a negative Poisson's ratio into graphene, resulting in the thinnest auxetic material known so far.
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.
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. In 2010, researchers from Brown University computationally predicted that as the tilt-angle increases, the grain boundary strength also increases. They showed that the weakest link in the grain boundary is at the critical bonds of the heptagon rings. As the grain boundary angle increases, the strain in these heptagon rings decreases, causing the grain boundary to be stronger than lower-angle GBs. They proposed that, in fact, for sufficiently large angle GB, the strength of the GB is similar to pristine graphene. In 2012, it was further shown that the strength can increase or decrease, depending on the detailed arrangements of the defects. These predictions have since been supported by experimental evidence. In a 2013 study led by James Hone's group, researchers probed the elastic stiffness and strength of CVD-grown graphene by combining nano-indentation and high-resolution TEM. They found that the elastic stiffness is identical and strength is only slightly lower than those in pristine graphene. In the same year, researchers from University of California, Berkeley and University of California, Los Angeles probed bi-crystalline graphene with TEM and AFM. They found that the strength of grain boundaries indeed tends to increase with the tilt angle.
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.
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. In fact, three notable theoretical or computational studies on this topic have led to three different conclusions. First, in 2012, Kolakowski and Myer studied the mechanical properties of polycrystalline graphene with "realistic atomistic model", using molecular-dynamics (MD) simulation. To emulate the growth mechanism of CVD, they first randomly selected nucleation sites that are at least 5A (arbitrarily chosen) apart from other sites. Polycrystalline graphene was generated from these nucleation sites and was subsequently annealed at 3000K, 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. 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 pseudo Hall-Petch relationship. 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 using Voronoi 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. Experimental observations and other theoretical predictions also gave differing conclusions, similar to the three given above. 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 related carbon nanotubes, early measurements of the thermal conductivity of suspended graphene reported an exceptionally large thermal conductivity up to 5300 W⋅m−1⋅K−1, compared with the thermal conductivity of pyrolytic graphite of approximately 2000 W⋅m−1⋅K−1 at room temperature. 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 between 1500 – 2500 W⋅m−1⋅K−1 for suspended single-layer graphene. The large range in the reported thermal conductivity can be caused by large measurement uncertainties as well as variations in the graphene quality and processing conditions. In addition, it is known that when single-layer graphene is supported on an amorphous material, the thermal conductivity is reduced to about 500 – 600 W⋅m−1⋅K−1 at room temperature as a result of scattering of graphene lattice waves by the substrate, and can be even lower for few-layer graphene encased in amorphous oxide. Likewise, polymeric residue can contribute to a similar decrease in the thermal conductivity of suspended graphene to approximately 500 – 600 W⋅m−1⋅K−1 for bilayer graphene.
Graphene can self-repair holes in its sheets, when exposed to molecules containing carbon, such as hydrocarbons. Bombarded with pure carbon atoms, the atoms perfectly align into hexagons, filling the holes.
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. 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.
There are indications that graphene has promise as a useful material for interacting with neural cells; studies on cultured neural cells show limited success.
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.
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. 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. The process is based on graphene growth on a liquid metal matrix. The product of this process was called High 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.
It has been shown that the two graphene layers can withstand important strain or doping mismatch 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 by Raman spectroscopy. The D peak is very weak, whereas the 2D and G peaks remain prominent.
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 the Raman spectrum. 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. 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). 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.
Graphene oxide is usually produced through chemical exfoliation of graphite. A particularly popular technique is the improved Hummers' method. Using paper-making techniques on dispersed, oxidized and chemically processed graphite in water, the monolayer flakes form a single sheet and create strong bonds. These sheets, called graphene oxide paper, have a measured tensile modulus of 32 GPa. The chemical property of graphite oxide is related to the functional groups attached to graphene sheets. These can change the polymerization pathway and similar chemical processes. Graphene oxide flakes in polymerss display enhanced photo-conducting properties. Graphene is normally hydrophobic 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.
In 2022, researchers evaluated the biological effects of low doses on graphene oxide on larvae and imago of Drosophila 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.
Soluble fragments of graphene can be prepared in the laboratory through chemical modification of graphite. First, microcrystalline graphite is treated with an acidic mixture of sulfuric acid and nitric acid. A series of oxidation and exfoliation steps produce small graphene plates with carboxyl groups at their edges. These are converted to acid chloride groups by treatment with thionyl chloride; next, they are converted to the corresponding graphene amide via treatment with octadecyl amine. The resulting material (circular graphene layers of 5.3 Å or 5.3×10−10 m thickness) is soluble in tetrahydrofuran, tetrachloromethane and dichloroethane.
In 2011, researchers reported a novel yet simple approach to fabricating graphene fibers from chemical vapor deposition-grown graphene films. The method was scalable and controllable, delivering tunable morphology and pore structure by controlling the evaporation of solvents with suitable surface tension. Flexible all-solid-state supercapacitors based on these graphene fibers were demonstrated in 2013.
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).
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 by graphitization through a full-scale synergetic defect-engineering strategy. The graphene fibers with superior performances promise wide applications in functional textiles, lightweight motors, microelectronic devices, etc.
Three dimensional bilayer graphene has also been reported.
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 the University 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.
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 functional carbon groups decompose into graphene, while the nanotubes partially split and form in-plane covalent bonds with the graphene, adding strength. π–π stacking domains add more strength. The nanotubes can overlap, making the material a better conductor than standard CVD-grown graphene. The nanotubes effectively bridge the grain boundaries found in conventional graphene. The technique eliminates the traces of substrate on which later-separated sheets were deposited using epitaxy.
Stacks of a few layers have been proposed as a cost-effective and physically flexible replacement for indium tin oxide (ITO) used in displays and photovoltaic cells.
In 2015, a coiled form of graphene was discovered in graphitic carbon (coal). The spiraling effect is produced by defects in the material's hexagonal grid that causes it to spiral along its edge, mimicking a Riemann surface, with the graphene surface approximately perpendicular to the axis. When voltage is applied to such a coil, current flows around the spiral, producing a magnetic field. The phenomenon applies to spirals with either zigzag or armchair patterns, although with different current distributions. Computer simulations indicated that a conventional spiral inductor of 205 microns in diameter could be matched by a nanocoil just 70 nanometers wide, with a field strength reaching as much as 1 tesla.
A rapidly increasing list of production techniques have been developed to enable graphene's use in commercial applications.
Isolated 2D crystals cannot be grown via chemical synthesis beyond small sizes even in principle, because the rapid growth of phonon density with increasing lateral size forces 2D crystallites to bend into the third dimension. In all cases, graphene must bond to a substrate to retain its two-dimensional shape.
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).
The most famous, clean and rather straight-forward 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 uses adhesive tape to mechanically cleave high-quality graphite crystals into successively thinner platelets. Other methods do exist like exfoliation.
As of 2014, exfoliation produced graphene with the lowest number of defects and highest electron mobility. Alternatively, a sharp single-crystal diamond wedge can penetrate onto the graphite source to cleave layers. In the same year, defect-free, unoxidized graphene-containing liquids were made from graphite using mixers that produce local shear rates greater than 10×104.
Shear exfoliation is another method in which by using a rotor-stator mixer the scalable production of defect-free graphene has become possible. It has been shown that, as turbulence is not necessary for mechanical exfoliation, ResonantAcoustic mixing or low speed ball milling is effective in the production of high-yield and water-soluble graphene.
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.
Liquid-phase exfoliation can also be done by a less-known process of intercalating supercritical 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 100 atm. Carbon dioxide turns gaseous as soon as the vessel is depressurized and makes the graphite explode into few-layered graphene.
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.
P. Boehm reported producing monolayer flakes of reduced graphene oxide in 1962. Rapid heating of graphite oxide and exfoliation yields highly dispersed carbon powder with a few percent of graphene flakes.
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.
Graphite particles can be corroded in molten salts to form a variety of carbon nanostructures including graphene. 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.
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.
In 2012, microwave energy was reported to directly synthesize graphene in one step. 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. Microwave heating can dramatically shorten the reaction time from days to seconds.
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.
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.
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.
CVD graphene is scalable and has been grown on deposited Cu thin film catalyst on 100 to 300 mm standard Si/SiO2 wafers 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.
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. SITM has been reported for a variety of applications such conductive polymer-graphene foams, conductive polymer-graphene microspheres, conductive thin films and conductive inks.
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. More recent works demonstrated the use of mixed plastic waste, waste rubber tires, and pyrolysis ash as carbon feedstocks. 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.
In addition to experimental investigation of graphene and graphene-based devices, numerical modeling and simulation of graphene has also been an important research topic. The Kubo 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. 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.
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 of computational 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.
Graphene analogs (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, microwave photons, plasmons, microcavity polaritons, or even atoms. Also, the honeycomb structure in which those particles evolve can be of a different nature than carbon atoms in graphene. It can be, respectively, a photonic crystal, an array of metallic rods, metallic nanoparticles, a lattice of coupled microcavities, or an optical lattice.
Graphene is a transparent and flexible conductor that holds great promise for various material/device applications, including solar cells, light-emitting diodes (LED), integrated photonic circuit devices, touch panels, and smart windows or phones. Smartphone products with graphene touch screens are already on the market.
In 2013, Head announced their new range of graphene tennis racquets.
As of 2015, there is one product available for commercial use: a graphene-infused printer powder. Many other uses for graphene have been proposed or are under development, in areas including electronics, biological engineering, filtration, lightweight/strong composite materials, photovoltaics and energy storage. Graphene is often produced as a powder and as a dispersion in a polymer matrix. This dispersion is supposedly suitable for advanced composites, 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.
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. The van der Waals nature of graphene and other two-dimensional (2D) materials also permits van der Waals heterostructures and integrated circuits based on Van der Waals integration of 2D materials.
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. Graphene's transparency also enhances optical sensors, making them more effective in imaging and spectroscopy.
One review on graphene toxicity published in 2016 by Lalwani et al. summarizes the in vitro, in vivo, antimicrobial and environmental effects and highlights the various mechanisms of graphene toxicity. 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, and necrosis.
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.
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USA Active 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
https://patents.google.com/patent/US11038172B2/en
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