One sentence summary:We describe a general liquid-phase method to exfoliate layered compounds to give monoand few-layer flakes in large quantities. TMDs consist of hexagonal layers of metal atoms, M, sandwiched between two layers of chalcogen atoms, X, with stoichiometry MX 2 . While the bonding within these tri-layer sheets is covalent, adjacent sheets stack via van der Waals interactions to form a 3D crystal. TMDs occur in more than 40 different types (2, 3) depending on the combination of chalcogen (S, Se or Te) and transition metal(3). Depending on the co-ordination and oxidation state of the metal atoms, TMDs can be metallic, semi-metallic or semiconducting(2, 3), e.g. WS 2 is a semiconductor while NbSe 2 is a metal(3). In addition, superconductivity(4) and charge density wave effects(5) have been observed in some TMDs. This versatility makes them potentially useful in many areas of electronics.However, like graphene(6), layered materials must be exfoliated to fulfil their full potential. For example, films of exfoliated Bi 2 Te 3 should display enhanced thermoelectric efficiency by suppression of thermal conductivity(7). Exfoliation of 2D topological insulators such as Bi 2 Te 3 and Bi 2 Se 3 would reduce residual bulk conductance, 4 highlighting surface effects. In addition, we can expect changes in electronic properties as the number of layers is reduced e.g. the indirect bandgap of bulk MoS 2 becomes direct in few-layer flakes(8). Although exfoliation can be achieved mechanically on a small scale(9, 10), liquid phase exfoliation methods are required for many applications(11).Critically, a simple liquid exfoliation method would allow the formation of novel hybrid and composite materials. While TMDs can be chemically exfoliated in liquids(12-14), this method is time consuming, extremely sensitive to the environment and incompatible with most solvents.We demonstrate exfoliation of bulk TMD crystals in common solvents to give mono-and few layer nano-sheets. This method is insensitive to air and water and can potentially be scaled up to give large quantities of exfoliated material. In addition, we show that this procedure allows the formation of hybrid films with enhanced properties.We initially sonicated commercial MoS 2 , WS 2 and BN (15, 16) powders in a number of solvents with varying surface tensions. The resultant dispersions were centrifuged and the supernatant decanted (Section S3). Optical absorption spectroscopy showed that the amount of material retained (characterised by / A l C α = , where A/l is the absorbance per length, α is the extinction coefficient and C is the concentration) was maximised for solvents with surface tension close to 40 mJ/m 2 (17, 18) ( Fig. 1A-C). Detailed analysis, within the framework of Hansen solubility parameter theory(19), shows successful solvents to be those with dispersive, polar and H-bonding components of the cohesive energy density within certain well-defined ranges (Section S4, Figs. S2-S3). This can be interpreted to mean that successful solvents are those w...
Graphene is at the centre of nanotechnology research. In order to fully exploit its outstanding properties, a mass production method is necessary. Two main routes are possible: large-scale growth or large-scale exfoliation. Here, we demonstrate graphene dispersions with concentrations up to ~0.01 mg/ml by dispersion and exfoliation of graphite in organic solvents such as N-methylpyrrolidone. This occurs because the energy required to exfoliate graphene is balanced by the solvent-graphene interaction for solvents whose surface energy matches that of graphene. We confirm the presence of individual graphene sheets with yields of up to 12% by mass, using absorption spectroscopy, transmission electron microscopy and electron diffraction. The absence of defects or oxides is confirmed by X-ray photoelectron, infra-red and Raman spectroscopies. We can produce conductive, semi-transparent films and conductive composites. Solution processing of graphene opens up a whole range of potential large-scale applications from device or sensor fabrication to liquid phase chemistry. Hernandez et al 2Graphene is one of the most exciting nano-materials due to the cascade of unique physical properties that have recently been demonstrated. For example, due to the details of its electronic structure, charge carriers in graphene behave as massless Dirac fermions 1 . Furthermore, novel effects such as an ambipolar field effect 2 , room temperature quantum Hall effect 3 , breakdown of the Born-Oppenheimer approximation 4 are observed. However, as was the case in the early days of nanotube and nanowire research, graphene at present still suffers from one problem, critical for its mass-scale exploitation: it cannot yet be made with high yield. The standard procedure used to make graphene is micromechanical cleavage 5 . This yields the best samples to date, with mobilities up to 200,000 cm 2 /Vs. 6 However, single layers are a negligible fraction amongst large quantities of thin graphite flakes. Furthermore, it is difficult to see how to scale up this process to mass production. Alternatively, growth of graphene is also commonly achieved by annealing SiC substrates, but these samples are in fact composed of a multitude of domains, most of them sub-micrometer, and not spatially uniform in number, or in size over larger length scales 7 . A number of works have also reported graphene growth on metal substrates 8,9 , but this would require the sample transfer to insulating substrates in order to make useful devices, either via mechanical transfer or, via solution processing.Recently, a large number of papers have described the dispersion and exfoliation of graphene oxide (GO) [10][11][12][13] . This material consists of graphene-like sheets, chemically functionalised with compounds such as hydroxyls and epoxides, which stabilise the sheets in water 14 . However, this functionalisation results in considerable disruption of the electronic structure of the graphene. In fact GO is an insulator 15 rather than a semi-metal and is conceptually differen...
We present the science and technology roadmap for graphene, related two-dimensional crystals, and hybrid systems, targeting an evolution in technology, that might lead to impacts and benefits reaching into most areas of society. This roadmap was developed within the framework of the European Graphene Flagship and outlines the main targets and research areas as best understood at the start of this ambitious project. We provide an overview of the key aspects of graphene and related materials (GRMs), ranging from fundamental research challenges to a variety of applications in a large number of sectors, highlighting the steps necessary to take GRMs from a state of raw potential to a point where they might revolutionize multiple industries. We also define an extensive list of acronyms in an effort to standardize the nomenclature in this emerging field.
We have demonstrated a method to disperse and exfoliate graphite to give graphene suspended in water-surfactant solutions. Optical characterisation of these suspensions allowed the partial optimisation of the dispersion process. Transmission electron microscopy showed the dispersed phase to consist of small graphitic flakes. More than 40% of these flakes had <5 layers with ~3% of flakes consisting of monolayers. These flakes are stabilised against reaggregation by Coulomb repulsion due to the adsorbed surfactant. However, the larger flakes tend to sediment out over ~6 weeks, leaving only small flakes dispersed. It is possible to form thin films by vacuum filtration of these dispersions. Raman and IR spectroscopic analysis of these films suggests the flakes to be largely free of defects and oxides. The deposited films are reasonably conductive and are semi-transparent. Further improvements may result in the development of cheap transparent conductors.
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