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 have used aqueous dispersions of silver nanowires to prepare thin, flexible, transparent, conducting films. The nanowires are of length and diameter close to 6.5 µm and 85 nm respectively. At low thickness, the films consist of networks but appear to become bulk-like for mean film thicknesses above ~160 nm. These films can be very transparent with optical transmittance reaching as high as 92% for low thickness. The transmittance (550 nm) decreases with increasing thickness, consistent with an optical conductivity of 6472 S/m. The films are also very uniform; the transmittance varies spatially by typically <2%. The sheet resistance decreases with increasing thickness, falling below 1 Ω/ for thicknesses above 300 nm. The DC conductivity increases from 2×10 5 S/m for very thin films before saturating at 5×10 6 S/m for thicker films.Similarly, the ratio of DC to optical conductivity increases with increasing thickness from 25 for the thinnest films, saturating at ~500 for thicknesses above ~160 nm. We believe this is the highest conductivity ratio ever observed for nanostructured films and is matched only by doped metal oxide films. These nanowire films are electromechanically very robust, with all but the thinnest films showing no change in sheet resistance when flexed over >1000 cycles. Such results make these films ideal as replacements for indium tin oxide as transparent electrodes. We have prepared films with optical transmittance and sheet resistance of 85% and 13 Ω/ respectively. This is very close to that displayed by commercially available indium tin oxide.
Nanowires have attracted considerable interest as nanoscale interconnects and as the active components of both electronic and electromechanical devices. Nanomechanical measurements are a challenge, but remain key to the development and processing of novel nanowire-based devices. Here, we report a general method to measure the spectrum of nanowire mechanical properties based on nanowire bending under the lateral load from an atomic force microscope tip. We find that for Au nanowires, Young's modulus is essentially independent of diameter, whereas the yield strength is largest for the smallest diameter wires, with strengths up to 100 times that of bulk materials, and substantially larger than that reported for bulk nanocrystalline metals (BNMs). In contrast to BNMs, nanowire plasticity is characterized by strain-hardening, demonstrating that dislocation motion and pile-up is still operative down to diameters of 40 nm. Possible origins for the different mechanical properties of nanowires and BNMs are discussed.
Transport in single-walled carbon nanotubes (SWCNTs) networks is shown to be dominated by resistance at network junctions which scale with the size of the interconnecting bundles. Acid treatment, known to dope individual tubes, actually produces a dramatic reduction in junction resistances, whereas annealing significantly increases this resistance. Measured junction resistances for pristine, acid-treated and annealed SWCNT bundles correlate with conductivities of the corresponding films, in excellent agreement with a model in which junctions control the overall network performance.
Spontaneous exfoliation of single‐walled carbon nanotubes on dilution of dispersions in a common solvent, N‐methyl‐pyrrolidone, is demonstrated. The free‐energy of mixing is negative, confirming athermal solubility. Scanning tunneling microscopy measurements show physisorption of the solvent to the nanotube (see figure). Experiments, supported by a simple model, show that successful solvents for nanotubes are those with surface tensions close to that of graphite.
We have prepared flexible, transparent, and very conducting thin composite films from poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate), filled with both arc discharge and HIPCO single-walled nanotubes, at high loading level. The films are of high optical uniformity. The arc discharge nanotube-filled composites were significantly more conductive, demonstrating DC conductivities of >10(5) S/m for mass fractions >50 wt %. The ratio of DC to optical conductivity was higher for composites with mass fractions of 55-60 wt % than for nanotube-only films. For an 80 nm thick composite, filled with 60 wt % arc discharge nanotubes, this conductivity ratio was maximized at sigma(DC)/sigma(Op) = 15. This translates into transmittance (550 nm) and sheet resistance of 75 and 80 Omega/square, respectively. These composites were electromechanically very stable, showing <1% resistance change over 130 bend cycles.
To exploit the novel size-dependent mechanical properties of nanowires, it is necessary for one to develop strategies to control the strength and toughness of these materials. Here, we report on the mechanical properties of silver nanowires with a unique fivefold twin structure using a lateral force atomic force microscopy (AFM) method in which wires are held in a double-clamped beam configuration. Force-displacement curves exhibit super elastic behavior followed by unexpected brittle failure without significant plastic deformation. Thermal annealing resulted in a gradual transition to weaker, more ductile materials associated with the elimination of the twinned boundary structure. These results point to the critical roles of microstructure and confinement in engineering the mechanical properties of nanoscale materials.
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