Scalable production of large quantities of defect-free few-layer graphene by shear exfoliation in liquids.

To progress from the laboratory to commercial applications, it will be necessary to develop industrially scalable methods to produce large quantities of defect-free graphene. Here we show that high-shear mixing of graphite in suitable stabilizing liquids results in large-scale exfoliation to give dispersions of graphene nanosheets. X-ray photoelectron spectroscopy and Raman spectroscopy show the exfoliated flakes to be unoxidized and free of basal-plane defects. We have developed a simple model that shows exfoliation to occur once the local shear rate exceeds 10(4) s(-1). By fully characterizing the scaling behaviour of the graphene production rate, we show that exfoliation can be achieved in liquid volumes from hundreds of millilitres up to hundreds of litres and beyond. The graphene produced by this method performs well in applications from composites to conductive coatings. This method can be applied to exfoliate BN, MoS2 and a range of other layered crystals.

Measuring the lateral size of liquid-exfoliated nanosheets with dynamic light scattering.

We have developed an in situ method to estimate the lateral size of exfoliated nanosheets dispersed in a liquid. Using standard liquid exfoliation and size-selection techniques, we prepared a range of dispersions of graphene, MoS2 and WS2 nanosheets with different mean lateral sizes. The mean nanosheet length was measured using transmission electron microscopy (TEM) to vary from ∼40 nm to ∼1 µm. These dispersions were characterized using a standard dynamic light scattering (DLS) instrument. We found a well-defined correlation between the peak of the particle size distribution as outputted by the DLS instrument and the nanosheet length as measured by TEM. This correlation is consistent with the DLS instrument outputting the radius of a sphere with volume equal to the mean nanosheet volume. This correlation allows the mean nanosheet length to be extracted from DLS data.

Transparent conducting films from NbSe3 nanowires.

We have developed methods to disperse and partially size separate NbSe(3) nanowires in aqueous surfactant solutions. These dispersions can easily be formed into thin films. Optical and electrical studies show these films to display sheet resistances and transmittances ranging from (460 Ω/□, 22%) to (12 kΩ/□, 79%) depending on thickness. For thicker films, we measured the transparent conducting figure of merit to be σ(DC, B)/σ(Op) = 0.32, similar to graphene networks. Thickness measurements gave individual values of σ(Op) = 17,800 S m(-1) and σ(DC, B) = 5700 S m(-1). Films thinner than ∼ 70 nm displayed reduced DC conductivity due to percolative effects.

High-concentration solvent exfoliation of graphene.

A method is demonstrated to prepare graphene dispersions at high concentrations, up to 1.2 mg mL(-1), with yields of up to 4 wt% monolayers. This process relies on low-power sonication for long times, up to 460 h. Transmission electron microscopy shows the sonication to reduce the flake size, with flake dimensions scaling as t(-1/2). However, the mean flake length remains above 1 microm for all sonication times studied. Raman spectroscopy shows defects are introduced by the sonication process. However, detailed analysis suggests that predominantly edge, rather than basal-plane, defects are introduced. These dispersions are used to prepare high-quality free-standing graphene films. The dispersions can be heavily diluted by water without sedimentation or aggregation. This method facilitates graphene processing for a range of applications.

Flexible, transparent, conducting films of randomly stacked graphene from surfactant-stabilized, oxide-free graphene dispersions.

Graphite is exfoliated in water to give dispersions of mono- and few-layer graphene stabilized by surfactant. These dispersions can be used to form thin, disordered films of randomly stacked, oxide-free, few-layer graphenes. These films are transparent with a direct current conductivity of up to 1.5 x 10(4) S m(-1). The conductivity is stable under flexing for at least 2000 cycles. The electrical properties are limited by disorder and aggregation suggesting future routes for improvement.

Measurement of multicomponent solubility parameters for graphene facilitates solvent discovery.

We have measured the dispersibility of graphene in 40 solvents, with 28 of them previously unreported. We have shown that good solvents for graphene are characterized by a Hildebrand solubility parameter of delta(T) approximately 23 MPa(1/2) and Hansen solubility parameters of delta(D) approximately 18 MPa(1/2), delta(P) approximately 9.3 MPa(1/2), and delta(H) approximately 7.7 MPa(1/2). The dispersibility is smaller for solvents with Hansen parameters further from these values. We have used transmission electron microscopy (TEM) analysis to show that the graphene is well exfoliated in all cases. Even in relatively poor solvents, >63% of observed flakes have <5 layers.

Liquid phase production of graphene by exfoliation of graphite in surfactant/water solutions.

We have demonstrated a method to disperse and exfoliate graphite to give graphene suspended in water-surfactant solutions. Optical characterization of these suspensions allowed the partial optimization 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 approximately 3% of flakes consisting of monolayers. Atomic resolution transmission electron microscopy shows the monolayers to be generally free of defects. The dispersed graphitic flakes are stabilized against reaggregation by Coulomb repulsion due to the adsorbed surfactant. We use DLVO and Hamaker theory to describe this stabilization. However, the larger flakes tend to sediment out over approximately 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, although X-ray photoelectron spectroscopy shows evidence of a small oxide population. Individual graphene flakes can be deposited onto mica by spray coating, allowing statistical analysis of flake size and thickness. Vacuum filtered films are reasonably conductive and are semitransparent. Further improvements may result in the development of cheap transparent conductors.

Inkjet printing of silver nanowire networks.

The development of printed electronics will require the ability to deposit a wide range of nanomaterials using printing techniques. Here we demonstrate the controlled deposition of networks of silver nanowires in well-defined patterns by inkjet printing from an optimized isopropyl alcohol-diethylene glycol dispersion. We find that great care must be taken while producing the ink and during solvent evaporation. The resultant networks have good electrical properties, displaying sheet resistances as low as 8 Ω/□ and conductivities as high as 10(5) S/m. Such optimized performances were achieved for line widths of 1-10 mm and network thicknesses of 0.5-2 µm deposited from ∼10-20 passes while using processing temperatures of no more than 110 °C. Thin networks are semitransparent with dc to optical conductivity ratios of ∼40.

Experimental and theoretical study of the influence of the state of dispersion of graphene on the percolation threshold of conductive graphene/polystyrene nanocomposites.

The effect of the dispersed state of graphene is studied as a factor influencing the electrical percolation threshold of graphene/polystyrene nanocomposites. We find the percolation threshold of our nanocomposites, prepared with graphene dispersions with different thermodynamic stabilities, degrees of exfoliation, and size polydispersities, to range from 2 to 4.5 wt %. Connectedness percolation theory is applied to calculate percolation thresholds of the corresponding nanocomposites, based on the premise that size polydispersity of graphene platelets in the corresponding solutions must have a strong influence on it. Theory and experimental results agree qualitatively.

Ultrafast saturable absorption of two-dimensional MoS2 nanosheets.

Employing high-yield production of layered materials by liquid-phase exfoliation, molybdenum disulfide (MoS2) dispersions with large populations of single and few layers were prepared. Electron microscopy verified the high quality of the two-dimensional MoS2 nanostructures. Atomic force microscopy analysis revealed that ~39% of the MoS2 flakes had thicknesses of less than 5 nm. Linewidth and frequency difference of the E(1)2g and A1g Raman modes confirmed the effective reduction of flake thicknesses from the bulk MoS2 to the dispersions. Ultrafast nonlinear optical (NLO) properties were investigated using an open-aperture Z-scan technique. All experiments were performed using 100 fs pulses at 800 nm from a mode-locked Ti:sapphire laser. The MoS2 nanosheets exhibited significant saturable absorption (SA) for the femtosecond pulses, resulting in the third-order NLO susceptibility Imχ((3)) ~ 10(-15) esu, figure of merit ~10(-15) esu cm, and free-carrier absorption cross section ~10(-17) cm(2). Induced free carrier density and the relaxation time were estimated to be ~10(16) cm(-3) and ~30 fs, respectively. At the same excitation condition, the MoS2 dispersions show better SA response than the graphene dispersions.

Solvent exfoliation of transition metal dichalcogenides: dispersibility of exfoliated nanosheets varies only weakly between compounds.

We have studied the dispersion and exfoliation of four inorganic layered compounds, WS(2), MoS(2), MoSe(2), and MoTe(2), in a range of organic solvents. The aim was to explore the relationship between the chemical structure of the exfoliated nanosheets and their dispersibility. Sonication of the layered compounds in solvents generally gave few-layer nanosheets with lateral dimensions of a few hundred nanometers. However, the dispersed concentration varied greatly from solvent to solvent. For all four materials, the concentration peaked for solvents with surface energy close to 70 mJ/m(2), implying that all four have surface energy close to this value. Inverse gas chromatography measurements showed MoS(2) and MoSe(2) to have surface energies of ∼75 mJ/m(2), in good agreement with dispersibility measurements. However, this method suggested MoTe(2) to have a considerably larger surface energy (∼120 mJ/m(2)). While surface-energy-based solubility parameters are perhaps more intuitive for two-dimensional materials, Hansen solubility parameters are probably more useful. Our analysis shows the dispersed concentration of all four layered materials to show well-defined peaks when plotted as a function of Hansen's dispersive, polar, and H-bonding solubility parameters. This suggests that we can associate Hansen solubility parameters of δ(D) ∼ 18 MPa(1/2), δ(P) ∼ 8.5 MPa(1/2), and δ(H) ∼ 7 MPa(1/2) with all four types of layered material. Knowledge of these properties allows the estimation of the Flory-Huggins parameter, χ, for each combination of nanosheet and solvent. We found that the dispersed concentration of each material falls exponentially with χ as predicted by solution thermodynamics. This work shows that solution thermodynamics and specifically solubility parameter analysis can be used as a framework to understand the dispersion of two-dimensional materials. Finally, we note that in good solvents, such as cyclohexylpyrrolidone, the dispersions are temporally stable with >90% of material remaining dispersed after 100 h.

Percolation scaling in composites of exfoliated MoS2 filled with nanotubes and graphene.

Applications of films of exfoliated layered compounds in many areas will be limited by their relatively low electrical conductivity. To address this, we have prepared and characterised composites of a nano-conductor (nanotubes or graphene) embedded in a matrix of exfoliated MoS(2) nanosheets. Solvent exfoliation of MoS(2) nanosheets, followed by blending with dispersions of graphene or nanotubes allowed the formation of such composite films by vacuum filtration. This gave spatially uniform mixtures with fully tuneable nano-conductor content. By addition of the nano-conducting phase, it was possible to vary the electrical conductivity of the composite over nine orders of magnitude. For both filler types the conductivity followed percolation scaling laws both above and below the percolation threshold. In the case of SWNT-filled composites, conductivities as high as ~40 S m(-1) were achieved at volume fractions as low as ~4%.

Two-dimensional nanosheets produced by liquid exfoliation of layered materials.

If they could be easily exfoliated, layered materials would become a diverse source of two-dimensional crystals whose properties would be useful in applications ranging from electronics to energy storage. We show that layered compounds such as MoS(2), WS(2), MoSe(2), MoTe(2), TaSe(2), NbSe(2), NiTe(2), BN, and Bi(2)Te(3) can be efficiently dispersed in common solvents and can be deposited as individual flakes or formed into films. Electron microscopy strongly suggests that the material is exfoliated into individual layers. By blending this material with suspensions of other nanomaterials or polymer solutions, we can prepare hybrid dispersions or composites, which can be cast into films. We show that WS(2) and MoS(2) effectively reinforce polymers, whereas WS(2)/carbon nanotube hybrid films have high conductivity, leading to promising thermoelectric properties.

Improvement of transparent conducting nanotube films by addition of small quantities of graphene.

We demonstrate a water-based method to prepare transparent, conducting graphene/single-walled nanotube hybrid films. While the transmittance decreases slightly with increasing graphene content, the DC conductivity, sigma(DC), and sheet resistance scale non-monotonically with film composition. We observe an optimum composition of approximately 3 wt % graphene, which results in a peak in the DC conductivity. We have calculated the figure of merit, the DC to optical conductivity ratio, sigmaDC/sigmaOp, which also shows a peak at this composition. We find that this effect is only present for small graphene flakes. In addition, acid treatment increases both the sigmaDC and sigmaDC/sigmaOp by x2.5. Interestingly, acid treatment is more effective for films close to the optimum composition. This has the effect of sharpening the peaks in both sigmaDC and sigmaDC/sigmaOp. For acid-treated films, addition of 3 wt % graphene results in a 40% increase in sigmaDC/sigmaOp compared to the nanotube-only film, from 12.5 to 18. Optimized, acid-treated films display transmittance of 80% coupled with a sheet resistance of 100 Omega/[square].

High-concentration, surfactant-stabilized graphene dispersions.

A method is presented to produce graphene dispersions, stabilized in water by the surfactant sodium cholate, at concentrations up to 0.3 mg/mL. The process uses low power sonication for long times (up to 400 h) followed by centrifugation to yield stable dispersions. The dispersed concentration increases with sonication time while the best quality dispersions are obtained for centrifugation rates between 500 and 2000 rpm. Detailed TEM analysis shows the flakes to consist of 1-10 stacked monolayers with up to 20% of flakes containing just one layer. The average flake consists of approximately 4 stacked monolayers and has length and width of approximately 1 mum and approximately 400 nm, respectively. These dimensions are surprisingly stable under prolonged sonication. However, the mean flake length falls from approximately 1 mum to approximately 500 nm as the centrifugation rate is increased from 500 to 5000 rpm. Raman spectroscopy shows the flake bodies to be relatively defect-free for centrifugation rates below 2000 rpm. The dispersions can be easily cast into high-quality, free-standing films. The method extends the scope for scalable liquid-phase processing of graphene for a wide range of applications.

High-yield production of graphene by liquid-phase exfoliation of graphite.

Fully exploiting the properties of graphene will require a method for the mass production of this remarkable material. Two main routes are possible: large-scale growth or large-scale exfoliation. Here, we demonstrate graphene dispersions with concentrations up to approximately 0.01 mg ml(-1), produced by dispersion and exfoliation of graphite in organic solvents such as N-methyl-pyrrolidone. This is possible because the energy required to exfoliate graphene is balanced by the solvent-graphene interaction for solvents whose surface energies match that of graphene. We confirm the presence of individual graphene sheets by Raman spectroscopy, transmission electron microscopy and electron diffraction. Our method results in a monolayer yield of approximately 1 wt%, which could potentially be improved to 7-12 wt% with further processing. The absence of defects or oxides is confirmed by X-ray photoelectron, infrared and Raman spectroscopies. We are able to produce semi-transparent conducting films and conducting composites. Solution processing of graphene opens up a range of potential large-area applications, from device and sensor fabrication to liquid-phase chemistry.