Sub-5 nm graphene nanopore fabrication by nitrogen ion etching induced by a low-energy electron beam.

A flexible and efficient method to fabricate nanopores in graphene has been developed. A focused, low-energy (5 keV) electron beam was used to locally activate etching of a graphene surface in a low pressure (0.3 Pa) N2 environment. Nanopores with sub-5 nm diameters were fabricated. The lattice structure of the graphene was observed to recover within 20 nm of the nanopore edge. Nanopore growth rates were investigated systematically. The effects of nitrogen pressure, electron beam dwell time and beam current were characterised in order to understand the etching mechanism and enable optimisation of the etching parameters. A model was developed which describes how the diffusion of ionised nitrogen affects the nanopore growth rate. Etching of other two-dimensional materials was attempted as demonstrated with MoS2. The lack of etching observed supports our model of a chemical reaction-based mechanism. The understanding of the etching mechanism will allow more materials to be etched by selection of an appropriate ion species.

Nanopatterning and Electrical Tuning of MoS2 Layers with a Subnanometer Helium Ion Beam.

We report subnanometer modification enabled by an ultrafine helium ion beam. By adjusting ion dose and the beam profile, structural defects were controllably introduced in a few-layer molybdenum disulfide (MoS2) sample and its stoichiometry was modified by preferential sputtering of sulfur at a few-nanometer scale. Localized tuning of the resistivity of MoS2 was demonstrated and semiconducting, metallic-like, or insulating material was obtained by irradiation with different doses of He(+). Amorphous MoSx with metallic behavior has been demonstrated for the first time. Fabrication of MoS2 nanostructures with 7 nm dimensions and pristine crystal structure was also achieved. The damage at the edges of these nanostructures was typically confined to within 1 nm. Nanoribbons with widths as small as 1 nm were reproducibly fabricated. This nanoscale modification technique is a generalized approach that can be applied to various two-dimensional (2D) materials to produce a new range of 2D metamaterials.

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.

Covalently functionalized hexagonal boron nitride nanosheets by nitrene addition.

The covalent functionalization of exfoliated hexagonal boron nitride (h-BN) nanosheets by nitrene addition is described. Integration of functionalized h-BN nanosheets within a polycarbonate matrix is demonstrated and was found to afford significant increases in mechanical properties. This integration methodology was further extended by the covalent modification of the h-BN nanosheets with polymer chains of a polycarbonate analogue, and the integration of the polymer modified h-BN within the polymer matrix.

Using solution thermodynamics to describe the dispersion of rod-like solutes: application to dispersions of carbon nanotubes in organic solvents.

We report a simple model describing the solubility of rods in solvents, expressing the final result explicitly in terms of the surface entropy and the enthalpy of mixing. This model can be combined with any expression for the mixing enthalpy depending on the requirements. For example, in one instance it predicts the dispersed concentration of rods to decrease exponentially with the Flory-Huggins parameter of the dispersion. Using a different enthalpy function, it predicts a Gaussian peak when concentration is plotted versus solvent surface energy. The model also suggests specific solvent-rod interactions to be important and shows the dispersed concentration to be very sensitive to ordering at the solvent-rod interface. We have used this model to describe experimental results for the concentration of dispersed nanotubes in various solvents. Qualitative agreement with these predictions is observed experimentally. However, we suggest that the fact that quantitative agreement is not found may be explained by solvent ordering at the nanotube surface.

Tuning the mechanical properties of composites from elastomeric to rigid thermoplastic by controlled addition of carbon nanotubes.

A commercial thermoplastic polyurethane is identified for which the addition of nanotubes dramatically improves its mechanical properties. Increasing the nanotube content from 0% to 40% results in an increase in modulus, Y, (0.4-2.2 GPa) and stress at 3% strain, σ(ϵ = 3%) , (10-50 MPa), no significant change in ultimate tensile strength, σ(B) , (≈50 MPa) and decreases in strain at break, ϵ(B) , (555-3%) and toughness, T, (177-1 MJ m(-3) ). This variation in properties spans the range from compliant and ductile, like an elastomer, at low mass fractions to stiff and brittle, like a rigid thermoplastic, at high nanotube content. For mid-range nanotube contents (≈15%) the material behaves like a rigid thermoplastic with large ductility: Y = 1.5 GPa, σ(ϵ = 3%) = 36 MPa, σ(B) = 55 MPa, ϵ(B) = 100% and T = 50 MJ m(-3) . Analysis suggests that soft polyurethane segments are immobilized by adsorption onto the nanotubes, resulting in large changes in mechanical properties.

Solvent-exfoliated graphene at extremely high concentration.

We describe three related methods to disperse graphene in solvents with concentrations from 2 to 63 mg/mL. Simply sonicating graphite in N-methyl-2-pyrrolidinone, followed by centrifugation, gives dispersed graphene at concentrations of up to 2 mg/mL. Filtration of a sonicated but uncentrifuged dispersion gives a partially exfoliated powder that can be redispersed at concentrations of up to 20 mg/mL. However, this process can be significantly improved by removing any unexfolaited graphite from the starting dispersion by centrifugation. The centrifuged dispersion can be filtered to give a powder of exfoliated few-layer graphene. This powder can be redispersed at concentrations of at least 63 mg/mL. The dispersed flakes are ~1 µm long and ~3 to 4 layers thick on average. Although some sedimentation occurs, ~26-28 mg/mL of the dispersed graphene appears to be indefinitely stable.

DMF-exfoliated graphene for electrochemical NADH detection.

The electrochemical detection of NADH is of considerable interest because it is required as a cofactor in a large number of dehydrogenase-based biosensors. However, the presence of oxygenated functionalities on the electrode often causes fouling due to the adsorption of the oxidised form, NAD(+). Here we report an electroanalytical NADH sensor based on DMF-exfoliated graphene. The latter is shown to have a very low oxygen content, facilitating the exceptionally stable and sensitive detection of this important analyte.

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.

The relationship of child neglect and physical maltreatment to placement outcomes and behavioral adjustment in children in foster care: a Canadian perspective.

Dramatic increases in child welfare rates in Canada over recent years have been largely driven by an increased reporting of neglect cases (Trocmé, Fallon, MacLaurin, & Neves, 2005). To a large extent, exploring the importance of neglect separate from physical maltreatment has been ignored in the child maltreatment literature. This study examined the differential effects of foster care in the child welfare system with children who presented as either experiencing physical maltreatment or neglect prior to their admission to care. Findings from this study are important to child welfare decision making about the differential needs of these two groups of children. The files of a sample of 110 children (79 neglected children and 31 physically maltreated children) were examined for differences in their adjustment while in foster care and on discharge. Some distinct differences in presentation were noted between the children experiencing the two types of maltreatment. Children experiencing neglect were younger, were more likely to have caregivers diagnosed with a substance abuse disorder, and had higher rates of exposure to spousal violence than maltreated children. Physically maltreated children displayed greater difficulty during their foster care adjustment. Once discharged from care, neglected children were more likely to be returned to the care of the agency. This study draws attention to the differential needs of children who experience neglect prior to their admission to a child welfare agency. Longer-term outcome studies are necessary to more completely understand how these two types of maltreatment influence the outcomes of children who are provided care within the child welfare system.

Sensitive, high-strain, high-rate bodily motion sensors based on graphene-rubber composites.

Monitoring of human bodily motion requires wearable sensors that can detect position, velocity and acceleration. They should be cheap, lightweight, mechanically compliant and display reasonable sensitivity at high strains and strain rates. No reported material has simultaneously demonstrated all the above requirements. Here we describe a simple method to infuse liquid-exfoliated graphene into natural rubber to create conducting composites. These materials are excellent strain sensors displaying 10(4)-fold increases in resistance and working at strains exceeding 800%. The sensitivity is reasonably high, with gauge factors of up to 35 observed. More importantly, these sensors can effectively track dynamic strain, working well at vibration frequencies of at least 160 Hz. At 60 Hz, we could monitor strains of at least 6% at strain rates exceeding 6000%/s. We have used these composites as bodily motion sensors, effectively monitoring joint and muscle motion as well and breathing and pulse.

Edge and confinement effects allow in situ measurement of size and thickness of liquid-exfoliated nanosheets.

Two-dimensional nanomaterials such as MoS2 are of great interest both because of their novel physical properties and their applications potential. Liquid exfoliation, an important production method, is limited by our inability to quickly and easily measure nanosheet size, thickness or concentration. Here we demonstrate a method to simultaneously determine mean values of these properties from an optical extinction spectrum measured on a liquid dispersion of MoS2 nanosheets. The concentration measurement is based on the size-independence of the low-wavelength extinction coefficient, while the size and thickness measurements rely on the effect of edges and quantum confinement on the optical spectra. The resultant controllability of concentration, size and thickness facilitates the preparation of dispersions with pre-determined properties such as high monolayer-content, leading to first measurement of A-exciton MoS2 luminescence in liquid suspensions. These techniques are general and can be applied to a range of two-dimensional materials including WS2, MoSe2 and WSe2.

Polymer reinforcement using liquid-exfoliated boron nitride nanosheets.

We have exfoliated hexagonal boron nitride by ultrasonication in solutions of polyvinylalcohol in water. The resultant nanosheets are sterically stabilised by adsorbed polymer chains. Centrifugation-based size-selection was used to give dispersions of nanosheets with aspect ratio (length/thickness) of ∼1400. Such dispersions can be used to produce polyvinylalcohol-BN composite films. Helium ion microscopy of fracture surfaces shows the nanosheets to be well dispersed and the composites to fail by pull-out. We find both modulus, Y, and strength, σ(B), of these composites to increase linearly with volume fraction, V(f), up to V(f)∼ 0.1 vol% BN before falling off. The rates of increase are extremely high; dY/dV(f) = 670 GPa and dσ(B)/dV(f) = 47 GPa. The former value matches theory based on continuum mechanics while the latter value is consistent with remarkably high polymer-filler interfacial strength. However, because the mechanical properties increase over such a narrow volume fraction range, the maximum values of both modulus and strength are only ∼40% higher than the pure polymer. This phenomenon has also been observed for graphene-filled composites and represents a serious hurdle to the production of high performance polymer-nanosheet composites.

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.

Hydrogen evolution across nano-Schottky junctions at carbon supported MoS2 catalysts in biphasic liquid systems.

The activities of a series of MoS(2)-based hydrogen evolution catalysts were studied by biphasic reactions monitored by UV/Vis spectroscopy. Carbon supported MoS(2) catalysts performed best due to an abundance of catalytic edge sites and strong electronic coupling of catalyst to support.

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.