Precise milling of nano-gap chains in graphene with a focused helium ion beam.

A focused helium ion beam was used to introduce nano-sized gap chains in graphene. The effect of beam scanning strategies in the fabrication of the nano-gap chains was investigated. The tuning of graphene conductivity has been achieved by modulating the magnitude and uniformity of the ion dose and hence the morphology of the nano-gap chains. A model based on the site-specific and dose-dependent conductivity was built to understand the tuning of the conductivity, taking into account the nanoscale non-uniformity of irradiation.

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.

Effect of localized helium ion irradiation on the performance of synthetic monolayer MoS2 field-effect transistors.

Helium ion irradiation is a known method of tuning the electrical conductivity and charge carrier mobility of novel two-dimensional semiconductors. Here, we report a systematic study of the electrical performance of chemically synthesized monolayer molybdenum disulfide (MoS2) field-effect transistors irradiated with a focused helium ion beam as a function of increasing areal irradiation coverage. We determine an optimal coverage range of approx. 10%, which allows for the improvement of both the carrier mobility in the transistor channel and the electrical conductance of the MoS2, due to doping with ion beam-created sulfur vacancies. Larger areal irradiations introduce a higher concentration of scattering centers, hampering the electrical performance of the device. In addition, we find that irradiating the electrode-channel interface has a deleterious impact on charge transport when contrasted with irradiations confined only to the transistor channel.

MoS2 Memtransistors Fabricated by Localized Helium Ion Beam Irradiation.

Two-dimensional (2D) layered semiconductors have recently emerged as attractive building blocks for next-generation low-power nonvolatile memories. However, challenges remain in the controllable fabrication of bipolar resistive switching circuit components from these materials. Here, the experimental realization of lateral memtransistors from monolayer single-crystal molybdenum disulfide (MoS2) utilizing a focused helium ion beam is reported. Site-specific irradiation with the focused probe of a helium ion microscope creates a nanometer-scale defect-rich region, bisecting the MoS2 lattice. The reversible drift of these defects in the applied electric field modulates the resistance of the channel, enabling versatile memristive functionality. The device can reliably retain its resistance ratios and set/reset biases for 1180 switching cycles. Long-term potentiation and depression with sharp habituation are demonstrated. This work establishes the feasibility of ion irradiation for controllable fabrication of 2D memristive devices with promising key performance parameters, such as low power consumption. The applicability of these devices for synaptic emulation may address the demands of future neuromorphic architectures.

Oxide-mediated recovery of field-effect mobility in plasma-treated MoS2.

Precise tunability of electronic properties of two-dimensional (2D) nanomaterials is a key goal of current research in this field of materials science. Chemical modification of layered transition metal dichalcogenides leads to the creation of heterostructures of low-dimensional variants of these materials. In particular, the effect of oxygen-containing plasma treatment on molybdenum disulfide (MoS2) has long been thought to be detrimental to the electrical performance of the material. We show that the mobility and conductivity of MoS2 can be precisely controlled and improved by systematic exposure to oxygen/argon plasma and characterize the material using advanced spectroscopy and microscopy. Through complementary theoretical modeling, which confirms conductivity enhancement, we infer the role of a transient 2D substoichiometric phase of molybdenum trioxide (2D-MoO x ) in modulating the electronic behavior of the material. Deduction of the beneficial role of MoO x will serve to open the field to new approaches with regard to the tunability of 2D semiconductors by their low-dimensional oxides in nano-modified heterostructures.

Elemental preference and atomic scale site recognition in a Co-Al-W-base superalloy.

Using state-of-the-art atomic scale super energy dispersive X-ray spectroscopy and high angle annular dark field imaging this study reveals the elemental partitioning preference between the γ' and γ phases in a Co-Al-W-Ti-Ta superalloy and the site preference of its alloying elements in the ordered L12 γ' phase. A semi-quantitative analysis of atomic column compositions in the ordered L12 γ' structure is provided. Co atoms were found to occupy the {1/2, 1/2, 0} face-center positions whereas Al, W, Ti and Ta atoms prefer to occupy the {0, 0, 0} cube corner positions in the L12 γ phase. These findings agree well with predictions from first principles simulations in the literature.

Correlation of Emulsion Structure with Cellular Uptake Behavior of Encapsulated Bioactive Nutrients: Influence of Droplet Size and Interfacial Structure.

In this study, an in vitro Caco-2 cell culture assay was employed to evaluate the correlation between emulsion structure and cellular uptake of encapsulated ß-carotene. After 4 h of incubation, an emulsion stabilized with whey protein isolate showed the highest intracellular accumulation of ß-carotene (1.06 µg), followed by that stabilized with sodium caseinate (0.60 µg) and Tween 80 (0.20 µg), which are 13-, 7.5-, and 2.5-fold higher than that of free ß-carotene (0.08 µg), respectively. Emulsions with small droplet size (239 ± 5 nm) showed a higher cellular uptake of ß-carotene (1.56 µg) than emulsiond with large droplet size (489 ± 9 nm) (0.93 µg) (p < 0.01). The results suggested that delivery in an emulsion significantly improved the cellular uptake of ß-carotene and thus potentially its bioavailability; uptake was closely correlated with the interfacial composition and droplet size of emulsions. The findings support the potential for achieving optimal controlled and targeted delivery of bioactive nutrients by structuring emulsions.

Enhancing capacitance behaviour of CoOOH nanostructures using transition metal dopants by ambient oxidation.

Cobalt hydrate and doped binary Co0.9M0.1OOH (M = Ni, Mn, Fe) nanorings of 100-300 nm were fabricated in solution through a facile ambient oxidation method. A transformation from Co0.9Ni0.1(OH)2 nanodiscs to hollow Co0.9Ni0.1OOH nanorings was observed with prolonged reaction time. Core-shell nanodiscs have elemental segregation with a Co(OH)2 core and Ni(OH)2 shell. Co0.9Ni0.1OOH nanorings displayed a higher electrochemical capacitance than Mn and Fe doped nanorings materials or materials with disc-like geometries.

Quantitative secondary electron imaging for work function extraction at atomic level and layer identification of graphene.

Two-dimensional (2D) materials usually have a layer-dependent work function, which require fast and accurate detection for the evaluation of their device performance. A detection technique with high throughput and high spatial resolution has not yet been explored. Using a scanning electron microscope, we have developed and implemented a quantitative analytical technique which allows effective extraction of the work function of graphene. This technique uses the secondary electron contrast and has nanometre-resolved layer information. The measurement of few-layer graphene flakes shows the variation of work function between graphene layers with a precision of less than 10 meV. It is expected that this technique will prove extremely useful for researchers in a broad range of fields due to its revolutionary throughput and accuracy.

Effects of a nanoceria fuel additive on the physicochemical properties of diesel exhaust particles.

Nanoceria (i.e., CeO2 nanoparticles) fuel additives have been used in Europe and elsewhere to improve fuel efficiency. Previously we have shown that the use of a commercial fuel additive Envirox™ in a diesel-powered electricity generator reduced emissions of diesel exhaust particle (DEP) mass and other pollutants. However, such additives are currently not permitted for use in on-road vehicles in North America, largely due to limited data on the potential health impact. In this study, we characterized a variety of physicochemical properties of DEPs emitted from the same engine. Our methods include novel techniques such as Raman spectrometry for analyzing particle surface structure and an assay for DEP oxidative potential. Results show that with increasing Envirox™ concentrations in the fuel (0×, 0.1×, 1×, and 10× of manufacturer recommended 0.5 mL Envirox™ per liter fuel), DEP sizes decreased from 194.6 ± 20.1 to 116.3 ± 14.8 nm; the zeta potential changed from -28.4 mV to -22.65 mV; DEP carbon content decreased from 91.8% to 79.4%; cerium and nitrogen contents increased from 0.3% to 6.5% and 0.2% to 0.6%, respectively; the ratio of organic carbon (OC) to elemental carbon (EC) increased from 22.9% to 38.7%; and the ratio of the disordered carbon structure to the ordered carbon structure (graphitized carbon) in DEPs decreased. Compared to DEPs emitted from 0×, 0.1×, and 1× fuels, DEPs from the 10× fuel had a lower oxidative potential likely due to the increased ceria content because pure ceria nanoparticles exhibited the lowest oxidative potential compared to all the DEPs. Since the physicochemical parameters tested here are among the determinants of particle toxicity, our findings imply that adding ceria nanoparticles into diesel may alter the toxicity of DEPs. The findings from the present study, hence, can help future studies that will examine the impact of nanoceria additives on DEP toxicities.

Electrical-field-driven metal-insulator transition tuned with self-aligned atomic defects.

Recently, significant attention has been paid to the resistance switching (RS) behaviour in Fe3O4 and it was explained through the analogy of the electrically driven metal-insulator transition based on the quantum tunneling theory. Here, we propose a method to experimentally support this explanation and provide a way to tune the critical switching parameter by introducing self-aligned localized impurities through the growth of Fe3O4 thin films on stepped SrTiO3 substrates. Anisotropic behavior in the RS was observed, where a lower switching voltage in the range of 10(4) V cm(-1) is required to switch Fe3O4 from a high conducting state to a low conducting state when the electrical field is applied along the steps. The anisotropic RS behavior is attributed to a high density array of anti-phase boundaries (APBs) formed at the step edges and thus are aligned along the same direction in the film which act as a train of hotspot forming conduits for resonant tunneling. Our experimental studies open an interesting window to tune the electrical-field-driven metal-insulator transition in strongly correlated systems.

High throughput secondary electron imaging of organic residues on a graphene surface.

Surface organic residues inhibit the extraordinary electronic properties of graphene, hindering the development of graphene electronics. However, fundamental understanding of the residue morphology is still absent due to a lack of high-throughput and high-resolution surface characterization methods. Here, we demonstrate that secondary electron (SE) imaging in the scanning electron microscope (SEM) and helium ion microscope (HIM) can provide sub-nanometer information of a graphene surface and reveal the morphology of surface contaminants. Nanoscale polymethyl methacrylate (PMMA) residues are visible in the SE imaging, but their contrast, i.e. the apparent lateral dimension, varies with the imaging conditions. We have demonstrated a quantitative approach to readily obtain the physical size of the surface features regardless of the contrast variation. The fidelity of SE imaging is ultimately determined by the probe size of the primary beam. HIM is thus evaluated to be a superior SE imaging technique in terms of surface sensitivity and image fidelity. A highly efficient method to reveal the residues on a graphene surface has therefore been established.