Colloidal Synthesis of Carbon Dot-ZnSe Nanoplatelet Van der Waals Heterostructures for Boosting Photocatalytic Generation of Methanol-Storable Hydrogen.

Methanol is not only a promising liquid hydrogen carrier but also an important feedstock chemical for chemical synthesis. Catalyst design is vital for enabling the reactions to occur under ambient conditions. This study reports a new class of van der Waals heterojunction photocatalyst, which is synthesized by hot-injection method, whereby carbon dots (CDs) are grown in situ on ZnSe nanoplatelets (NPLs), i.

Evaluation of the X-ray/EUV Nanolithography Facility at AS through wavefront propagation simulations.

Synchrotron light sources can provide the required spatial coherence, stability and control to support the development of advanced lithography at the extreme ultraviolet and soft X-ray wavelengths that are relevant to current and future fabricating technologies. Here an evaluation of the optical performance of the soft X-ray (SXR) beamline of the Australian Synchrotron (AS) and its suitability for developing interference lithography using radiation in the 91.8 eV (13.

2D Ferromagnetic MGeTe (M = Ni/Fe) for Boosting Intermediates Adsorption toward Faster Water Oxidation.

In this work, 2D ferromagnetic MGeTe (MGT, M = Ni/Fe) nanosheets with rich atomic Te vacancies (2D-MGT) are demonstrated as efficient OER electrocatalyst via a general mechanical exfoliation strategy. X-ray absorption spectra (XAS) and scanning transmission electron microscope (STEM) results validate the dominant presence of metal-O moieties and rich Te vacancies, respectively. The formed Te vacancies are active for the adsorption of OH* and O* species while the metal-O moieties promote the O* and OOH* adsorption, contributing synergistically to the faster oxygen evolution kinetics.

Stabilizing Cobalt-free Li-rich Layered Oxide Cathodes through Oxygen Lattice Regulation by Two-phase Ru Doping.

The application of Li-rich layered oxides is hindered by their dramatic capacity and voltage decay on cycling. This work comprehensively studies the mechanistic behaviour of cobalt-free Li Ni Mn O and demonstrates the positive impact of two-phase Ru doping. A mechanistic transition from the monoclinic to the hexagonal behaviour is found for the structural evolution of Li Ni Mn O and the improvement mechanism of Ru doping is understood using the combination of in operando and post-mortem synchrotron analyses.

Introducing 4s-2p Orbital Hybridization to Stabilize Spinel Oxide Cathodes for Lithium-Ion Batteries.

Oxides composed of an oxygen framework and interstitial cations are promising cathode materials for lithium-ion batteries. However, the instability of the oxygen framework under harsh operating conditions results in fast battery capacity decay, due to the weak orbital interactions between cations and oxygen (mainly 3d-2p interaction). Here, a robust and endurable oxygen framework is created by introducing strong 4s-2p orbital hybridization into the structure using LiNi Mn O oxide as an example.

Epitaxial growth of an atom-thin layer on a LiNiMnO cathode for stable Li-ion battery cycling.

Transition metal dissolution in cathode active material for Li-based batteries is a critical aspect that limits the cycle life of these devices. Although several approaches have been proposed to tackle this issue, this detrimental process is not yet overcome. Here, benefitting from the knowledge developed in the semiconductor research field, we apply an epitaxial method to construct an atomic wetting layer of LaTMO (TM = Ni, Mn) on a LiNiMnO cathode material.

Validating the Electronic Structure of Vanadium Phosphate Cathode Materials.

Investigation of the electronic structure of contending battery electrode materials is an essential step for developing a detailed mechanistic understanding of charge-discharge properties. Herein, we use synchrotron soft X-ray absorption spectroscopy (XAS) in combination with complementary experiments and density functional theory calculations to map the electronic structure, band positioning, and band gap of prototype vanadium(III) phosphate cathode materials, NaV(PO), LiV(PO), and KV(PO)·HO, for alkali-ion rechargeable batteries. XAS fluorescence yield and electron yield measurements reveal substantial variation in surface-to-bulk atomic structure, vanadium oxidation states, and density of oxygen hole states across all samples.

A Simplified Method for Patterning Graphene on Dielectric Layers.

The large-scale formation of patterned, quasi-freestanding graphene structures supported on a dielectric has so far been limited by the need to transfer the graphene onto a suitable substrate and contamination from the associated processing steps. We report μm scale, few-layer graphene structures formed at moderate temperatures (600-700 °C) and supported directly on an interfacial dielectric formed by oxidizing Si layers at the graphene/substrate interface. We show that the thickness of this underlying dielectric support can be tailored further by an additional Si intercalation of the graphene prior to oxidation.

Room temperature conductance switching in a molecular iron(iii) spin crossover junction.

Herein, we report the first room temperature switchable Fe(iii) molecular spin crossover (SCO) tunnel junction. The junction is constructed from [Fe(qsal-I)]NTf (qsal-I = 4-iodo-2-[(8-quinolylimino)methyl]phenolate) molecules self-assembled on graphene surfaces with conductance switching of one order of magnitude associated with the high and low spin states of the SCO complex. Normalized conductance analysis of the current-voltage characteristics as a function of temperature reveals that charge transport across the SCO molecule is dominated by coherent tunnelling.

Mechanistic implications of Li-S cell function through modification of organo-sulfur cathode architectures.

Copolymeric organo-sulfur based electrodes provide a unique framework to explore and subsequently improve lithium-sulfur (Li-S) cells. There is a general difference in the way copolymers trap lithium during cell function compared to inorganic carbon-sulfur composites. Using a chain-like polyterpene copolymeric architecture involving the copolymerization of squalene monomer with sulfur (poly(S-r-squalene)), the first evidence for distinguishable differences in the entrapment of lithiated species, when using different copolymeric architectures, is provided.

Bias-Polarity-Dependent Direct and Inverted Marcus Charge Transport Affecting Rectification in a Redox-Active Molecular Junction.

This paper describes the transition from the normal to inverted Marcus region in solid-state tunnel junctions consisting of self-assembled monolayers of benzotetrathiafulvalene (BTTF), and how this transition determines the performance of a molecular diode. Temperature-dependent normalized differential conductance analyses indicate the participation of the HOMO (highest occupied molecular orbital) at large negative bias, which follows typical thermally activated hopping behavior associated with the normal Marcus regime. In contrast, hopping involving the HOMO dominates the mechanism of charge transport at positive bias, yet it is nearly activationless indicating the junction operates in the inverted Marcus region.

Effect of Long- and Short-Range Disorder on the Oxygen Ionic Conductivity of Tm(TiTm)O "Stuffed" Pyrochlores.

The long-range average and short-range local structures in the Tm(TiTm)O ( = 0.00-0.67) series were studied using a combination of diffraction and spectroscopic techniques.

Outstanding Thermal Conductivity of Single Atomic Layer Isotope-Modified Boron Nitride.

Materials with high thermal conductivities (κ) are valuable to solve the challenge of waste heat dissipation in highly integrated and miniaturized modern devices. Herein, we report the first synthesis of atomically thin isotopically pure hexagonal boron nitride (BN) and its one of the highest κ among all semiconductors and electric insulators. Single atomic layer (1L) BN enriched with ^{11}B has a κ up to 1009  W/mK at room temperature.

Ablation in Externally Applied Electric and Magnetic Fields.

To harness light-matter interactions at the nano-/micro-scale, better tools for control must be developed. Here, it is shown that by applying an external electric and/or magnetic field, ablation of Si and glass under ultra-short (sub-1 ps) laser pulse irradiation can be controlled via the Lorentz force F = e E + e [ v × B ] , where v is velocity of charge , E is the applied electrical bias and B is the magnetic flux density. The external electric E-field was applied during laser ablation using suspended micro-electrodes above a glass substrate with an air gap for the incident laser beam.

External Field-Controlled Ablation: Magnetic Field.

The femtosecond laser ablation of silicon amidst an externally applied magnetic field in different orientations was investigated with respect to the scanning direction and polarisation of the laser beam, by observation of ablation patterns and debris displacement in a range of fluences, magnetic fields strengths, and geometries. Ultra-short ∼ 230 fs laser pulses of 1030 nm wavelengths were utilised in the single and multi-pulse irradiation modes. Ablation with an externally applied magnetic B-field B e x t ≈ 0.

Elucidation of structures and lithium environments for an organo-sulfur cathode.

Composite organo-sulfur cathodes provide a unique platform for the realization of lithium-sulfur (Li-S) cells. However, difficulties arise in the interpretation of the function of these electrodes in Li-S cells and the role they play in suppressing the so-called 'shuttle effect'. This work focuses on monitoring in detail the structural evolution and lithium environments during charge-discharge cycles in a lithium half-cell of an organo-sulfur cathode, which was synthesised by inverse vulcanisation with 1,3-diisopropenylbenzene.

Author Correction: Chemical nature of alkaline polyphosphate boundary film at heated rubbing surfaces.

A correction to this article has been published and is linked from the HTML and PDF versions of this paper. The error has been fixed in the paper.

Chemical nature of alkaline polyphosphate boundary film at heated rubbing surfaces.

Alkaline polyphosphate has been demonstrated to be able to reduce significant wear and friction of sliding interfaces under heavy loads (>1 GPa) and elevated temperature (800 °C and above) conditions, e.g. hot metal manufacturing.

Quick AS NEXAFS Tool (QANT): a program for NEXAFS loading and analysis developed at the Australian Synchrotron.

An analysis program for near-edge X-ray absorption fine-structure (NEXAFS) spectra has been developed and implemented at the soft X-ray beamline of the Australian Synchrotron. The program allows for instant viewing of corrected data channels including normalizations to a standard, double normalizations when the standard itself has an undesired spectral response, and background subtraction. The program performs simple compositional analysis and peak fitting and includes rapid common calculations such as the average tilt angle of molecules with respect to the surface, and the determination of the complex index of refraction, which previously required intensive manual analysis.

Black-CuO: surface-enhanced Raman scattering and infrared properties.

Large surface area samples of nanotextured black CuO were prepared by chemical etching of Cu for use in surface-enhanced Raman scattering (SERS). The SERS intensity of a self-assembled monolayer (SAM) of thiophenol was proportional to the thickness of a nanoscale-conformal Au film deposited by magnetron sputtering over the black CuO. A very high SERS yield of ∼10(4) counts per s per mW was observed for the thiophenol SAM on the thickest Au films studied here.

An unconventional method for measuring the Tc L3-edge of technetium compounds.

Tc L3-edge XANES spectra have been collected on powder samples of SrTcO3 (octahedral Tc(4+)) and NH4TcO4 (tetrahedral Tc(7+)) immobilized in an epoxy resin. Features in the Tc L3-edge XANES spectra are compared with the pre-edge feature of the Tc K-edge as well as other 4d transition metal L3-edges. Evidence of crystal field splitting is obvious in the Tc L3-edge, which is sensitive to the coordination number and oxidation state of the Tc cation.

Determining the electronic confinement of a subsurface metallic state.

Dopant profiles in semiconductors are important for understanding nanoscale electronics. Highly conductive and extremely confined phosphorus doping profiles in silicon, known as Si:P δ-layers, are of particular interest for quantum computer applications, yet a quantitative measure of their electronic profile has been lacking. Using resonantly enhanced photoemission spectroscopy, we reveal the real-space breadth of the Si:P δ-layer occupied states and gain a rare view into the nature of the confined orbitals.