Rhenium monoselenide:an investigation by density functional theory

Rhenium monoselenide: an investigation by density functional theory: supporting data for publicationSee R. M. Martin, "Electronic Structure: Basic Theory and Practical Methods", Cambridge UP, for a tutorial introduction to the computational methodology, plus citations in the associated article to the publications of the authors of the Quantum Espresso code

Spin-order-dependent magneto-elastic coupling in two dimensional antiferromagnetic MnPSe3_3 observed through Raman spectroscopy

Layered antiferromagnetic materials have emerged as a novel subset of the two-dimensional family providing a highly accessible regime with prospects for layer-number-dependent magnetism. Furthermore, transition metal phosphorous trichalcogenides, MPX3 (M = transition metal; X = chalcogen) provide a platform for investigating fundamental interactions between magnetic and lattice degrees of freedom providing new insights for developing fields of spintronics and magnonics. Here, we use a combination of temperature dependent Raman spectroscopy and density functional theory to explore magnetic-ordering-dependent interactions between the manganese spin degree of freedom and lattice vibrations of the non-magnetic sub-lattice via a Kramers-Anderson super-exchange pathway in both bulk, and few-layer, manganese phosphorous triselenide (MnPSe$_3$). We observe a nonlinear temperature dependent shift of phonon modes predominantly associated with the non-magnetic sub-lattice, revealing their non-trivial spin-phonon coupling below the N{\'e}el temperature at 74 K, allowing us to extract mode-specific spin-phonon coupling constants.Comment: 20 pages, 4 figures, Submitted to ACS Nano Letter

Nanoimprint lithography of Al nanovoids for deep-UV SERS.

Deep-ultraviolet surface-enhanced Raman scattering (UV-SERS) is a promising technique for bioimaging and detection because many biological molecules possess UV absorption lines leading to strongly resonant Raman scattering. Here, Al nanovoid substrates are developed by combining nanoimprint lithography of etched polymer/silica opal films with electron beam evaporation, to give a high-performance sensing platform for UV-SERS. Enhancement by more than 3 orders of magnitude in the UV-SERS performance was obtained from the DNA base adenine, matching well the UV plasmonic optical signatures and simulations, demonstrating its suitability for biodetection.We acknowledge financial support from EPSRC grant EP/G060649/1, EP/I012060/1, EP/J007552/1, ERC grant LINASS 320503.This is the final version of the article. It first appeared from ACS via http://dx.doi.org/10.1021/am505511

Using in-plane anisotropy to engineer Janus monolayers of rhenium dichalcogenides

The new class of Janus two-dimensional (2D) transition-metal dichalcogenides with two different interfaces are currently gaining increasing attention due to their distinct properties different from the typical 2D materials. Here, we show that in-plane anisotropy of a 2D atomic crystal, like ReS$_{2}$ or ReSe$_{2}$, allows formation of a large number of inequivalent Janus monolayers. We use first-principles calculations to investigate the structural stability of 29 distinct ReX$_{2-x}$Y$_{x}$ ($\mathrm{X,Y \in \{S,Se\}}$) structures, which can be obtained by selective exchange of exposed chalcogens in a ReX$_{2}$ monolayer. We also examine the electronic properties and work function of the most stable Janus monolayers and show that the large number of inequivalent structures provides a way to engineer spin-orbit splitting of the electronic bands. We find that the breaking of inversion symmetry leads to sizable spin splittings and spontaneous diople moments than are larger than those in other Janus dichalcogenides. Moreover, our caluclations suggest that the work function of the Janus monolayers can be tuned by varying the content of the substituting chalcogen. Our work demonstrates that in-plane anisotropy provides additional flexibility in sub-layer engineering of 2D atomic crystals

Investigating nanostructures in carbon fibres using Raman spectroscopy

Nanostructures in the PAN-based carbon fibres were investigated by means of the Raman spectroscopy which was performed using a series of different excitation wavelengths. UV-Raman measurements showed the predominance of sp2 carbon for the carbon fibres with Young’s moduli ranging from 55 to 440 GPa. The excitation wavelength dependence of the spectral line shape implied the presence of the graphitic (sp2 carbon layers) as well as the amorphous carbon-like component (sp2 carbon clusters) in these fibres. An analytical modelbased upon the Tuinstra-Koenig relation and the rule-of-mixtures concept was proposed to account for the observed behaviour of the peak intensity ratio ID/IG. It was suggested that the carbonisation heat treatment led to the sp2 carbon layers extending rapidly throughout the nanostructure, resulting in the complete loss of the sp2 carbon clusters for the higher-modulus carbon fibres. These new findings together with the proposed analytical model are believed to be essential keys towards the development of new generation carbon fibres

Surface enhanced Raman scattering of crystal violet

Despite the ubiquity of Raman spectroscopy, fluorescence, poor signal strength and photobleaching pose a significant challenge to researchers in the biomedical field. Here, we demonstrate a 17-fold signal enhancement in Raman spectra of crystal violet via surface-enhanced Raman scattering (SERS). The SERS substrate was fabricated by electron beam lithography (EBL); the nanostructured surface was an array of G-shaped elements made of Au on SiO2/Si. In addition to the SERS spectra, finite-difference time-domain simulations were performed to illustrate the distribution of electric-field hot-spots on the SERS substrate. The electric-field hot-spots were prominent at the vertices and edges of the nanostructured G-shaped motifs. The results presented here demonstrate that EBL is a high-end choice for SERS substrate fabrication that opens the way for more complex Raman spectroscopies, for instance involving nonlinear optics or chiral analytes

Observation of oxygen dimers via energy transfer from silicon nanoparticles

Energy transfer from photo-excited excitons confined in silicon nanoparticles to oxygen dimers adsorbed on the nanoparticle surfaces is studied as a function of temperature and magnetic field.</p

First-Principles Estimation of Core Level Shifts for Hf, Ta, W, and Re

A simple first-principles approach is used to estimate the core level shifts observed in X-ray photoelectron spectroscopy for the 4f electrons of Hf, Ta, W, and Re; these elements were selected because their 4f levels are relatively close to the Fermi energy. The approach is first tested by modeling the surface core level shifts of low-index surfaces of the four elemental metals, followed by its application to the well-studied material TaSe2 in the commensurate charge density wave (CDW) phase, where agreement with experimental data is found to be good, showing that this approach can yield insights into modifications of the CDW. Finally, unterminated surface core level shifts in the hypothetical MXene Ta3C2 are modeled, and the potential of XPS for the investigation of the surface termination of MXenes is demonstrated

Interplay of crystal thickness and in-plane anisotropy and evolution of quasi-one dimensional electronic character in ReSe₂

We study the valence band structure of ReSe2 crystals with varying thickness down to a single layer using nanoscale angle-resolved photoemission spectroscopy and density functional theory. The width of the top valence band in the direction perpendicular to the rhenium chains decreases with decreasing number of layers, from ~200 meV for the bulk to ~80 meV for monolayer. This demonstrates increase of in-plane anisotropy induced by changes in the interlayer coupling and suggests progressively more one-dimensional character of electronic states in few-layer rhenium dichalcogenides