Dense Arrays of Nanohelices: Raman Scattering from Achiral Molecules Reveals the Near-Field Enhancements at Chiral Metasurfaces.

Against the background of the current healthcare and climate emergencies, surface enhanced Raman scattering (SERS) is becoming a highly topical technique for identifying and fingerprinting molecules, e.g., within viruses, bacteria, drugs, and atmospheric aerosols. Crucial for SERS is the need for substrates with strong and reproducible enhancements of the Raman signal over large areas and with a low fabrication cost. Here, dense arrays of plasmonic nanohelices (≈100 nm in length), which are of interest for many advanced nanophotonics applications, are investigated, and they are shown to present excellent SERS properties. As an illustration, two new ways to probe near-field enhancement generated with circular polarization at chiral metasurfaces are presented, first using the Raman spectra of achiral molecules (crystal violet) and second using a single, element-specific, achiral molecular vibrational mode (i.e., a single Raman peak). The nanohelices can be fabricated over large areas at a low cost and they provide strong, robust and uniform Raman enhancement. It is anticipated that these advanced materials will find broad applications in surface enhanced Raman spectroscopies and material science.

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.

Singlet oxygen generation by nanoporous silicon: photoluminescence dynamics in magnetic field.

Singlet oxygen generation in porous silicon (PSi) was investigated by a magneto-optical experiment. Photoluminescence (PL) quenching due to an energy transfer (ET) process mediated by an exchange interaction was monitored in the spectral range 1.4-2.5 eV and in a magnetic field of 0-6 Tesla at different levels of oxygen concentration and excitation pump power. When a magnetic field was applied, both PL recovery and, for magnetic fields below 2 Tesla and high concentrations of oxygen, an unusual additional pump power dependent quenching of the PL was observed. A rate equation model describing the behavior of PL from PSi with oxygen adsorbed at cryogenic temperatures in magnetic field was developed. The model has been expanded to cover the ET process as a function of the nanoparticle size.

Raman Techniques: Fundamentals and Frontiers.

Driven by applications in chemical sensing, biological imaging and material characterisation, Raman spectroscopies are attracting growing interest from a variety of scientific disciplines. The Raman effect originates from the inelastic scattering of light, and it can directly probe vibration/rotational-vibration states in molecules and materials. Despite numerous advantages over infrared spectroscopy, spontaneous Raman scattering is very weak, and consequently, a variety of enhanced Raman spectroscopic techniques have emerged. These techniques include stimulated Raman scattering and coherent anti-Stokes Raman scattering, as well as surface- and tip-enhanced Raman scattering spectroscopies. The present review provides the reader with an understanding of the fundamental physics that govern the Raman effect and its advantages, limitations and applications. The review also highlights the key experimental considerations for implementing the main experimental Raman spectroscopic techniques. The relevant data analysis methods and some of the most recent advances related to the Raman effect are finally presented. This review constitutes a practical introduction to the science of Raman spectroscopy; it also highlights recent and promising directions of future research developments.

Electronic bandstructure and van der Waals coupling of ReSe2 revealed by high-resolution angle-resolved photoemission spectroscopy.

ReSe2 and ReS2 are unusual compounds amongst the layered transition metal dichalcogenides as a result of their low symmetry, with a characteristic in-plane anisotropy due to in-plane rhenium 'chains'. They preserve inversion symmetry independent of the number of layers and, in contrast to more well-known transition metal dichalcogenides, bulk and few-monolayer Re-TMD compounds have been proposed to behave as electronically and vibrational decoupled layers. Here, we probe for the first time the electronic band structure of bulk ReSe2 by direct nanoscale angle-resolved photoemission spectroscopy. We find a highly anisotropic in- and out-of-plane electronic structure, with the valence band maxima located away from any particular high-symmetry direction. The effective mass doubles its value perpendicular to the Re chains and the interlayer van der Waals coupling generates significant electronic dispersion normal to the layers. Our density functional theory calculations, including spin-orbit effects, are in excellent agreement with these experimental findings.

Lattice Dynamics of the Rhenium and Technetium Dichalcogenides.

The rhenium and technetium dichalcogenides are layered van der Waals semiconductors which show a large number of Raman-active zone-centre phonon modes as a result of their unusually large unit cells and deviation from hexagonal symmetry. They thus offer the possibility of introducing in-plane anisotropy into composite heterostructures based on van der Waals materials, and Raman spectroscopy is generally used to determine their in-plane orientation. We show that first-principles calculations give a good description of the lattice dynamics of this family of materials and thus predict the zone-centre phonon frequencies and Raman activities of TcS2. We consider the distribution of the phonon modes in frequency and their atomic displacements and give a unified understanding of the phonon frequencies and Raman spectra of ReS2, TcS2 and ReSe2 in terms of the scaling of Raman frequency with the chalcogen mass.

Rhenium Dichalcogenides: Layered Semiconductors with Two Vertical Orientations.

The rhenium and technetium diselenides and disulfides are van der Waals layered semiconductors in some respects similar to more well-known transition metal dichalcogenides (TMD) such as molybdenum sulfide. However, their symmetry is lower, consisting only of an inversion center, so that turning a layer upside-down (that is, applying a C2 rotation about an in-plane axis) is not a symmetry operation, but reverses the sign of the angle between the two nonequivalent in-plane crystallographic axes. A given layer thus can be placed on a substrate in two symmetrically nonequivalent (but energetically similar) ways. This has consequences for the exploitation of the anisotropic properties of these materials in TMD heterostructures and is expected to lead to a new source of domain structure in large-area layer growth. We produced few-layer ReS2 and ReSe2 samples with controlled "up" or "down" orientations by micromechanical cleavage and we show how polarized Raman microscopy can be used to distinguish these two orientations, thus establishing Raman as an essential tool for the characterization of large-area layers.

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. Quenching features in the nanoparticle photoluminescence spectrum arise from energy transfer to the oxygen dimers with and without the emission of Si TO(Δ) phonons and, also, with and without the vibrational excitation of the dimers. The dependence of the quenching on magnetic field shows that energy transfer is fast when a dimer is present, allowing an estimate of the proportion of the nanoparticles with adsorbed dimers.

Raman spectra of monolayer, few-layer, and bulk ReSe2: an anisotropic layered semiconductor.

Rhenium diselenide (ReSe2) is a layered indirect gap semiconductor for which micromechanical cleavage can produce monolayers consisting of a plane of rhenium atoms with selenium atoms above and below. ReSe2 is unusual among the transition-metal dichalcogenides in having a low symmetry; it is triclinic, with four formula units per unit cell, and has the bulk space group P1̅. Experimental studies of Raman scattering in monolayer, few-layer, and bulk ReSe2 show a rich spectrum consisting of up to 16 of the 18 expected lines with good signal strength, pronounced in-plane anisotropy of the intensities, and no evidence of degradation of the sample during typical measurements. No changes in the frequencies of the Raman bands with layer thickness down to one monolayer are observed, but significant changes in relative intensity of the bands allow the determination of crystal orientation and of monolayer regions. Supporting theory includes calculations of the electronic band structure and Brillouin zone center phonon modes of bulk and monolayer ReSe2 as well as the Raman tensors determining the scattering intensity of each mode. It is found that, as for other transition-metal dichalcogenides, Raman scattering provides a powerful diagnostic tool for studying layer thickness and also layer orientation in few-layer ReSe2.

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.

Magnetic field dependence of singlet oxygen generation by nanoporous silicon.

Energy transfer from photoexcited excitons localized in silicon nanoparticles to adsorbed oxygen molecules excites them to the reactive singlet spin state. This process has been studied experimentally as a function of nanoparticle size and applied external magnetic field as a test of the accepted understanding of this process in terms of the exchange coupling between the nano-Si exciton and the adsorbed O2 molecules.

Hydrothermal conversion of one-photon-fluorescent poly(4-vinylpyridine) into two-photon-fluorescent carbon nanodots.

A novel two-photon-fluorescent N,O-heteroatom-rich carbon nanomaterial has been synthesized and characterized. The new carbon nanoparticles were produced by hydrothermal conversion from a one-photon-fluorescent poly(4-vinylpyridine) precursor (P4VP). The carbonized particles (cP4VP dots) with nonuniform particle diameter (ranging from sub-6 to 20 nm with some aggregates up to 200 nm) exhibit strong fluorescence properties in different solvents and have also been investigated for applications in cell culture media. The cP4VP dots retain their intrinsic fluorescence in a cellular environment and exhibit an average excited-state lifetime of 2.0 ± 0.9 ns in the cell. The cP4VP dots enter HeLa cells and do not cause significant damage to outer cell membranes. They provide one-photon or two-photon fluorescent synthetic scaffolds for imaging applications and/or drug delivery.

Porous silicon nanocrystals in a silica aerogel matrix.

Silicon nanoparticles of three types (oxide-terminated silicon nanospheres, micron-sized hydrogen-terminated porous silicon grains and micron-size oxide-terminated porous silicon grains) were incorporated into silica aerogels at the gel preparation stage. Samples with a wide range of concentrations were prepared, resulting in aerogels that were translucent (but weakly coloured) through to completely opaque for visible light over sample thicknesses of several millimetres. The photoluminescence of these composite materials and of silica aerogel without silicon inclusions was studied in vacuum and in the presence of molecular oxygen in order to determine whether there is any evidence for non-radiative energy transfer from the silicon triplet exciton state to molecular oxygen adsorbed at the silicon surface. No sensitivity to oxygen was observed from the nanoparticles which had partially H-terminated surfaces before incorporation, and so we conclude that the silicon surface has become substantially oxidised. Finally, the FTIR and Raman scattering spectra of the composites were studied in order to establish the presence of crystalline silicon; by taking the ratio of intensities of the silicon and aerogel Raman bands, we were able to obtain a quantitative measure of the silicon nanoparticle concentration independent of the degree of optical attenuation.

Carbon nanoparticle surface functionalisation: converting negatively charged sulfonate to positively charged sulfonamide.

The surface functionalities of commercial sulfonate-modified carbon nanoparticles (ca. 9-18 nm diameter, Emperor 2000) have been converted from negatively charged to positively charged via sulfonylchloride formation followed by reaction with amines to give suphonamides. With ethylenediamine, the resulting positively charged carbon nanoparticles exhibit water solubility (in the absence of added electrolyte), a positive zeta-potential, and the ability to assemble into insoluble porous carbon films via layer-by-layer deposition employing alternating positive and negative carbon nanoparticles. Sulfonamide-functionalised carbon nanoparticles are characterised by Raman, AFM, XPS, and voltammetric methods. Stable thin film deposits are formed on 3 mm diameter glassy carbon electrodes and cyclic voltammetry is used to characterise capacitive background currents and the adsorption of the negatively charged redox probe indigo carmine. The Langmuirian binding constant K = 4000 mol(-1)dm(3) is estimated and the number of positively charged binding sites per particle determined as a function of pH.

Coherent Raman detected electron spin resonance spectroscopy of metalloproteins: linking electron spin resonance and magnetic circular dichroism.

The simultaneous excitation of paramagnetic molecules with optical (laser) and microwave radiation in the presence of a magnetic field can cause an amplitude, or phase, modulation of the transmitted light at the microwave frequency. The detection of this modulation indicates the presence of coupled optical and ESR transitions. The phenomenon can be viewed as a coherent Raman effect or, in most cases, as a microwave frequency modulation of the magnetic circular dichroism by the precessing magnetization. By allowing the optical and magnetic properties of a transition metal ion centre to be correlated, it becomes possible to deconvolute the overlapping optical or ESR spectra of multiple centres in a protein or of multiple chemical forms of a particular centre. The same correlation capability also allows the relative orientation of the magnetic and optical anisotropies of each species to be measured, even when the species cannot be obtained in a crystalline form. Such measurements provide constraints on electronic structure calculations. The capabilities of the method are illustrated by data from the dimeric mixed-valence Cu(A) centre of nitrous oxide reductase (N(2)OR) from Paracoccus pantotrophus.