Chirality conferral is fundamental for understanding the origin of life, and it is of direct importance for synthesizing new pharmaceuticals in the face of growing antibiotic resistance. Human-made, self-assembling nanostructures replicate the biological chirality conferral processes utilizing covalent and non-covalent bonds. However, chirality conferral from one form of matter to another via electromagnetic fields is more subtle and less explored. Here we report chirality conferral between gold nanohelices and achiral molecules (crystal violet). This conferral enables the experimental observation of a physical effect predicted in 1979-hyper-Raman optical activity. To benefit from Fermi's golden rule, the chirality conferral system was designed as doubly resonant, with the nanohelices and molecules resonating at the fundamental frequency and at the second-harmonic, respectively. We provide a theoretical framework for our results that expands the original mathematical formalism to include surface-enhanced hyper-Raman scattering and the chirality conferral process. Our results demonstrate that field-driven chirality conferral mechanisms are opening up entire fields of research, as exemplified by the discovery of a physical phenomenon. Theoretically predicted in 1979, hyper-Raman optical activity is now experimentally observed through chirality conferral from the electromagnetic field of chiral plasmonic gold nanohelices to crystal violet molecules that are achiral, sparking new science at the organic-inorganic interface.

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.

There is a pressing need for reliable, reproducible and accurate measurements of graphene’s properties, through international standards, to facilitate industrial growth. However, trustworthy and verified standards require rigorous metrological studies, determining, quantifying and reducing the sources of measurement uncertainty. Towards this effort, we report the procedure and the results of an international interlaboratory comparison (ILC) study, conducted under Versailles Project on Advanced Materials and Standards. This ILC focusses on the comparability of Raman spectroscopy measurements of chemical vapour deposition (CVD) grown graphene using the same measurement protocol across different institutes and laboratories. With data gathered from 17 participants across academia, industry (including instrument manufacturers) and national metrology institutes, this study investigates the measurement uncertainty contributions from both Raman spectroscopy measurements and data analysis procedures, as well as provides solutions for improved accuracy and precision. While many of the reported Raman metrics were relatively consistent, significant and meaningful outliers occurred due to differences in the instruments and data analysis. These variations resulted in inconsistent reports of peak intensity ratios, peak widths and the coverage of graphene. Due to a lack of relative intensity calibration, the relative difference reported in the 2D- and G peak intensity ratios ( I2D/IG ) was up to 200%. It was also shown that the standard deviation for Γ2D values reported by different software packages, was 15× larger for Lorentzian fit functions than for pseudo-Voigt functions. This study has shown that by adopting a relative intensity calibration and consistent peak fitting and data analysis methodologies, these large, and previously unquantified, variations can be significantly reduced, allowing more reproducible and comparable measurements for the graphene community, supporting fundamental research through to the growing graphene industry worldwide. This project and its findings directly underpin the development of the ISO/IEC standard ‘DTS 21356-2—Nanotechnologies—Structural Characterisation of CVD-grown Graphene’.

We demonstrate a non-destructive approach to understanding the growth modes of a GaN thin film and simultaneously quantify its residual strains and their effect on optical and electrical properties using correlative scanning electron microscopy techniques and Raman microscopy. Coincident strain maps derived from electron backscatter diffraction, cathodoluminescence, and confocal Raman techniques reveal strain variations with similar magnitude and directions, especially in the proximity of dislocations. Correlating confocal Raman imaging with electron channeling contrast imaging suggests that the dislocations organize themselves to form a distinctive pattern as a result of the underlying growth mask, where some of them align along the [0001] growth direction and some are inclined. The methodology presented in this work can be adopted to investigate any heteroepitaxial growth, in particular, those using selective masks on the growth substrates, where the morphology influences the subsequent growth.

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.

Lumerical data includes a text file with the electric field strength data in a plane 26 nm from the silicon substrate surface as presented in graphical form in the paper. The associated material models and fit settings in Lumerical are included in a screen shot. The spectra presented in the paper are included in text file format.

Plasmonic nanowires are key building-blocks for plasmonic based devices, such as nano-sources and nano-sensors. They can take advantage of the propagative nature of surface plasmon polaritons (SPP) in a guided way, and the strong field enhancement at the nanowire tips. Here, the proof-of-concept of a SPP-mediated remote Raman effect with a coaxial nanowire is reported [1]. The remote Raman spectroscopy consists in probing a species at a distanced place from the excitation. The metallic nanowire geometry promotes a guiding of the surface plasmon polaritons along several micrometers, while the required momentum matching for exciting SPP is allowed by the discontinuity at the nanowire tip. The proposed systems are cylindrical coaxial nanowires consisting of a gold core to propagate SPP and a Raman-emitting shell of poly(3,4-ethylene-dioxythiophene) (PEDOT) grown only at one tip of the gold nanowire. A second challenge has been tackled, dealing with the weakness of the Raman signal to be detected. It was proposed to enlarge the nanowire tips in order to enhance the in-coupling of an excitation optical signal with the nanowire, and the out-coupling of the plasmon-mediated signal at a remote location. It has been achieved by transforming the gold nanowire tips with dry laser heating treatments to obtain dumbbell-like nanowires. The plasmonic properties of these original nanowires have been determined by an EELS-STEM study and interpreted by finite-element modeling. The benefits of these enlarged tips on the optical signal has been investigated by a Rayleigh backscattering study. [1] D. Funes-Hernando, M. Peláez-Fernández, D. Winterauer, J.-Y. Mevellec, R. Arenal, T. Batten, B. Humbert and J.L. Duvail Nanoscale (2018) 10, 6437 – 6444

This work introduces hyper-resolution (HyRes), a numerical approach for spatial resolution enhancement that combines hyperspectral unmixing and super-resolution image restoration (SRIR). HyRes yields a substantial increase in spatial resolution of Raman spectroscopy while simultaneously preserving the undistorted spectral information. The resolving power of this technique is demonstrated on Raman spectroscopic data from a polymer nanowire sample. Here, we demonstrate an achieved resolution of better than 14 nm, a more than eightfold improvement on single-channel image-based SRIR and 25 × better than regular far-field Raman spectroscopy, and comparable to near-field probing techniques.

In this chapter we explore the possibilities of using MoS2 for chemical gas sensing. We first introduce monolayer MoS2 and discuss the different reconstructed phases that can be produced in terms of their atomic and electronic structure. We show how these properties can vary drastically from their bulk counterparts, and how MoS2 can be taken as a useful model for other transition metal dichalcogenides (TMDs). We next explore different routes to tune the material properties through chemical functionalisation, before summarising the current literature on gas sensing using MoS2. We discuss the possibilities for Raman spectroscopy of MoS2 as a highly selective route to gas sensing, and the future possibilities for this as-yet largely unexplored application for this important family of monolayer TMDs.

Nicola Bannister, Jonathan Skelton, Gabriele Kociok-Köhn, Tim Batten, Enrico Da Como, and Simon Crampin Department of Physics, University of Bath, Claverton Down, Bath, BA2 7AY, UK School of Chemistry, University of Manchester, Manchester, M13 9PL, UK Department of Chemistry and Material and Chemical Characterisation Facility (MC ), University of Bath, Claverton Down, Bath, BA2 7AY, UK Renishaw plc, Wotton-under-Edge, Gloucestershire, GL12 7DW, UK (Dated: October 10, 2019)

Understanding collective electronic states such as superconductivity and charge density waves is pivotal for fundamental science and applications. The layered transition metal dichalcogenide 1T-TiSe2 hosts a unique charge density wave (CDW) phase transition whose origins are still not fully understood. Here, we present ultrafast time- and angle-resolved photoemission spectroscopy (TR-ARPES) measurements complemented by time-resolved reflectivity (TRR) which allows us to establish the contribution of excitonic and electron-phonon interactions to the CDW. We monitor the energy shift of the valence band (VB) and coupling to coherent phonons as a function of laser fluence. The VB shift, directly related to the CDW gap closure, exhibits a markedly slower recovery dynamics at fluences above F-th = 60 mu J cm(-2). This observation coincides with a shift in the relative weight of coherently coupled phonons to higher-frequency modes in TRR, suggesting a phonon bottleneck. Using a rate equation model, the emergence of a high-fluence bottleneck is attributed to an abrupt reduction in coupled phonon damping and an increase in exciton dissociation rate linked to the loss of CDW superlattice phonons. Thus, our work establishes the important role of both excitonic and phononic interactions in the CDW phase transition and the advantage of combining complementary femtosecond techniques to understand the complex interactions in quantum materials.

The growth of >100-μm-thick diamond layers adherent on aluminum nitride with low thermal boundary resistance between diamond and AlN is presented in this work. The thermal barrier resistance was found to be in the range of 16 m2·K/GW, which is a large improvement on the current state-of-the-art. While thick films failed to adhere on untreated AlN films, AlN films treated with hydrogen/nitrogen plasma retained the thick diamond layers. Clear differences in ζ-potential measurement confirm surface modification due to hydrogen/nitrogen plasma treatment. An increase in non-diamond carbon in the initial layers of diamond grown on pretreated AlN is seen by Raman spectroscopy. The presence of non-diamond carbon has minimal effect on the thermal barrier resistance. The surfaces studied with X-ray photoelectron spectroscopy revealed a clear distinction between pretreated and untreated samples. The surface aluminum goes from a nitrogen-rich environment to an oxygen-rich environment after pretreatment. A clean interface between diamond and AlN is seen by cross-sectional transmission electron microscopy.

Raman microscopy is a valuable tool for detecting physical and chemical properties of a sample material. When probing nanomaterials or nanocomposites the spatial resolution of Raman microscopy is not always adequate as it is limited by the optical diffraction limit. Numerical post-processing with super-resolution algorithms provides a means to enhance resolution and can be straightforwardly applied. The aim of this work is to present interior point least squares (IPLS) as a powerful tool for super-resolution in Raman imaging through constrained optimization. IPLS’s potential for super-resolution is illustrated on numerically generated test images. Its resolving power is demonstrated on Raman spectroscopic data of a polymer nanowire sample. Comparison to atomic force microscopy data of the same sample substantiates that the presented method is a promising technique for analyzing nanomaterial samples.

Nicola Bannister, Jonathan Skelton, Gabriele Kociok-Köhn, Tim Batten, Enrico Da Como, and Simon Crampin Department of Physics, University of Bath, Claverton Down, Bath, BA2 7AY, UK School of Chemistry, University of Manchester, Manchester, M13 9PL, UK Department of Chemistry and Material and Chemical Characterisation Facility (MC ), University of Bath, Claverton Down, Bath, BA2 7AY, UK Renishaw plc, Wotton-under-Edge, Gloucestershire, GL12 7DW, UK (Dated: October 10, 2019)

We combine polarization-resolved low frequency Raman microscopy and dispersion-corrected density-functional calculations (DFT-D3) to study polymorph-dependent lattice vibrations in coronene, a model molecular system for nanographenes and disc-like organic semiconductors that exhibits two crystalline structures with distinct electronic and optical properties. Changes in low energy Raman-active lattice phonons are followed across the {\gamma}- to \b{eta}-phase transition at 150 K. Raman frequencies calculated using DFT-D3 agree to within 4 cm-1, and on the basis of polarisation dependence of peak positions and intensities we achieve a clear mode assignment. Studies of the associated atomic motions show how the pure librational and rotational modes of {\gamma}-coronene change into mixed roto-librations in the \b{eta}-phase, explaining the remarkable differences in Raman spectra of the two phases.

Raman images are restored using interior point least squares (IPLS). Bounding hyperplane-based hyperspectral unmixing reduces the dimensionality of the data cube, substantially decreasing computation time. IPLS is then independently applied to all resulting map images. The proposed method is first validated on simulated data and then being applied to real Raman spectroscopic data. The results allow for better physical characterisation of the sample and the spatial resolution is enhanced from 400nm to better than 50nm.

This study reports on the plasmon-mediated remote Raman sensing promoted by specially designed coaxial nanowires. This unusual geometry for Raman study is based on the separation, by several micrometres, of the excitation laser spot, on one tip of the nanowire, and the Raman detection at the other tip. The very weak efficiency of Raman emission makes it challenging in a remote configuration. For the proof-of-concept, we designed coaxial nanowires consisting of a gold core to propagate surface plasmon polaritons and a Raman-emitting shell of poly(3,4-ethylene-dioxythiophene). The success of the fabrication was demonstrated by correlating, for the same single nanowire, a morphological analysis by electron microscopy and Raman spectroscopy analysis. Importantly for probing the remote-Raman effect, the original hard template-based process allows one to control the location of the polymer shell all along the nanowire, or only close to one or the two nanowire tips. Such all-in-one single nanowires could have applications in the remote detection of photo-degradable substances and for exploring 1D nanosources for integrated photonic and plasmonic systems.

III-nitride nanostructures are of interest for a new generation of light-emitting diodes (LEDs). However, the characterization of doping incorporation in nanorod (NR) structures, which is essential for creating the p-n junction diodes, is extremely challenging. This is because the established electrical measurement techniques (such as capacitance–voltage or Hall-effect methods) require a simple sample geometry and reliable ohmic contacts, both of which are difficult to achieve in nanoscale devices. The need for homogenous, conformal n-type or p-type layers in core–shell nanostructures magnifies these challenges. Consequently, we demonstrate how a combination of non-contact methods (micro-photoluminescence, micro-Raman and cathodoluminescence), as well as electron-beam-induced-current, can be used to analyze the uniformity of magnesium incorporation in core–shell NRs and make a first estimate of doping levels by the evolution of band transitions, strain and current mapping. These techniques have been used to optimize the growth of core–shell nanostructures for electrical carrier injection, a significant milestone for their use in LEDs.