Correction: Rosales et al. Non-Absorbing Dielectric Materials for Surface-Enhanced Spectroscopies and Chiral Sensing in the UV. Nanomaterials 2020, 10, 2078.

In the published study [...].

Stability of Nanometer-Thick Layered Gallium Chalcogenides and Improvements via Hydrogen Passivation.

The gallium monochalcogenides family, comprising gallium sulfide (GaS), gallium selenide (GaSe), and gallium telluride (GaTe), is capturing attention for its applications in energy storage and production, catalysis, photonics, and optoelectronics. This interest originates from their properties, which include an optical bandgap larger than those of most common transition metal dichalcogenides, efficient light absorption, and significant carrier mobility. For any application, stability to air exposure is a fundamental requirement. Here, we perform a comparative study of the stability of layered GaS, GaSe, and GaTe nanometer-thick films down to a few layers with the goal of identifying the most suitable Ga chalcogenide for future integration in photonic and optoelectronic devices. Our study unveils a trend of decreasing air stability from sulfide to selenide and finally to telluride. Furthermore, we demonstrate a hydrogen passivation process to prevent the oxidation of GaSe with a higher feasibility and durability than other state-of-the-art passivation methods proposed in the literature.

Directional Scattering Switching from an All-Dielectric Phase Change Metasurface.

All-dielectric metasurfaces are a blooming field with a wide range of new applications spanning from enhanced imaging to structural color, holography, planar sensors, and directionality scattering. These devices are nanopatterned structures of sub-wavelength dimensions whose optical behavior (absorption, reflection, and transmission) is determined by the dielectric composition, dimensions, and environment. However, the functionality of these metasurfaces is fixed at the fabrication step by the geometry and optical properties of the dielectric materials, limiting their potential as active reconfigurable devices. Herein, a reconfigurable all-dielectric metasurface based on two high refractive index (HRI) materials like silicon (Si) and the phase-change chalcogenide antimony triselenide (Sb2Se3) for the control of scattered light is proposed. It consists of a 2D array of Si-Sb2Se3-Si sandwich disks embedded in a SiO2 matrix. The tunability of the device is provided through the amorphous-to-crystalline transition of Sb2Se3. We demonstrate that in the Sb2Se3 amorphous state, all the light can be transmitted, as it is verified using the zero-backward condition, while in the crystalline phase most of the light is reflected due to a resonance whose origin is the contribution of the electric (ED) and magnetic (MD) dipoles and the anapole (AP) of the nanodisks. By this configuration, a contrast in transmission (ΔT) of 0.81 at a wavelength of 980 nm by governing the phase of Sb2Se3 can be achieved.

Layered gallium sulfide optical properties from monolayer to CVD crystalline thin films.

Interest in layered van der Waals semiconductor gallium monosulfide (GaS) is growing rapidly because of its wide band gap value between those of two-dimensional transition metal dichalcogenides and of insulating layered materials such as hexagonal boron nitride. For the design of envisaged optoelectronic, photocatalytic and photonic applications of GaS, the knowledge of its dielectric function is fundamental. Here we present a combined theoretical and experimental investigation of the dielectric function of crystalline 2H-GaS from monolayer to bulk. Spectroscopic imaging ellipsometry with micron resolution measurements are corroborated by first principle calculations of the electronic structure and dielectric function. We further demonstrate and validate the applicability of the established dielectric function to the analysis of the optical response of c-axis oriented GaS layers grown by chemical vapor deposition (CVD). These optical results can guide the design of novel, to our knowledge, optoelectronic and photonic devices based on low-dimensional GaS.

Plasmonic hot-electron reconfigurable photodetector based on phase-change material Sb2S3.

Hot-carrier based photodetectors and enhanced by surface plasmons (SPs) hot-electron injection into semiconductors, are drawing significant attention. This photodetecting strategy yields to narrowband photoresponse while enabling photodetection at sub-bandgap energies of the semiconductor materials. In this work, we analyze the design of a reconfigurable photodetector based on a metal-semiconductor (MS) configuration with interdigitated dual-comb Au electrodes deposited on the semiconducting Sb2S3 phase-change material. The reconfigurability of the device relies on the changes of refractive index between the amorphous and crystalline phases of Sb2S3 that entail a modulation of the properties of the SPs generated at the dual-comb Au electrodes. An exhaustive numerical study has been realized on the Au grating parameters formed by the dual-comb electrodes, and on the SP order with the purpose of optimizing the absorption of the device, and thus, the responsivity of the photodetector. The optimized photodetector layout proposed here enables tunable narrowband photodetection from the O telecom band (λ = 1310 nm) to the C telecom band (λ = 1550 nm).

Interlaboratory study on Sb2S3 interplay between structure, dielectric function, and amorphous-to-crystalline phase change for photonics.

Antimony sulfide, Sb2S3, is interesting as the phase-change material for applications requiring high transmission from the visible to telecom wavelengths, with its band gap tunable from 2.2 to 1.6 eV, depending on the amorphous and crystalline phase. Here we present results from an interlaboratory study on the interplay between the structural change and resulting optical contrast during the amorphous-to-crystalline transformation triggered both thermally and optically. By statistical analysis of Raman and ellipsometric spectroscopic data, we have identified two regimes of crystallization, namely 250°C ≤ T < 300°C, resulting in Type-I spherulitic crystallization yielding an optical contrast Δn ∼ 0.4, and 300 ≤ T < 350°C, yielding Type-II crystallization bended spherulitic structure with different dielectric function and optical contrast Δn ∼ 0.2 below 1.5 eV. Based on our findings, applications of on-chip reconfigurable nanophotonic phase modulators and of a reconfigurable high-refractive-index core/phase-change shell nanoantenna are designed and proposed.

Interplay between Thickness, Defects, Optical Properties, and Photoconductivity at the Centimeter Scale in Layered GaS.

From the group-III monochalcogenide (MX, M = Ga, In; X = S, Se, Te) layered semiconductors, gallium monosulfide, GaS, has emerged as a promising material for electronics, optoelectronics, and catalysis applications. In this work, GaS samples of various thicknesses in the range from 38 to 1665 nm have been obtained by mechanical exfoliation to study the interplay between structural, morphological, optical, and photoresponsivity properties as a function of thickness. This interplay has been established by analyzing the structure through Raman spectroscopy and X-ray diffraction, the morphology through scanning electron microscopy and atomic force microscopy, the density and optical properties through spectroscopic ellipsometry, and the photoresponsivity through current-voltage measurements under UV light. This work shows that photoresponsivity increases with increases in GaS thickness, resulting in a UV photoresponsivity of 1.5·10-4 AW-1 stable over several on/off cycles.

Exploring the Thickness-Dependence of the Properties of Layered Gallium Sulfide.

Group III layered monochalcogenide gallium sulfide, GaS, is one of the latest additions to the two-dimensional (2D) materials family, and of particular interest for visible-UV optoelectronic applications due to its wide bandgap energy in the range 2.35-3.05 eV going from bulk to monolayer. Interestingly, when going to the few-layer regime, changes in the electronic structure occur, resulting in a change in the properties of the material. Therefore, a systematic study on the thickness dependence of the different properties of GaS is needed. Here, we analyze mechanically exfoliated GaS layers transferred to glass substrates. Specifically, we report the dependence of the Raman spectra, photoluminescence, optical transmittance, resistivity, and work function on the thickness of GaS. Those findings can be used as guidance in designing devices based on GaS.

Gallium Plasmonic Nanoantennas Unveiling Multiple Kinetics of Hydrogen Sensing, Storage, and Spillover.

Hydrogen is the key element to accomplish a carbon-free based economy. Here, the first evidence of plasmonic gallium (Ga) nanoantennas is provided as nanoreactors supported on sapphire (α-Al2 O3 ) acting as direct plasmon-enhanced photocatalyst for hydrogen sensing, storage, and spillover. The role of plasmon-catalyzed electron transfer between hydrogen and plasmonic Ga nanoparticle in the activation of those processes is highlighted, as opposed to conventional refractive index-change-based sensing. This study reveals that, while temperature selectively operates those various processes, longitudinal (LO-LSPR) and transverse (TO-LSPR) localized surface plasmon resonances of supported Ga nanoparticles open selectivity of localized reaction pathways at specific sites corresponding to the electromagnetic hot-spots. Specifically, the TO-LSPR couples light into the surface dissociative adsorption of hydrogen and formation of hydrides, whereas the LO-LSPR activates heterogeneous reactions at the interface with the support, that is, hydrogen spillover into α-Al2 O3 and reverse-oxygen spillover from α-Al2 O3. This Ga-based plasmon-catalytic platform expands the application of supported plasmon-catalysis to hydrogen technologies, including reversible fast hydrogen sensing in a timescale of a few seconds with a limit of detection as low as 5 ppm and in a broad temperature range from room-temperature up to 600 °C while remaining stable and reusable over an extended period of time.

Non-Absorbing Dielectric Materials for Surface-Enhanced Spectroscopies and Chiral Sensing in the UV.

Low-loss dielectric nanomaterials are being extensively studied as novel platforms for enhanced light-matter interactions. Dielectric materials are more versatile than metals when nanostructured as they are able to generate simultaneously electric- and magnetic-type resonances. This unique property gives rise to a wide gamut of new phenomena not observed in metal nanostructures such as directional scattering conditions or enhanced optical chirality density. Traditionally studied dielectrics such as Si, Ge or GaP have an operating range constrained to the infrared and/or the visible range. Tuning their resonances up to the UV, where many biological samples of interest exhibit their absorption bands, is not possible due to their increased optical losses via heat generation. Herein, we report a quantitative survey on the UV optical performance of 20 different dielectric nanostructured materials for UV surface light-matter interaction based applications. The near-field intensity and optical chirality density averaged over the surface of the nanoparticles together with the heat generation are studied as figures of merit for this comparative analysis.

Sustainable and Tunable Mg/MgO Plasmon-Catalytic Platform for the Grand Challenge of SF6 Environmental Remediation.

Sulfur hexafluoride (SF6) is one of the most harmful greenhouse gases producing environmental risks. Therefore, developing ways of degrading SF6 without forming hazardous products is increasingly important. Herein, we demonstrate for the first time the plasmon-catalytic heterogeneous degradation of SF6 into nonhazardous MgF2 and MgSO4 products by nontoxic and sustainable plasmonic magnesium/magnesium oxide (Mg/MgO) nanoparticles, which are also effective as a plasmon-enhanced SF6 chemometric sensor. The main product depends on the excitation wavelength; when the localized surface plasmon resonance (LSPR) is in the ultraviolet, then MgF2 forms, while visible light LSPR results in MgSO4. Furthermore, Mg/MgO platforms can be regenerated in few seconds by hydrogen plasma treatment and can be reused in a new cycle of air purification. Therefore, this research first demonstrates effectiveness of Mg/MgO plasmon-catalysis enabling environmental remediation with the concurrent functionalities of monitoring, degrading, and detecting sulfur and fluorine gases in the atmosphere.

Optically addressing interaction of Mg/MgO plasmonic systems with hydrogen.

Magnesium-based films and nanostructures are being studied in order to improve hydrogen reversibility, storage capacity, and kinetics, because of their potential in the hydrogen economy. Some challenges with magnesium (Mg) samples are their unavoidable oxidation by air exposure and lack of direct in situ real time measurements of hydrogen interaction with Mg and MgO surfaces and Mg plasmonic nanoparticles. Given these challenges, the present article investigates direct interaction of Mg with hydrogen, as well as implications of its inevitable oxidation by real-time spectroscopic ellipsometry for exploiting the optical properties of Mg, MgH2 and MgO. The direct hydrogenation measurements have been performed in a reactor that combines a remote hydrogen plasma source with an in situ spectroscopic ellipsometer, which allows optical monitoring of the hydrogen interaction and results in optical property modification. The hydrogen plasma dual use is to provide the hydrogen-atoms and to reduce barriers to heterogeneous hydrogen reactions.

Plasmon-Enhanced Catalysis: Distinguishing Thermal and Nonthermal Effects.

In plasmon-enhanced heterogeneous catalysis, illumination accelerates reaction rates by generating hot carriers and hot surfaces in the constituent nanostructured metals. In order to understand how photogenerated carriers enhance the nonthermal reaction rate, the effects of photothermal heating and thermal gradients in the catalyst bed must be confidently and quantitatively characterized. This is a challenging task considering the conflating effects of light absorption, heat transport, and reaction energetics. Here, we introduce a methodology to distinguish the thermal and nonthermal contributions from plasmon-enhanced catalysts, demonstrated by illuminated rhodium nanoparticles on oxide supports to catalyze the CO2 methanation reaction. By simultaneously measuring the total reaction rate and the temperature gradient of the catalyst bed, the effective thermal reaction rate may be extracted. The residual nonthermal rate of the plasmon-enhanced reaction is found to grow with a superlinear dependence on illumination intensity, and its apparent quantum efficiency reaches ∼46% on a Rh/TiO2 catalyst at a surface temperature of 350 °C. Heat and light are shown to work synergistically in these reactions: the higher the temperature, the higher the overall nonthermal efficiency in plasmon-enhanced catalysis.

The UV Plasmonic Behavior of Distorted Rhodium Nanocubes.

For applications of surface-enhanced spectroscopy and photocatalysis, the ultraviolet (UV) plasmonic behavior and charge distribution within rhodium nanocubes is explored by a detailed numerical analysis. The strongest plasmonic hot-spots and charge concentrations are located at the corners and edges of the nanocubes, exactly where they are the most spectroscopically and catalytically active. Because intense catalytic activity at corners and edges will reshape these nanoparticles, distortions of the cubical shape, including surface concavity, surface convexity, and rounded corners and edges, are also explored to quantify how significantly these distortions deteriorate their plasmonic and photocatalytic properties. The fact that the highest fields and highest carrier concentrations occur in the corners and edges of Rh nanocubes (NCs) confirms their tremendous potential for plasmon-enhanced spectroscopy and catalysis. It is shown that this opportunity is fortuitously enhanced by the fact that even higher field and charge concentrations reside at the interface between the metal nanoparticle and a dielectric or semiconductor support, precisely where the most chemically active sites are located.

Light guiding and switching using eccentric core-shell geometries.

High Refractive Index (HRI) dielectric nanoparticles have been proposed as an alternative to metallic ones due to their low absorption and magnetodielectric response in the VIS and NIR ranges. For the latter, important scattering directionality effects can be obtained. Also, systems constituted by dimers of HRI dielectric nanoparticles have shown to produce switching effects by playing with the polarization, frequency or intensity of the incident radiation. Here, we show that scattering directionality effects can be achieved with a single eccentric metallo-HRI dielectric core-shell nanoparticle. As an example, the effect of the metallic core displacements for a single Ag-Si core-shell nanoparticle has been analyzed. We report rotation of the main scattering lobe either clockwise or counterclockwise depending on the polarization of the incident radiation leading to new scattering configurations for switching purposes. Also, the efficiency of the scattering directionality can be enhanced. Finally, chains of these scattering units have shown good radiation guiding effects, and for 1D periodic arrays, redirection of diffracted intensity can be observed as a consequence of blazing effects. The proposed scattering units constitute new blocks for building systems for optical communications, solar energy harvesting devices and light guiding at the nanoscale level.

How an oxide shell affects the ultraviolet plasmonic behavior of Ga, Mg, and Al nanostructures.

The ultraviolet (UV) range presents new challenges for plasmonics, with interesting applications ranging from engineering to biology. In previous research, gallium, aluminum, and magnesium were found to be very promising UV plasmonic metals. However, a native oxide shell surrounds nanostructures of these metals that affects their plasmonic response. Here, through a nanoparticle-oxide core-shell model, we present a detailed electromagnetic analysis of how oxidation alters the UV-plasmonic response of spherical or hemisphere-on-substrate nanostructures made of those metals by analyzing the spectral evolution of two parameters: the absorption efficiency (far-field analysis) and the enhancement of the local intensity averaged over the nanoparticle surface (near-field analysis).

Polarimetric response of magnetodielectric core-shell nanoparticles: an analysis of scattering directionality and sensing.

The influence of increasing the core size of Ag-Si core-shell nanoparticles has been investigated by using the values of the linear polarization degree at a right-angle scattering configuration, [Formula: see text]. Changes in dipolar resonances and scattering directionality conditions as a function of the core radius (R int) for a fixed shell size ([Formula: see text] nm) have been analysed. An empirical formula to obtain the ratio [Formula: see text] by monitoring the influence of the magnetic dipolar resonance in [Formula: see text] has been found. The effect of the refractive index of the surrounding medium, m med, in the zero backward and almost-zero forward scattering conditions has also been studied. We have weighed up the sensitivity of [Formula: see text] to m med. It has been demonstrated that multipolar contributions strongly influence [Formula: see text]. This influence can be used as a fast m med estimate. In all cases, the results show that the bigger the cores, the higher the sensitivity to m med.

Near- and far-field scattering resonance frequency shift in dielectric and perfect electric conducting cylinders.

The ability to infer near-field scattering properties from far-field measurements is of paramount importance in nano-optics. Recently we derived an approximate formula for predicting the frequency shift between near- and far-field intensity peaks in the case of a dielectric sphere. In this work we demonstrate that almost an identical formula can be used to predict the resonance shift of a dielectric cylinder and a perfectly conducting cylinder. We find the redshift of the resonance peak of the perfect electric conducting cylinder to be approximately 2 orders of magnitude greater than for the dielectric cylinder. The errors in our approximate analytic formula for predicting the redshift are approximately only twice as great. Furthermore, we apply the redshift formula to a silicon cylinder and discuss its magneto-dielectric properties, which may be of interest in design of metamaterials.

Size-tunable rhodium nanostructures for wavelength-tunable ultraviolet plasmonics.

Polydisperse rhodium nanoparticles have recently shown promise for ultraviolet (UV) plasmonics, but controlling the size and morphology of metal nanoparticles is essential for tuning surface plasmon resonances. Here we report the use of slow-injection polyol methods to synthesize monodisperse Rh nanocubes with unprecedentedly large sizes and slightly concave faces. The associated local surface plasmon resonances (LSPRs) red-shifted with increasing sizes in the UV region from deep UV to around 400 nm, consistent with numerical simulations. UV illumination of p-aminothiophenol attached to the Rh nanocubes generated surface-enhanced Raman spectra and accelerated photo-decomposition, and these enhancements were largest for nanocubes whose LSPR was resonant with the UV laser. The lack of a native oxide coating, the precise control of nanocube size and morphology demonstrated here, and the ability to tune the surface plasmon resonance from the deep UV to near UV spectral region, make rhodium a compelling choice for UV plasmonic applications.

Frequency shift between near- and far-field scattering resonances in dielectric particles.

The near-field electromagnetic scattering intensity resonances are redshifted in frequency with respect to their far-field counterparts. We derive simple, approximate, analytical formulas for this shift in the case of a plane wave interacting with a dielectric sphere. Numerical results comparing the approximate formulas to the numerically exact solutions show that the two are in good agreement. We also consider the Rayleigh limit of the formulas to gain more insight into the phenomenon.