Yael Gutiérrez

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).

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.

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.

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.

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.

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.

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.

Recent advances in metals for plasmonics applications in the UV range

Plasmonics in the UV-range constitutes a new focus of research due to new challenges arising in fields such as biology, chemistry or spectroscopy. Very recent studies point out gallium and rhodium as good candidates for these purposes because of their low oxidation tendency and at the same time, having a good plasmonic response in the UV and excellent photocatalytic properties. Here we present an overview of the current state of UV-plasmonics with our latest findings in the plasmonic activity of materials like gallium and rhodium.

The extended Kubelka-Munk theory and its application to colloidal systems

The use of nanoparticles is spreading in many fields and a frequent way of preparing them is in the form of colloids, whose characterization becomes increasingly important. The spectral reflectance and transmittance curves of such colloids exhibit a strong dependence with the main parameters of the system. By means of a two-flux model we have performed a colorimetric study of gold colloids varying several parameters of the system, including the radius of the particles, the particle number density, the thickness of the system and the refractive index of the surrounding medium. In all cases, trajectories in the L*a*b* color space have been obtained, as well as the evolution of the luminosity, chroma and hue, either for reflectance or transmittance. The observed colors agree well with typical colors found in the literature for colloidal gold, and could allow for a fast assessment of the parameters involved, e.g., the radius of the nanoparticle during the fabrication process.

Spectral response of dielectric nano-antennas in the far- and near-field regimes

Recent studies show that the spectral behaviour of localized surface plasmon resonances (LPSRs) in metallic nanoparticles suffer from both a redshift and a broadening in the transition from the far- to the near-field regimes. An interpretation of this effect was given in terms of the evanescent and propagating components of the angular spectrum representation of the radiated field. Due to the increasing interest awakened by magnetodielectric materials as a both low-loss material option for nanotechnology applications, and also for their particular scattering properties, here we study the spectral response of a magnetodielectric nanoparticle as a basic element of a dielectric nano-antenna. This study is made by analyzing the changes suffered by the scattered electromagnetic field when propagating from the surface of this dielectric nanostructure to the far-zone in terms of propagating and evanescent plane wave components of the radiated fields.