Using optical resonances to control heat generation and propagation in silicon nanostructures

Here we propose a new computational approach to light-to-matter interactions in silicon nanopillars, which simulates heat generation and propagation dynamics occurring in continuous wave laser processing over a wide temporal range (from 1 fs to about 25 hours). We show that visible light can be exploited to selectively crystallize internal region of the pillars, which is not possible by conventional treatments. A detailed study on lattice crystallization and reconstruction dynamics reveals that local heating drives the formation of secondary antennas embedded into the pillars, highlighting the importance of taking into account the spatial and temporal evolution of the optical properties of the material under irradiation. This approach can be easily extended to many types of nanostructured materials and interfaces, offering a unique computational tool for many applications involving optothermal processes.Comment: 21 pages, 4 figure

Sodium Doped LaMnO3 Thin Films: Influence of Substrate and Thickness on Physical Properties

In this paper we report the results about the synthesis and characterization of optimally doped La1-xNaxMnO3 thin films grown onto SrTiO3 (100), NdGaO3 (100) and NdGaO3 (110) for thickness ranging from 11 to 82 nm. The effect of substrate nature and orientation, film thickness and annealing procedure was investigated in order to optimize their magnetoresistance (MR). We obtained very smooth films displaying MR values greater than 70%, near to room temperature.Comment: 31 pages, 9 figures Final version to appear in J. Phys. Chem.

"RaMassays": Synergistic Enhancement of Plasmon-Free Raman Scattering and Mass Spectrometry for Multimodal Analysis of Small Molecules

SiO2/TiO2 core/shell (T-rex) beads were exploited as "all-in-one" building-block materials to create analytical assays that combine plasmon-free surface enhanced Raman scattering (SERS) and surface assisted laser desorption/ionization (SALDI) mass spectrometry (RaMassays). Such a multi-modal approach relies on the unique optical properties of T-rex beads, which are able to harvest and manage light in both UV and Vis range, making ionization and Raman scattering more efficient. RaMassays were successfully applied to the detection of small (molecular weight, M.W. <400 Da) molecules with a key relevance in biochemistry and pharmaceutical analysis. Caffeine and cocaine were utilized as molecular probes to test the combined SERS/SALDI response of RaMassays, showing excellent sensitivity and reproducibility. The differentiation between amphetamine/ephedrine and theophylline/theobromine couples demonstrated the synergistic reciprocal reinforcement of SERS and SALDI. Finally, the conversion of L-tyrosine in L-DOPA was utilized to probe RaMassays as analytical tools for characterizing reaction intermediates without introducing any spurious effects. RaMassays exhibit important advantages over plasmonic nanoparticles in terms of reproducibility, absence of interference and potential integration in multiplexed devices

Alginate-Derived Active Blend Enhances Adsorption and Photocatalytic Removal of Organic Pollutants in Water

The ever-increasing need for clean water is one of the most urgent sustainable development goals, which requires environmentally-friendly strategies for water remediation against different types of pollutants. In this work, the possibility of using alginate, a biocompatible and natural polysaccharide, is explored for the preparation of both oxide (TiO2, Al2O3, and yttria-stabilized ZrO2 (YSZ)) macrobeads and an active blend of rich carbon nanoparticles, depolymerized alginate, formic acid, and a complex mixture of other organic acids. In particular, the active blend is obtained through low-energy-demanding microwave assisted digestion of sodium alginate solution, and it is used to enhance the decontamination activity of oxide macrobeads in mild conditions (e.g., low temperature, no pH buffers, and visible illumination). It is demonstrated that the alginate-derived active blend obtained without the addition of any other chemicals increases primarily the adsorption capability of oxide macrobeads toward positively charged pollutants (methylene blue, crystal violet, and tetracaine) and, also, the photocatalytic activity of TiO2 during their degradation. Interestingly, functionalization with the obtained alginate-derived active blend enables better performance in comparison with functionalization of its single components or with carbon-dots (C-Dots) obtained with conventional and more energy-demanding hydrothermal methods, enabling them to obtain a fully sustainable, environmentally-friendly system for water remediation

Why PEDOT:PSS Should Not Be Used for Raman Sensing of Redox States (and How It Could Be)

Poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) has been recently proposed for Raman sensing of redox-active species in solution. Here, we investigated the rationale of this approach through systematic experiments, in which the Raman spectrum of PEDOT:PSS was analyzed in the presence of either nonoxidizing or oxidizing electrolytes. The results demonstrated that Raman spectra precisely reflect the conformation of PEDOT units and their interactions with PSS. Two different responses were observed. In the case of oxidizing electrolytes, the effect of charge transfer is accurately transduced in Raman spectrum changes. On the other hand, reduction induces a progressive separation between the PEDOT and PSS chains, which decreases their mutual interaction. This stimulus determines characteristic variations in the intensity, shape, and position of the Raman spectra. However, we demonstrated that the same effects can be obtained either by increasing the concentration of nonoxidizing electrolytes or by deprotonating PSS chains. This poses severe limitations to the use of PEDOT:PSS for this type of Raman sensing. This study allows us to revise most of the Raman results reported in the literature with a clear model, setting a new basis for investigating the dynamics of mixed electronic/ionic charge transfer in conductive polymers

Giant photoinduced reflectivity modulation of nonlocal resonances in silicon metasurfaces

Metasurfaces offer a unique playground to tailor the electromagnetic field at subwavelength scale to control polarization, wavefront, and nonlinear processes. Tunability of the optical response of these structures is challenging due to the nanoscale size of their constitutive elements. A long-sought solution to achieve tunability at the nanoscale is all-optical modulation by exploiting the ultrafast nonlinear response of materials. However, the nonlinear response of materials is inherently very weak, and, therefore, requires optical excitations with large values of fluence. We show that by properly tuning the equilibrium optical response of a nonlocal metasurface, it is possible to achieve sizable variation of the photoinduced out-of-equilibrium optical response on the picosecond timescale employing fluences smaller than 250 μJ / cm2, which is 1 order of magnitude lower than previous studies with comparable reflectivity variations in silicon platforms. Our results pave the way to fast devices with large modulation amplitude.<br/

Enhanced Electrocatalytic Oxygen Evolution in Au–Fe Nanoalloys

Oxygen evolution reaction (OER) is the most critical step in water splitting, still limiting the development of efficient alkaline water electrolyzers. Here we investigate the OER activity of Au–Fe nanoalloys obtained by laser-ablation synthesis in solution. This method allows a high amount of iron (up to 11 at %) to be incorporated into the gold lattice, which is not possible in Au–Fe alloys synthesized by other routes, due to thermodynamic constraints. The Au0.89Fe0.11 nanoalloys exhibit strongly enhanced OER in comparison to the individual pure metal nanoparticles, lowering the onset of OER and increasing up to 20 times the current density in alkaline aqueous solutions. Such a remarkable electrocatalytic activity is associated to nanoalloying, as demonstrated by comparative examples with physical mixtures of gold and iron nanoparticles. These results open attractive scenarios to the use of kinetically stable nanoalloys for catalysis and energy conversion

Switchable Stimuli-Responsive Heterogeneous Catalysis

Heterogeneous catalytic systems based on the use of stimuli-responsive materials can be switched from an “on” active state to an “off” inactive state, which contributes to endowing the catalysts with unique functional properties, such as adaptability, recyclability and precise spatial and temporal control on different types of chemical reactions. All these properties constitute a step toward the development of nature-inspired catalytic systems. Even if this is a niche area in the field of catalysis, it is possible to find in literature intriguing examples of dynamic catalysts, whose systematic analysis and review are still lacking. The aim of this work is to examine the recent developments of stimuli-responsive heterogeneous catalytic systems from the viewpoint of different approaches that have been proposed to obtain a dynamic control of catalytic efficiency. Because of the variety of reactions and conditions, it is difficult to make a quantitative comparison between the efficiencies of the considered systems, but the analysis of the different strategies can inspire the preparation of new smart catalytic systems

Surface Chemical Analysis of Ceramics and Ceramic‐Enhanced Analytics

This chapter gives a brief overview of methods used to analyze functionalized surfaces with a comparison among different working principles and performances. The schematic, yet nonexhaustive summary, can guide a nonexpert reader in evaluating potential and limitations of some of the most used analytical tools. Most significant methods such as electron and X-ray spectroscopy, secondary ion mass spectrometry, and vibrational spectroscopy (Raman and Infrared) are in focus. These techniques will be described in general terms, to provide a concise overview of their working principles, capabilities, and applications. The second part of this chapter will present exciting examples in which ceramic nanostructures are exploited to enhance the chemical sensitivity in optical sensing, vibrational spectroscopy (IR and Raman), and mass spectrometry and enable novel surface analytical tools based on their versatile properties