Complex metal nanoparticles offer a great playground for plasmonic nanoengineering, where it is possible to cover plasmon resonances from ultraviolet to near infrared by modifying the morphologies from solid nanocubes to nanoframes, multiwalled hollow nanoboxes or even nanotubes with hybrid (alternating solid and hollow) structures. We experimentally show that structural modifications, i.e. void size and final morphology, are the dominant determinants for the final plasmonic properties, while compositional variations allow us to get a fine tuning. EELS mappings of localized surface plasmon resonances (LSPRs) reveal an enhanced plasmon field inside the voids of hollow AuAg nanostructures along with a more homogeneous distributions of the plasmon fields around the nanostructures. With the present methodology and the appropriate samples we are able to compare the effects of hybridization at the nanoscale in hollow nanostructures.
Boundary element method (BEM) simulations also reveal the effects of structural nanoengineering on plasmonic properties of hollow metal nanostructures. Possibility of tuning the LSPR properties of hollow metal nanostructures in a wide range of energy by modifying the void size/shell thickness is shown by BEM simulations, which reveals that void size is the dominant factor for tuning the LSPRs. As a proof of concept for enhanced plasmonic properties, we show effective label free sensing of bovine serum albumin (BSA) with some of our hollow nanostructures. In addition, the different plasmonic modes observed have also been studied and mapped in 3D.
The modification of the surface reception properties of nanocrystalline structures is of great interest in environmental, catalysis and energy related applications. For instance, an oxide surface covered with a layer of another oxide opens the possibility of creating the nanosized counterparts of bulk catalytic systems. A relevant example is the TiO<sub>2</sub>-WO<sub>3</sub>, which is an active catalysts in a broad range of reactions. The chemical synthesis of the colloidal, nanocrystalline version of such system will first be exposed, by coupling suitable sol-gel chemistry with solvothermal processing. Then, the range of obtained structures will be discussed, ranging from WO<sub>x</sub>-surface modified TiO<sub>2</sub> to TiO<sub>2</sub>-WO<sub>3</sub> heterojunctions. The complex structural evolution of the materials will be discussed, depending on the W concentration. A summary of the acetone sensing properties of these systems will be shown. In particular, the surface activation of the otherwise almost inactive pure TiO<sub>2</sub> by surface deposition of WO<sub>3</sub>-like layers will be highlighted. Addition of the smallest W concentration boosted the sensor response to values comparable to those of pure WO<sub>3</sub>, ranging over 2-3 orders of magnitude of conductance variation in presence of ethanol or acetone gases. Simple analysis of the sensing data will evidence that the combination of such nanocrystalline oxides results in catalytic activation effects, with exactly opposite trend, with respect to pure TiO<sub>2</sub>, of the activation energies and best responses.
We present a structural, magnetic and magneto-optical (MO) study of Co nanoparticles sputter-deposited at different temperatures and embedded in three different matrices (two insulators such as MgO and AlN and a metal such as Pt). MgO capping layer does not affect the magnetism of the nanoparticles as demonstrated by <i>in situ</i> transversal and <i>ex situ</i> polar Kerr loops. The structure of the nanoparticles was investigated by TEM and a Co crystalline core surrounded by an amorphous crust was observed. From the analysis of the MO spectral response of the nanoparticles we demonstrate that the evolution of the MO constants as a function of Co concentration can be explained with the Maxwell-Garnett model. It is also observed that the reduction of nanoparticles size gives rise to a decrease of the relaxation time of the electrons into them. The deposition of Pt capping gives rise to the magnetic connection of the islands mediated by the polarised Pt, with the formation of different Co-Pt compounds as was observed with TEM. We observe that in the case of AlN capping destroys the magnetism of the samples due to a strong nitridation of Co.
Due to their simple implementation, low cost and good reliability for real-time control systems, semiconductor gas sensors offer good advantages with respect to other gas sensor devices. As gas adsorption is a surface effect, one of the most important parameter to tailor the sensitivity of the sensor material is to increase the surface area. For these propose, mesoporous oxides have been synthesized. Nanostructured mesoporous materials present a large and controllable pore size and high surface are. For the preparation of ordered nanostructure arrays, a hard template method has been used. This method presents some advantages when compared with a soft template method, especially in its specific topological stability, veracity, predictability and controllability. Moreover, with this hard template method we can obtain crystalline mesoporous oxides, with small particle size and high surface area. We have used SBA-15 (two-dimensional hexagonal structure) and KIT-6 (three-dimensional cubic structure) as a template for the synthesis of different crystalline mesoporous WO<sub>3</sub> with a particle size about 8-10 nm and high surface area. Low angle XRD spectra show a high order mesoporous structure, without rests of silica template. TEM confirms that the silica host has been completely removed; therefore, the nanowires constitute a self-supported superlattice. HRTEM studies have been focused on the detailed structural characterization of these materials. Electrical characterization of the sensor response in front of NO<sub>2</sub> has been performed. Some catalytic additives have been also introduced, in order to increase the sensitivity of the material.