We present a new colloidal synthesis of gallium-doped zinc oxide nanocrystals that are transparent in the visible and absorb in the near-infrared. Thermal decomposition of zinc stearate and gallium nitrate after hot injection of the precursors in a mixture of organic amines leads to nanocrystals with tunable properties according to gallium amount. Substitutional Ga(3+) ions trigger a plasmonic resonance in the infrared region resulting from an increase in the free electrons concentration. These nanocrystals can be deposited by spin coating, drop casting, and spray coating resulting in homogeneous and high-quality thin films. The optical transmission of the Ga-ZnO nanoparticle assemblies in the visible is greater than 90%, and at the same time, the near-infrared absorption of the nanocrystals is maintained in the films as well. Several strategies to improve the films electrical and optical properties have been presented, such as UV treatments to remove the organic compounds responsible for the observed interparticle resistance and reducing atmosphere treatments on both colloidal solutions and thin films to increase the free carriers concentration, enhancing electrical conductivity and infrared absorption. The electrical resistance of the nanoparticle assemblies is about 30 kΩ/sq for the as-deposited, UV-exposed films, and it drops down to 300 Ω/sq after annealing in forming gas at 450 °C, comparable with state of the art tin-doped indium oxide coatings deposited from nanocrystal inks.

We used dark field spectroscopy to monitor the dissociation of hydrogen on single gold nanoparticles embedded in metal oxide supports. Individual gold nanorods were monitored in real time to reveal the peak position, the full width at half-maximum, and the relative intensity of the surface plasmon resonances during repeated N2-H2-N2 and air-H2-air cycles. Shifts in the spectra are shown to be due to changes in electron density and not to refractive index shifts in the environment. We demonstrate that hydrogen does not dissociate on gold nanorods (13 nm × 40 nm) at room temperature when in contact with silica and that electrons or hydrogen atoms migrate from Pt nanoparticles to Au nanoparticles through the supporting metal oxide at room temperature. However, this spillover mechanism only occurs for semiconducting oxides (anatase TiO2 and ZnO) and does not occur for Au and Pt nanoparticles embedded in silica. Finally, we show that hydrogen does dissociate directly on anatase surfaces at room temperature during air-H2-air cycles. Our results show that hydrogen spillover, surface dissociation of reactants, and surface migration of chemical intermediates can be detected and monitored in real time at the single particle level.

No abstract

The combination of water-based titanate nanosheets dispersion and silk fibroin solution allows the realization of a versatile nanocomposite. Different fabrication techniques can be easily applied on these nanocomposites to manipulate the end form of these materials on the micro- and nanoscale. Easy tunability of the refractive index from n = 1.55 up to n = 1.97 is achieved, making it attractive for flexible, biopolymer-based optical devices.

Nanostructured plasmonic sensors are fabricated as sinusoidal surface plasmon metallic gratings (SPGs) embedded in a functional and porous hybrid sol-gel material, phenyl-bridged polysilsesquioxane (ph-PSQ). The metal layer is in contact with the environment through the sol-gel film, which works as sensitive element, changing its dielectric properties upon interaction with aromatic hydrocarbons. The combination of sensitivity, transparency and patternability offered by ph-PSQs gives the exceptional possibility to fabricate innovative optical sensors with straightforward processes. An embedded SPG is a thin metal slab waveguide, in which the surface plasmon polaritons (SPPs) at the two metal-dielectric interfaces superpose, resulting in two physical coupled modes: the long range SPPs (LRSPPs) and the short range SPPs (SRSPPs). An extended experimental and theoretical characterization of the optical properties of the plasmonic device was performed. The sensor performance was tested against the detection of 30 ppm xylene, monitoring the influence of the target gas on the SPPs modes. A reversible red-shift of the reflectance dips of both LRSPP and SRSPP resonances in the 1.9-2.9 nm range was observed and correlated to the interaction with the analyte. An enhancement in sensitivity associated with the rotation of the grating grooves with respect to the scattering plane (azimuthal rotation) was verified within the experimental errors. Collected data are compatible with theoretical predictions assuming a variation of the film refractive index of 0.011 ± 0.005.