Resonant Localization, Enhancement, and Polarization of Optical Fields in Nano-Scale Interface Regions for Photo-Catalytic Applications

We report results of theoretical simulations of optical field enhancement in a system consisting of spherical and hemispherical noble metal nanoparticles on a smooth titania surface, which is a model system relevant to applications in photo-catalysis and solar energy harvesting. Simulations conducted using Finite-Difference Time-Domain (FDTD) technique reveal presence of resonant optical extinction bands at visible wavelengths, whose optical scattering is weak, but the associated localization and intensity enhancement of optical near-field are significant. For hemispheres, the field is strongly localized at the metal-substrate interface, where intensity enhancement of up to 10⁴ times is reached. Moreover, the field is predominantly polarized along the normal to the substrate. These findings indicate potential of the hemisphere-substrate system for applications relying on optically promoted charge transport through the metal-substrate interface, such as photochemical reactions and light-to-current conversion. The results of theoretical analysis are compared with reported experimental data on photo-catalytic reactions.