Limiting efficiencies of solar energy conversion and photo-detection via internal emission of hot electrons and hot holes in gold

We evaluate the limiting efficiency of full and partial solar spectrum harvesting via the process of internal photoemission in Au-semiconductor Schottky junctions. Our results based on the ab initio calculations of the electron density of states (e-DOS) reveal that the limiting efficiency of the full-spectrum Au converter based on hot electron injection is below 4%. This value is even lower than previously established limit based on the parabolic approximation of the Au electron energy bands. However, we predict limiting efficiency exceeding 10% for the hot holes collection through the Schottky junction between Au and p-type semiconductor. Furthermore, we demonstrate that such converters have more potential if used as a part of the hybrid system for harvesting high- and low-energy photons of the solar spectrum.Comment: Proc. SPIE 9608, Infrared Remote Sensing and Instrumentation XXIII, 960816 (September 1, 2015) 7 pages, 4 figure

Optical Excitation of a Nanoparticle Cu/p-NiO Photocathode Improves Reaction Selectivity for CO₂ Reduction in Aqueous Electrolytes

We report the light-induced modification of catalytic selectivity for photoelectrochemical CO₂ reduction in aqueous media using copper (Cu) nanoparticles dispersed onto p-type nickel oxide (p-NiO) photocathodes. Optical excitation of Cu nanoparticles generates hot electrons available for driving CO₂ reduction on the Cu surface, while charge separation is accomplished by hot-hole injection from the Cu nanoparticles into the underlying p-NiO support. Photoelectrochemical studies demonstrate that optical excitation of plasmonic Cu/p-NiO photocathodes imparts increased selectivity for CO₂ reduction over hydrogen evolution in aqueous electrolytes. Specifically, we observed that plasmon-driven CO₂ reduction increased the production of carbon monoxide and formate, while simultaneously reducing the evolution of hydrogen. Our results demonstrate an optical route toward steering the selectivity of artificial photosynthetic systems with plasmon-driven photocathodes for photoelectrochemical CO₂ reduction in aqueous media