Analysis of the operation of thin nanowire photoelectrodes for solar energy conversion

The solar energy conversion properties of thin Si and GaP nanowire photoelectrodes in photoelectrochemical cells have been examined through sets of finite-element simulations. A discussion describing the motivation behind nanostructured, high aspect ratio semiconductor photoelectrode designs and a brief survey of current experimental results reported for nanostructured semiconductor photoelectrodes in photoelectrochemical cells are presented first. An analysis is then shown that outlines the primary recombination pathways governing the steady-state current-potential behaviors of thin, cylindrical nanowire photoelectrodes, with explicit expressions detailing the differences between planar and cylindrical photoelectrodes arising from the solution of carrier fluxes in planar and cylindrical geometries. Results from finite-element simulations used to model the key features of thin nanowire photoelectrodes under low-level injection conditions are shown that illustrate which recombination pathway(s) is operative under various experimental conditions. Specifically, the respective effects of non-uniform doping, tapering along the length, variation in charge carrier mobilities and lifetimes, changes in nanowire radius, and changes in the density of surface defects on the observable photocurrent-potential responses are reported. These cumulative results serve as guides for future experimental work aimed at improving the attainable solar energy conversion efficiencies of doped semiconductor nanowire photoelectrodes. Lastly, separate simulations that model lightly doped nanowire photoelectrodes under high-level injection conditions are discussed. These results suggest discrete, ohmic-selective contacts may afford a way to circumvent the stringent doping requirements discussed herein for thin nanowire photoelectrodes.