Nanostructured Silicon Photocathodes for Solar Water Splitting Patterned by the Self-Assembly of Lamellar Block Copolymers.

We studied a type of nanostructured silicon photocathode for solar water splitting, where one-dimensionally periodic lamellar nanopatterns derived from the self-assembly of symmetric poly(styrene-block-methyl methacrylate) block copolymers were incorporated on the surface of single-crystalline silicon in configurations with and without a buried metallurgical junction. The resulting nanostructured silicon photocathodes with the characteristic lamellar morphology provided suppressed front-surface reflection and increased surface area, which collectively contributed to the enhanced photocatalytic performance in the hydrogen evolution reaction. The augmented light absorption in the nanostructured silicon directly translated to the increase of the saturation current density, while the onset potential decreased with the etching depth because of the increased levels of surface recombination. The pp(+)-silicon photocathodes, compared to the n(+)pp(+)-silicon with a buried solid-state junction, exhibited a more pronounced shift of the current density-potential curves upon the introduction of the nanostructured surface owing to the corresponding increase in the liquid/silicon junction area. Systematic studies on the morphology, optical properties, and photoelectrochemical characteristics of nanostructured silicon photocathodes, in conjunction with optical modeling based on the finite-difference time-domain method, provide quantitative description and optimal design rules of lamellar-patterned silicon photocathodes for solar water splitting.