Microstructure-regulated inverted pyramidal Si photocathodes for efficient hydrogen generation

Black silicon electrodes with inverted pyramid arrays (SiIPs) are promising for efficient photoelectrochemical water splitting due to their excellent photoelectric properties and quasi-hydrophilicity. In this work, an elaborate study on microstructure regulation of SiIP photocathodes is reported. We find that on SiIPs where sidewalls have been processed with copper-assisted chemical etching (Cu-ACE), there are vast numbers of micro-pits distributed (deep holes and shallow grooves) that exactly determine electrode performance, which is a result of homogeneous Cu²⁺ oxidation of Si. Furthermore, SiIP microstructural features can be effectively adjusted via controlling the etchant composition and introducing alkali post-treatment. Taking the trade-off between light trapping ability and charge separation capacity into consideration, we optimized the hydrogen evolution reaction (HER) activity of a SiIP photocathode, and its onset potential was decreased to -0.35 V vs. RHE. On this basis, we constructed reliable heterojunctions to further improve the sluggish HER kinetics. The optimized SiIPs/TiO₂/MoS cathode exhibits a considerable photocurrent density of 9.45 mA cm^-2 at zero HER overpotential for 18 h in acidic media. Notably, our work presents a detailed physical insight into micro-pit formation and elimination in Cu-ACE, and describes the dependency of SiIP-based electrode performance on the microstructure morphology, paving a new way for its potential application in unbiased overall water splitting.