Oxidatively stable nanoporous silicon photocathodes with enhanced onset voltage for photoelectrochemical proton reduction.

Stable and high-performance nanoporous "black silicon" photoelectrodes with electrolessly deposited Pt nanoparticle (NP) catalysts are made with two metal-assisted etching steps. Doubly etched samples exhibit an ∼300 mV positive shift in photocurrent onset for photoelectrochemical proton reduction compared to oxide-free planar Si with identical catalysts. We find that the photocurrent onset voltage of black Si photocathodes prepared from single-crystal planar Si wafers by an Ag-assisted etching process increases in oxidative environments (e.g., aqueous electrolyte) owing to a positive flat-band potential shift caused by surface oxidation. However, within 24 h, the surface oxide layer becomes a kinetic barrier to interfacial charge transfer that inhibits proton reduction. To mitigate this issue, we developed a novel second Pt-assisted etch process that buries the Pt NPs deep into the nanoporous Si surface. This second etch shifts the onset voltage positively, from +0.25 V to +0.4 V versus reversible hydrogen electrode, and reduces the charge-transfer resistance with no performance decrease seen for at least two months. PEC performance was stable owing to Pt NP catalysts that were buried deeply in the photoelectrode by the second etch, below a thick surface layer comprised primarily of amorphous SiO2 along with some degree of remaining crystalline Si as observed by scanning and transmission electron micrographs. Electrochemical impedance studies reveal that the second etch leads to a considerably smaller interfacial charge-transfer resistance than samples without the additional etch, suggesting that burying the Pt NPs improves the interfacial contact to the crystalline silicon surface.