Composite p-Si/Al₂O₃/Ni Photoelectrode for Hydrogen Evolution Reaction

A photoelectrode for hydrogen evolution reaction (HER) is proposed, which is based on p-type silicon (p-Si) passivated with an ultrathin (10 nm) alumina (Al₂O₃) layer and modified with microformations of a nickel catalyst. The Al₂O₃ layer was formed using atomic layer deposition (ALD), while the nickel was deposited photoelectrochemically. The alumina film improved the electronic properties of the substrate and, at the same time, protected the surface from corrosion and enabled the deposition of nickel microformations. The Ni catalyst increased the HER rate up to one order of magnitude, which was comparable with the rate measured on a hydrogen-terminated electrode. Properties of the alumina film on silicon were comprehensively studied. Grazing incidence X-ray diffraction (GI-XRD) identified the amorphous structure of the ALD oxide layer. Optical profilometry and spectroscopic ellipsometry (SE) showed stability of the film in an acid electrolyte. Resistivity measurements showed that annealing of the film increases its electric resistance by four times.