Photoelectrochemistry of Self‐Limiting Electrodeposition of Ni Film onto GaAs

Abstract Gallium arsenide (GaAs) provides a suitable bandgap (1.43 eV) for solar spectrum absorption and allows a larger photovoltage compared to silicon, suggesting great potential as a photoanode toward water splitting. Photocorrosion under water oxidation condition, however, leads to decomposition or the formation of an insulating oxide layer, which limits the photoelectrochemical performance and stability of GaAs. In this work, a self‐limiting electrodeposition method of Ni on GaAs is reported to either generate ultra‐thin continuous film or nanoislands with high particle density by controlling deposition time. The self‐limiting growth mechanism is validated by potential transients, X‐ray photoelectron spectroscopy composition and depth profile measurements. This deposition method exhibits a rapid nucleation, forms an initial metallic layer followed by a hydroxide/oxyhydroxide nanofilm on the GaAs surface and is independent of layer thickness versus deposition time when coalescence is reached. A photocurrent up to 8.9 mA cm⁻² with a photovoltage of 0.11 V is obtained for continuous ultrathin films, while a photocurrent density of 9.2 mA cm⁻² with a photovoltage of 0.50 V is reached for the discontinuous nanoislands layers in an aqueous solution containing the reversible redox couple K₃Fe(CN)₆/K₄Fe(CN)₆.