Abstract

Photoelectrochemical (PEC) water splitting is an attractive approach to generate hydrogen as a clean chemical fuel from solar energy. But there remain many fundamental issues to be solved, including inadequate photon absorption, short carrier diffusion length, surface recombination, vulnerability to photo-corrosion, and unfavorable reaction kinetics. Owing to its self-limiting surface reaction mechanism, atomic layer deposition (ALD) is capable of depositing thin films in a highly controllable manner, which makes it an enabling technique to overcome some of the key challenges confronted by PEC water splitting. This tutorial review describes some unique and representative applications of ALD in fabricating high performance PEC electrodes with various nanostructures, including (i) coating conformal thin films on three-dimensional scaffolds to facilitate the separation and migration of photocarriers and enhance light trapping, as well as realizing controllable doping for bandgap engineering and forming homojunctions for carrier separation; (ii) achieving surface modification through deposition of anti-corrosion layers, surface state passivation layers, and surface catalytic layers; and (iii) identifying the main rate limiting steps with model electrodes with highly defined thickness, composition, and interfacial structure.

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