Controlled exposure of CuO thin films through corrosion-protecting, ALD-deposited TiO₂ overlayers

Abstract

Ultra-thin film coatings are used to protect semiconductor photoelectrodes from the harsh chemical environments common to photoelectrochemical energy conversion. These layers add contact transfer resistance to the interface that can result in a reduction of photoelectrochemical energy conversion efficiency of the photoelectrode. Here, we describe the concept of a partial protection layer, which allows for direct chemical access to a small fraction of the semiconductor underlayer for further functionalization by an electrocatalyst. The rest of the interface remains protected by a stable, inert protection layer. CuO is used as a model system for this scheme. Atomic layer deposition (ALD)-prepared TiO2 layers on CuO thin films prepared from electrodeposited Cu2O allow for the control of interfacial morphology to intentionally expose the CuO underlayer. The ALD-TiO2 overlayer shrinks during crystallization, while Cu2O in the underlayer expands during oxidation. As a result, the TiO2 protection layer cracks to expose the oxidized underlying CuO layer, which can be controlled by preceding thermal oxidation. This work demonstrates a potentially promising strategy for the parallel optimization of photoelectrochemical interfaces for chemical stability and high performance.