The Influence of Structure and Processing on the Behavior of TiO₂ Protective Layers for Stabilization of n-Si/TiO₂/Ni Photoanodes for Water Oxidation

Light absorbers with moderate band gaps (1-2 eV) are required for high-efficiency solar fuels devices, but most semiconducting photoanodes undergo photocorrosion or passivation in aqueous solution. Amorphous TiO₂ deposited by atomic-layer deposition (ALD) onto various n-type semiconductors (Si, GaAs, GaP, and CdTe) and coated with thin films or islands of Ni produces efficient, stable photoanodes for water oxidation, with the TiO₂ films protecting the underlying semiconductor from photocorrosion in pH = 14 KOH(aq). The links between the electronic properties of the TiO₂ in these electrodes and the structure and energetic defect states of the material are not yet well-elucidated. We show herein that TiO₂ films with a variety of crystal structures and midgap defect state distributions, deposited using both ALD and sputtering, form rectifying junctions with n-Si and are highly conductive toward photogenerated carriers in n-Si/TiO₂/Ni photoanodes. Moreover, the photovoltage of these electrodes can be modified by annealing the TiO₂ in reducing or oxidizing environments. All of the polycrystalline TiO₂ films with compact grain boundaries investigated herein protected the n-Si photoanodes against photocorrosion in pH = 14 KOH(aq). Hence, in these devices, conduction through the TiO₂ layer is neither specific to a particular amorphous or crystalline structure nor determined wholly by a particular extrinsic dopant impurity. The coupled structural and energetic properties of TiO₂, and potentially other protective oxides, can therefore be controlled to yield optimized photoelectrode performance.