High-quality dense ZnO thin films: work function and photo/electrochemical properties

Compact ZnO (wurtzite) thin films are prepared on four different substrates by (i) spray pyrolysis or (ii) pulsed reactive magnetron sputtering combined with a radio frequency electron cyclotron wave resonance plasma. Films are characterized by AFM, XRD, Kelvin probe, cyclic voltammetry, electrochemical impedance spectroscopy, and UV photoelectrochemistry. Film morphologies, defect concentrations, crystallite size, and orientation provided specific fingerprints for the electronic structure of ZnO close to the conduction band minimum. Fabricated films are referenced, if relevant, to a model system based on a wurtzite single crystal with either Zn-face or O-face termination. Kelvin probe measurements of the ZnO/air interface distinguished effects of annealing and UV excitation, which are attributed to removal of oxygen vacancies close to the surface. In turn, the work function, at the electrochemical interface, specifically addressed the growth protocol of the ZnO electrodes but not the effects of crystallinity and annealing. Finally, high photocurrents of water oxidation are observed exclusively on virgin films. This effect is then discussed in terms of photocorrosion, and work function changes due to UV light.