Ambient aging effects on the effective energy gap of ZnO thin films

Using photoconductance spectroscopy, we have studied the influence of different types of thermal annealing on epitaxial ZnO thin films where band bending effects play a major role. Once the film is exposed to ambient air conditions after a simple thermal annealing in oxygen at 600°C, the effective energy gap is stable with a value of ≃3.15 eV, while after a corresponding annealing in vacuum and subsequent air exposure, it starts at ≃3.24 eV, and then it evolves along the days until it reaches the bulk energy gap value of ZnO. By means of valence band x-ray photoemission spectroscopy (XPS), we have confirmed that these phenomena are related via the Franz–Keldysh effect to a downward band bending in the former case and a time dependent upward band bending in the latter one that slowly tends to a flat band condition, tracking the behavior observed in the effective energy gap. Core level XPS measurements suggest that for each type of thermal annealing, a different adsorption kinetics of water and hydrogen take place.