Cathodoluminescence insights into the ionic disorder of photocatalytic anatase films

The nature of ionic disorder and the effect of structural defects on the photocatalytic function of anatase are revisited in the light of direct experimental evidence retrieved on the molecular scale by cathodoluminescence (CL) spectroscopy. CL spectra, collected on different types of photocatalytically efficient or inefficient anatase films, embodied a composite optical response of electron-compensating majority types of ionic disorder in the anatase lattice. This paper describes the dual experimental output obtained by systematically monitoring optically active off-stoichiometry sites, as follows: (i) quantitative analyses of film stoichiometry including the interactions of different lattice-defect populations; and (ii) stability/evolution of off-stoichiometry sites upon post-fabrication annealing cycles and their effects on the photocatalytic activity of the films. CL experiments provided us with direct access to the structural state of the defective anatase lattice, thus unfolding some missing detail about the complex physicochemical interactions behind its photocatalytic efficiency.