XPS and SIMS characterisation of TiOxNy solar absorber films

Solar thermal collectors have been prepared with thin TiO_xN_y films deposited using ion beam assisted deposition, on Si and Cu substrates. The films are amorphous and x and y were controlled by altering the O₂/N₂ ratio in the gas source. After annealing at temperatures of 200 – 400 °C, films have been depth profiled using Secondary Ion Mass Spectrometry. Profiles reveal the degradation of the film, particularly for films on Cu substrates, by migration of the substrate atoms through the films, to the sample surface. In general, films with x<1 and y>1 show improved temperature stability, ultimately at the expense of a reduced transmission window. Contrary to previous suggestions in the literature, the degradation mechanism initially involves the formation of a nitrogen rich phase, rather than an oxide at the film surface. On copper substrates, the nature of the films and of this phase, formed by diffusion of the substrate atoms, have been investigated by X-ray photoelectron spectroscopy (XPS). These investigations reveal complex behaviour in the early stages of film failure, with the suggestion that the initial films, at least near the surface, are two phase, and the reaction layer mixes the TiO_xN_y with some Ti replacement by ions from the Cu substrate.