The structure of TiN/HfO2 nanofilms grown on In xGa1-xAs substrates was assessed through angular-resolved x-ray photoelectron spectroscopy. The quantitative analysis made possible determining the thickness and composition of the various layers constituting the nanofilms treated at different temperatures (un-annealed, 500 °C/120 s and 700 °C/10 s). The TiN layer is crucial to prevent oxygen desorption from the dielectric during annealing. Small amounts of oxidized gallium and metallic arsenic are located at the HfO2/InGaAs interface. The thickness of the HfO2 layer remains stable under the thermal treatments. Annealing affects the In 3d5/2 and Ga 3p signals. From the angular dependence of the peak intensities and the detailed knowledge of the structure of the films, it was possible to determine that annealing causes In and Ga out-diffusion into the metallic layer, and also to quantify the amount of transported matter. This, along with density functional theory calculations, allowed for an estimation of the activation energy of the diffusion of indium through HfO2. © 2013 AIP Publishing LLC.