Rare earth oxides (REOs) have lately received extensive attention in relation to the continuous scaling down of non-volatile memories (NVMs). In particular, La2O3 films are promising for integration into future NVMs because they are expected to crystallize above 400 °C in the hexagonal phase (h-La2O3) which has a higher κ value than the cubic phase (c-La2O3) in which most of REOs crystallize. In this work, La2O3 films are grown on Si by atomic layer deposition using La(C5H5)3 and H2O. Within the framework of the h-La2O3 formation, we systematically study the crystallographic evolution of La2O3 films versus annealing temperature (200–600 °C) by Fourier transform infrared spectroscopy (FTIR) and grazing incidence X-ray diffraction (GIXRD). As-grown films are chemically unstable in air since a rapid transformation into monoclinic LaO(OH) and hexagonal La(OH)3 occurs. Vacuum annealing of sufficiently …