Single-phase Ti2AlN thin films were obtained by annealing in vacuum of (Ti + Al)/AIN multilayers deposited at room temperature by magnetron sputtering onto single-crystalline (0001) 4H-SiC and (0001) Al2O3 substrates. In-situ X-ray diffraction experiments combined with ex-situ cross-sectional transmission electron microscopy observations reveal that interdiffusion processes occur in the multilayer at a temperature of similar to 400 degrees C leading to the formation of a (Ti, Al, N) solid solution, having the hexagonal structure of alpha-Ti, whereas the formation of Ti2AlN occurs at 550-600 degrees C. Highly oriented (0002) Ti2AlN thin films can be obtained after an annealing at 750 degrees C. (C) 2016 Elsevier Ltd. All rights reserved.