Temporally-resolved decomposition of Ti0.12Al0.21B0.67 thin films at 1000 °C

The thermal stability of stoichiometric Ti0.12Al0.21B0.67 thin films synthesized by magnetron sputtering was investigated by vacuum annealing at 1000 °C for 1 and 3 h. The as-deposited and post-annealed films were compared regarding changes in chemical composition, phase formation, and morphology. X-ray diffraction (XRD) data indicate the formation of a single-phase solid solution in the as-deposited Ti0.12Al0.21B0.67 thin film. After annealing for 1 h, scanning transmission electron microscopy (STEM), energy-dispersive X-ray mapping (EDX), and atom probe tomography (APT) investigations reveal segregation into Al- and Ti-rich (Ti,Al)B2 domains, consistent with spinodal decomposition. Furthermore, the formation of AlB12 with a concomitant reduction in Al concentration from 20.9 to 16.8 at. %, likely by evaporation, indicate the decomposition of Al-rich (Ti,Al)B2 domains during annealing for 1 h. Analysis of the film after annealing for 3 h shows evidence for continued spinodal decomposition as well as for further decomposition of Al-rich (Ti,Al)B2 domains, leading besides the formation of AlB12 to a reduction in Al concentration to 12.5 at. % by Al evaporation. The observed phase formation trend during in situ transmission electron microscopy (TEM) studies at 1100 °C is consistent with the above discussed decomposition processes. The here identified thermal stability limit, revealed with spatially resolved structure and composition probes, confines the application temperature range of Ti0.12Al0.21B0.67 in vacuum to temperatures