Phase stability and alloy-related trends in Ti–Al–N, Zr–Al–N and Hf–Al–N systems from first principles

Transition metal aluminium nitride (TM–Al–N) thin films are valued for their excellent mechanical (e.g. hardness) as well as protective (e.g. oxidation resistance) properties. This paper addresses the structure and phase stability of group IVB TM–Al–N systems Ti1−xAlxN, Zr1−xAlxN, and Hf1−xAlxN. The predicted stability regions of the rock salt cubic structures are x ≤ 0.7, x ≤ 0.45, and x ≤ 0.45, respectively, while the wurtzite-type single phase field is obtained for x ≥ 0.7, x ≥ 0.68, and x ≥ 0.62 respectively. The predicted phase stability regions and the broad dual-phase transition regions in the case of Zr1−xAlxN and Hf1−xAlxN are validated by experiments. Furthermore, the phase transition from cubic to wurtzite with increasing Al content in the alloys is correlated with changes of electronic structure and bonding in the systems.