Towards predictive modelling of near-edge structures in electron energy loss spectra of AlN based ternary alloys

Although electron energy loss near edge structure analysis provides a tool for experimentally probing unoccupied density of states, a detailed comparison with simulations is necessary in order to understand the origin of individual peaks. This paper presents a density functional theory based technique for predicting the N K-edge for ternary (quasi-binary) nitrogen alloys by adopting a core hole approach, a methodology that has been successful for binary nitride compounds. It is demonstrated that using the spectra of binary compounds for optimising the core hole charge ($0.35\,\mathrm{e}$ for cubic Ti$_{1-x}$Al$_x$N and $0.45\,\mathrm{e}$ for wurtzite Al$_x$Ga$_{1-x}$N), the predicted spectra evolutions of the ternary alloys agree well with the experiments. The spectral features are subsequently discussed in terms of the electronic structure and bonding of the alloys.Comment: 11 pages, 9 figures, 1 tabl

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