Stability and elasticity of metastable solid solutions and superlattices in the MoN-TaN system: a first-principles study

TL;DR

This study uses first-principles calculations to explore the stability, elastic properties, and structural phases of MoN-TaN solid solutions and superlattices, revealing new tetragonal phases and their potential for hard, stable materials.

Contribution

It introduces the stability and elastic properties of novel tetragonal phases in MoN-TaN systems, highlighting the role of superlattice architecture in stabilizing metastable structures.

Findings

Hexagonal structures are most stable across compositions.

Disordered cubic phases relax towards hexagonal NiAs-type ground state.

Superlattices favor a new tetragonal ζ-phase with enhanced stability.

Abstract

Employing ab initio calculations, we discuss chemical, mechanical, and dynamical stability of MoN-TaN solid solutions together with cubic-like MoN/TaN superlattices, as another materials design concept. Hexagonal-type structures based on low-energy modifications of MoN and TaN are the most stable ones over the whole composition range. Despite being metastable, disordered cubic polymorphs are energetically significantly preferred over their ordered counterparts. An in-depth analysis of atomic environments in terms of bond lengths and angles reveals that the chemical disorder results in (partially) broken symmetry, i.e., the disordered cubic structure relaxes towards a hexagonal NiAs-type phase, the ground state of MoN. Surprisingly, also the superlattice architecture is clearly favored over the ordered cubic solid solution. We show that the bi-axial coherency stresses in superlattices break the cubic symmetry beyond simple tetragonal distortions and lead to a new tetragonal $\zeta$-phase (space group P4/nmm), which exhibits a more negative formation energy than the symmetry-stabilized cubic structures of MoN and TaN. Unlike cubic TaN, the $\zeta\text{-TaN}$ is elastically and vibrationally stable, while $\zeta$-MoN is stabilized only by the superlattice structure. To map compositional trends in elasticity, we establish mechanical stability of various Mo$_{1-x}$Ta$_x$N systems and find the closest high-symmetry approximants of the corresponding elastic tensors. According to the estimated polycrystalline moduli, the hexagonal polymorphs are predicted to be extremely hard, however, less ductile than the cubic phases and superlattices. The trends in stability based on energetics and elasticity are corroborated by density of electronic states.