Impact of vacancies on structure, stability and properties of hexagonal transition metal diborides, MB2 (M = Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, and Fe)

Abstract

In this study, we have used density functional theory (DFT) calculations to characterize if and how defects influence the stability and electronic/mechanical properties of MB2 (AlB2-type) for different transition metal M. From a point defect analysis including vacancies, interstitials, and anti-sites, we identify vacancies to be most favored, or least unfavored. To provide insight into possible vacancy ordering, we focus on vacancies on M- and B-sublattices for nine metals (M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W), modelled both as disordered and ordered. We demonstrate and explain why vacancies have a significant impact for M from Group 4 (Ti, Zr, Hf), Group 5 (Nb, Ta) and 6 (Mo, W) with improved thermodynamical and dynamical stability as well as mechanical properties. This by diverging from the ideal composition through controlled off-stoichiometry in terms of vacancies in M- or B-deficient structures. Line compounds TiB2, ZrB2 and HfB2 account for B-poor or M-rich conditions by forming planar defects comprised of vacant B. This in contrast to the ordered M- and B vacancies identified for MoB2 and WB2, with an optimal result at 33.33% M- and 25% B-vacancies, respectively, which significantly improves the stability and concurrent properties through elimination of antibonding states and minimization of non-bonding states. Similar behavior with enhanced stability and properties is demonstrated for NbB2 and TaB2 with an optimum around 10% M- and 17% B-vacancies, respectively.