Electronic structure and magnetic ordering of NiN and Ni${}_2$N from first principles

Abstract

The results of first-principles electronic structure calculations for the nitrogen-rich nickel nitrides $\mathrm{NiN}$ and $\mathrm{N}{\mathrm{i}}_2\mathrm{N}$ are presented. The calculations are based on density functional theory and used the generalized gradient approximation (GGA) as well as the GGA$+U$ approach. The latter turned out to be crucial for a correct description of the crystal phase stability and magnetic instabilities of both compounds. While for $\mathrm{NiN}$ GGA calculations predict a non-magnetic ground state with the zincblende structure, GGA$+U$ calculations result in a half-metallic ferromagnet with the rocksalt structure in line with indications from the neighboring transition-metal nitrides making $\mathrm{NiN}$ a possible candidate for spin-filter devices. For $\mathrm{N}{\mathrm{i}}_2\mathrm{N}$ GGA calculations likewise lead to a non-magnetic behavior, which is contrasted with a ferrimagnetic ordering obtained from the GGA$+U$ approach. This ground state results from complex three-dimensional exchange interaction via $\sigma$-type and $\pi$-type overlap of the Ni $3d$ orbitals with the N $2p$ orbitals and may explain the reported sensitivity of the magnetic ordering to details of the crystal structure. For both nitrides, experimental data are called for to confirm our predictions.

arXiv comment8 pages, 8 figures, enthalpies of formation corrected inversion 2

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Cited by in corpus (1)

• Importance of bond exchange in MnC structural stability and half-metallic ferromagnetism: a comprehensive density functional benchmark study