Prediction of spinel structure and properties of single and double nitrides

Lattice constants, bulk moduli, band gaps, electronic bonding, and the stability of 20 new nitrides with spinel structure are studied by first-principles calculations. Double nitrides AB₂N₄ are found to be stable when the counterparts BA₂N₄ are metastable except for TiZr₂N₄. The four single nitrides C₃N₄, Si₃N₄, Ge₃N₄, and Sn₃N₄ have direct band gaps at the {Γ} point ranging from 1.14 to 3.45 eV while Zr₃N₄ and Ti₃N₄ have small indirect gaps. For double nitrides, both metallic and insulating band structures are possible. The total bond orders of the stable double nitrides are larger than those of constituent single nitrides. Among them, CSi₂N₄ shows exceptionally strong covalent bonding and a large bulk modulus. A simple scaling law based on bond lengths can describe the bulk moduli of these spinel nitrides quite well.