Interplay of Electronic Structure and Bulk Properties in 2D and 3D Ternary Carbonitrides from First Principles

The changes in electronic structure and hardness as inferred from the bulk modulus are investigated for model structures of ternary compounds XC 3 N 3 (X = B, Al, P, As, Ga) within the framework of density functional theory (DFT). The optimisations of the proposed two‐ (2D) and three‐dimensional (3D) structures and the calculations of the bulk moduli are performed by a pseudo potential method. The electronic structures are calculated with the augmented sphere wave method (ASW). The obtained hardness for 2D BC 3 N 3 system (B 0 ∼ 220 GPa) points to a magnitude close to that of graphitic C 3 N 4 . For heavier X atoms it decreases rapidly. This is equally observed for the 3D systems examined in the β‐C 3 N 4 structure for which B 0 (β‐BC 3 N 3 ) amounts to ∼330 GPa. Within the magnitude of the well known hard material cubic BN, the BC 3 N 3 phases can be predicted as candidates for ultra hard materials. The electronic effect induced by the chemical nature of the X substitutional was examined according to its position in the periodic table i.e. X III or X V . Both, band structures and the electron localisation function (ELF) were used for this analysis. The ELF plots show a decreasing covalency with heavier X‐atoms. Potential applications of the devised systems are proposed such as dopings with atoms (Li, rare gas) and molecules (N 2 ).