Novel superhard semiconducting structures of C8B2N2 predicted using the first-principles approach

Abstract

Using first-principles calculations, we predicted three novel superhard semiconducting structures of C₈B₂N₂ with a space group of P3m1. We investigated their mechanical properties and electronic structures up to 100 GPa. These three structures were successfully derived by substituting carbon (C) atoms with isoelectronic boron (B) and nitrogen (N) atoms in the P3m1 phase, which is the most stable structure of BCN and exhibits exceptional mechanical properties. Our results indicated that these structures had superior energy over previously reported t-C₈B₂N₂, achieved by replacing C atoms in the diamond supercell with B and N atoms. To ensure their stable existence, we thoroughly examined their mechanical and dynamical stabilities, and we found that their hardness values reached 82.4, 83.1, and 82.0 GPa, which were considerably higher than that of t-C₈B₂N₂ and even surpassing the hardness of c-BN. Calculations of the electron localization function revealed that the stronger carbon–carbon covalent bonds made them much harder than t-C₈B₂N₂. Additionally, our further calculations of band structures revealed that these materials had indirect bandgaps of 4.164, 4.692, and 3.582 eV. These findings suggest that these materials have the potential to be used as superhard semiconductors, potentially surpassing conventional superhard materials.