Abstract:
Due to the strong covalent bonds that can readily form among the light elements B, C, and O, B-C-O compounds are considered one of the ideal systems for exploring and designing novel superhard materials. In this work, the CALYPSO structure prediction method, combined with first-principles calculations, was employed to systematically investigate the stability of ternary B-C-O compounds under high pressure. Two novel metastable compounds, B
2CO
5 and B
3CO
3, were identified. Among them, the formation energy of B
2CO
5 is only 6 meV/atom above the thermodynamic convex hull. Both B
2CO
5 and B
3CO
3 are non-diamond isoelectronic compounds and exhibit novel bonding configurations. The crystal structure of B
2CO
5 consists of sp
2-hybridized planar triangular CO
3 units and sp
3-hybridized BO
4 tetrahedra, which are interconnected through shared O atoms. In contrast, the crystal structure of B
3CO
3 contains sp
3-hybridized BCO
3 tetrahedral units. Mechanical property analysis reveals that B
2CO
5 exhibits pronounced elastic anisotropy along different crystallographic planes, whereas B
3CO
3maintains elastic isotropy on the (001) plane. Hardness calculations indicate that B
3CO
3 has a Vickers hardness of approximately 36.4 GPa at 0 GPa, suggesting its potential for applications as a superhard material. Electronic structure calculations show that both B
2CO
5 and B
3CO
3 exhibit wide-band-gap semiconducting characteristics at 25 GPa, with PBE-calculated band gaps of 4.49 and 5.46 eV, respectively, while the corresponding values obtained using the HSE06 hybrid functional are 6.77 and 7.07 eV. This study enriches the diversity of bonding configurations in B-C-O compounds and provides theoretical insights and data for the design of novel superhard materials under high-pressure conditions.