Yilong Pan

Superhard sp2-sp3 hybridized BC2N: A 3D crystal with 1D and 2D alternate metallicity

A novel sp2-sp3 hybridized orthorhombic BC2N (o-BC2N) structure (space group: Pmm2, No. 25) is investigated using first-principles calculations. O-BC2N is constructed from multi-layers of C sandwiched between two layers of BN along the c axis; this structure contains sp2- and sp3-hybridized B-C, C-C, and C-N bonds. The structural stability of o-BC2N is confirmed based on the calculation results for elastic constants and phonon dispersions. On the basis of the semi-empirical microscopic model, we speculate that the o-BC2N compound is a potential superhard material with a Vickers hardness of 41.2 GPa. Calculated results for electronic band structures, density of states (DOS) and partial DOS (PDOS) show that the o-BC2N crystal is metallic. The conducting electrons at the Fermi level are mostly from the 2p orbits of sp2-hybridized B4, N1, and Ci (i = 2, 3, 4, 6, 7, 8) atoms, with slight contribution from the sp3-hybridizd B2 atoms. Furthermore, the calculated electron orbits of the o-BC2N crystal demonstrate ...

Superhard three-dimensional B3N4 with two-dimensional metallicity

As the stable compound in boron nitrides, stoichiometric BN is a well-known insulator, irrespective of its structure and dimensionality. The exploration of novel B–N compounds with various stoichiometric ratios can lead to the discovery of unexpected electrical and mechanical properties. To the best of our knowledge, previously reported graphite-like or diamond-like B–N compounds obtained from experimental synthesis and theoretical prediction are mostly insulators or semiconductors. In this paper, a sp2–sp3 hybridised tetragonal phase of B3N4 (t-B3N4) possessing unique two-dimensional (2D) metallicity in a 3D ultra-strong framework has been predicted through an unbiased swarm structure search. The structure of t-B3N4 can be considered as sp3-hybridised cubic BN blocks interlinked by sp2 N–N bonds. Noticeably, t-B3N4 is metastable at ambient pressure, but becomes stable under high pressure. The transition pressure from layered B3N4 to t-B3N4 is 14.7 GPa, and the calculated formation enthalpies of t-B3N4 with respect to h-BN and N2 become negative at pressures above 20 GPa, indicating its viability under pressure. Its structure stability has been confirmed by the criteria of both elastic constants and phonon frequency dispersions. The analyses of the band structure, density of states, and electron orbitals show that the metallic behaviour of t-B3N4 mainly originates from the N 2p electrons, and that the conduction is interrupted by the insulated boron sheets stacked along the c axis, giving rise to the 2D metallicity of the material. The theoretical Vickers hardness of t-B3N4 is estimated to reach 42.5 GPa, which is the highest among all proposed B3N4 polymorphs. Furthermore, t-B3N4 exhibits ultra-high axial incompressibility even beyond that of diamond, due to the existence of strong short N–N bonds.

3D hybrid carbon composed of multigraphene bridged by carbon chains

The element carbon possesses various stable and metastable allotropes; some of them have been applied in diverse fields. The experimental evidences of both carbon chain and graphdiyne have been reported. Here, we reveal the mystery of an enchanting carbon allotrope with sp-, sp2-, and sp3-hybridized carbon atoms using a newly developed ab initio particle-swarm optimization algorithm for crystal structure prediction. This crystalline allotrope, namely m-C12, can be viewed as braided mesh architecture interwoven with multigraphene and carbon chains. The m-C12 meets the criteria for dynamic and mechanical stabilities and is energetically more stable than carbyne and graphdiyne. Analysis of the B/G and Poisson’s ratio indicates that this allotrope is ductile. Notably, m-C12 is a superconducting carbon with Tc of 1.13 K, which is rare in the family of carbon allotropes.