The structure and multifunctionality of high-boron transition metal borides *

Abstract High boron content transition metal (TM) borides (HB-TMBs) have recently been regarded as the promising candidate for superhard multifunctional materials. High hardness stems from the covalent bond skeleton formed by high content of boron (B) atoms to resist deformation. High valence electron density of TM and special electronic structure from p-d hybridization of B and TM are the sources of multifunction. However, the reason of hardness variation in different HB-TMBs is still a puzzle because hardness is a complex property mainly associated with structures, chemical bonds, and mechanical anisotropy. Rich types of hybridization in B atoms ( sp, sp 2 , sp 3 ) generate abundant structures in HB-TMBs. Studying the intrinsic interaction of structures and hardness or multifunction is significant to search new functional superhard materials. In this review, the stable structure, hardness, and multifunctionality of HB-TMBs are summarized. It is concluded that the structures of HB-TMBs are mainly composed by sandwiched stacking of B and TM layers. The hardness of HB-TMBs shows a increasing tendency with the decreasing atom radius. The polyhedron in strong B skeleton provides hardness support for HB-TMBs, among which C2/ m is the most possible structure to meet the superhard standard. The shear modulus ( G 0 ) generates a positive effect for hardness of HB-TMBs, but the effect from bulk modulus ( G 0 ) is complex. Importantly, materials with a value of B 0 / G 0 less than 1.1 are more possible to achieve the superhard standard. As for the electronic properties, almost all TMB 3 and TMB 4 structures exhibit metallic properties, and their density of states near the Fermi level are derived from the d electrons of TM. The excellent electrical property of HB-TMBs with higher B ratio such as ZrB 12 comes from the channels between B–B π -bond and TM-d orbitals. Some HB-TMBs also indicate superconductivity from special structures, most of them have stronger hybridization of d electrons from TM atoms than p electrons from B atoms near the Fermi level. This work is meaningful to further understand and uncover new functional superhard materials in HB-TMBs.