Electronic Structure and Electrical Resistivity of α-Boron under High Pressure

Abstract

Recently, it has been discovered that the semiconductor α-boron becomes metallic at high pressures and finally undergoes a superconducting transition at 160 GPa, without causing any phase transition. Before the superconducting transition, a step is often observed in the pressure dependence of electrical resistivity in this class of boron crystals, which possess icosahedron-based structures. This step structure used to be thought to occur due to a phase transitions. In the present paper, we show that the step of α-boron at 50 GPa is not due to a phase transition. It is caused by a gradual change in the bonding character from semiconductor to metal. The increase in the metallic character is caused by the shortening of the three-center bond, which is a characteristic feature of icosahedron-based boron crystals. This shortening of the three-center bond enhances the bonding character of the conduction bottom band and finally closes the band gap. However, even far before the gap closing, the shortening has important consequences for the crystal properties of α-boron: for the changes in the deformation of the lattice and in the librational phonon mode at approximately 50 GPa. This change in structure affects the change in band structure, that is, the bottom of the conduction band initially moves from the Γ point toward the Z point until p =50 GPa and then almost terminates in the middle point. The step in resistivity is a direct consequence of the change in this energy gap. This provides a coherent understanding of the characteristic changes in resistivity, the deformation of the lattice, and the librational mode.