Chemical bond and electronic structure anisotropies in the graphitic and rhombohedral modifications of boron nitride

The pseudopotential method is used to calculate the band spectra, valence charge densities, and electroneutrality levels in the graphitic (h-BN) and rhombohedral (r-BN) modifications of boron nitride. It is shown that these compounds are indirect-band insulators with the minimum energies of the indirect (4.65 and 4.8 eV) and direct (5.27 and 5.5 eV) forbidden zones in h- and r-BN, respectively. The band energies of h-BN correlate well with the experimental data. Both crystals are characterized by ionic-covalent chemical bonds. In the plane of hexagonal layers, the bonds are more covalent in h-BN. In h- and r-BN, the electroneutrality levels correspond to the energy of about 1.9 eV over the top of the valence band, which is responsible for the hole conductivity of the substances. In superlattices based on these compounds, the rhombohedral phase is a quantum well for holes and a barrier for electrons. Translated fromZhumal Strukturnoi Khimii, Vol. 38, No. 1, pp. 32–42, January–February, 1997.