First surface electronic structure of a wurtzite-type semiconductor the polar and nonpolar surfaces of ZnO

We report the first calculations of the surface electronic structure for a Wurtzite-type semiconductor, namely ZnO. The bulk electronic properties of the material are described by a realistic empirical tight binding Hamiltonian which we obtained by fitting a selfconsistent pseudopotential bulk band structure and experimental bulk XPS and UPS data. Using the scattering theoretical method, we have calculated the surface band structures and wavevector-integrated as well as wavevector-resolved layer densities of states for polar and nonpolar ZnO surfaces. In agreement with experiment, we find no surface states in the gap on clean ZnO surfaces. Within the projection of the bulk valence and conduction bands, however, distinct surface features occur. First, there are ionic O-2p and Zn-4s surface states which have predominantly resonance character. In addition, more covalent back bond and anti back bond surface states are found which are occupied and empty, respectively. We find very good agreement with recent EELS and UPS surface data.