Electronic structure of ZnS, ZnSe, ZnTe, and their pseudobinary alloys

Abstract

Using the all-electron mixed-basis approach to the density-functional formalism for crystals, we calculate from first principles the electronic structure of zinc-blende ZnS, ZnSe, and ZnTe as well as that of their ordered pseudobinary alloys ${\mathrm{Zn}}_2$SSe, ${\mathrm{Zn}}_2$SeTe, and ${\mathrm{Zn}}_2$STe. For the latter we use as a model a CuAu I-like structure (space group $P\overline{4}m2\mathrm{}$), and analyze the observed optical bowing in terms of three contributions: (i) a volume deformation of the band structure due to the replacement of the lattice constants of the binary constituents by that of the alloy, (ii) a chemical-electronegativity contribution due to charge exchange in the alloy relative to its constituent binary subsystems, and (iii) a structural contribution due to the relaxation of the anion-cation bond lengths in the alloy. The total bowing effect [the sum of (i)-(iii) above] agrees well with observations, yet the present analysis suggests a physical mechanism for optical bowing which differs profoundly from that offered by the popular virtual-crystal approach. The maximum contribution of disorder to the optical bowing is calculated for $\mathrm{Zn}{\mathrm{S}}_x{\mathrm{Te}}_{1-x}$ using a cluster-averaging method, resulting in a reduction in the bowing of the fundamental gap. We further discuss the band structures, x-ray scattering factors, charge distribution, and deformation potentials of the binary zinc chalcogenides and their ordered alloys.