Influence of transition-metal type and content on local-order properties of ${\mathrm{Zn}}_{1\mathrm{-}\mathit{x}}$${\mathit{M}}_{\mathit{x}}$S (M=Mn,Fe,Co) alloys studied using XANES spectroscopy

X-ray-absorption near-edge-structure (XANES) spectra of the diluted-magnetic-semiconductor system ${\mathrm{Zn}}_{1\mathrm{-}\mathit{x}}$ ${\mathrm{Mn}}_{\mathit{x}}$S have been measured at the Zn ${\mathit{L}}_{\mathrm{I}\mathrm{I}\mathrm{I},\mathrm{I}\mathrm{I}}$ edge and of ${\mathrm{Zn}}_{1\mathrm{-}\mathit{x}}$ ${\mathit{M}}_{\mathit{x}}$S (M=Mn,Fe,Co) at the S K edge using the total-electron-yield mode. The Zn ${\mathit{L}}_{\mathrm{III}}$ edge results for ${\mathrm{Zn}}_{1\mathrm{-}\mathit{x}}$ ${\mathrm{Mn}}_{\mathit{x}}$S show a dramatic reduction in intensity of the first prominent feature, just above the edge, in the XANES spectra. Analysis of the S K-edge XANES spectra for ${\mathrm{Zn}}_{1\mathrm{-}\mathit{x}}$ ${\mathit{M}}_{\mathit{x}}$S revealed the appearance of a pre-edge peak, having linear x dependence in intensity and assigned to S 1s photoelectron excitations to an empty narrow band of S 3p–M 3d(${\mathit{t}}_2$) hybridized antibonding states. The rate of peak intensity with M concentration is associated with differences in the degree of p-d hybridization of states between the transition metal and sulfur. Features above the edge are generally found to decrease in intensity with an increase in transition-metal content in the alloys. The results are consistent with more S 3p–transition metal (M) 3d(${\mathit{t}}_2$) hybridized states and less S 3p–Zn 4(s,p) and S 3p–Zn 3d hybridized states becoming available as the transition-metal content increases in the alloys.