Cubic ZnS under pressure: Optical-absorption edge, phase transition, and calculated equation of state

Abstract

We have measured the effect of pressure on the energy of the direct-optical-absorption edge (${\mathit{E}}_{0}$ gap, ${\mathrm{\ensuremath{\Gamma}}}_{15}^{\mathit{v}}$\ensuremath{\rightarrow}${\mathrm{\ensuremath{\Gamma}}}_{1}^{\mathit{c}}$) of cubic ZnS, covering the full stability range (0--15 GPa) of the tetrahedral phase. The ${\mathit{E}}_{0}$ gap exhibits a sublinear increase under pressure, with the corresponding (linear) gap deformation potential being -5.0(2) eV. X-ray diffraction shows the high-pressure phase of ZnS to have the NaCl-type structure for pressures up to at least 27 GPa. In contrast to earlier reports, this phase is not metallic but shows a broad optical-absorption edge with onset near 2 eV, which is characteristic of an indirect-gap material. Experimental results for the equation of state and band-gap deformation potential are compared with ab initio calculations based on local-density theory and the relativistic linear-muffin-tin-orbital method.