Examining the Effect of Cu and Mn Dopants on the Structure of Zinc Blende ZnS Nanopowders

It is known that doping zinc sulfide (ZnS) nanoparticles with Mn or Cu ions significantly affects their luminescent properties. Herein, we investigated how dopant atoms are incorporated into the structure of ZnS using X-ray diffraction and multi-edge X-ray absorption spectroscopy. The observed broadening of the X-ray diffraction patterns indicates an average crystallite size of about 6 nm. By analyzing the Zn, Mn, and Cu K-edge extended X-ray absorption fine structure (EXAFS) spectra using the reverse Monte Carlo method, we were able to determine the relaxations of the local environments around the dopants. Our findings suggested that upon the substitution of Zn by Mn or Cu ions, there is a shortening of the Cu–S bonds by 0.08 Å, whereas the Mn–S bonds exhibited lengthening by 0.07 Å. These experimental results were further confirmed by first-principles density functional theory calculations, which explained the increase in the Mn–S bond lengths due to the high-spin state of Mn [Formula: see text] ions.