Synthesis of Mn2+-doped ZnS by a mechanically induced self-sustaining reaction

The mechanochemical process denoted as a mechanically induced self-sustaining reaction was successfully applied in obtaining Mn-doped ZnS samples with Mn content between 0 and 5 mol%. The process consists in milling Zn/Mn/S powder elemental mixtures with the appropriate stoichiometry, which promotes after approximately 80 min the induction of a combustion reaction. The doping level was properly adjusted by controlling the atomic ratio of the starting mixture. A complete characterization of samples was carried out, including X-ray diffraction, high-resolution transmission electron microscopy, selected area electron diffraction, energy-dispersive X-ray spectroscopy, Raman spectroscopy, diffuse reflectance UV–Vis spectroscopy and emission and excitation photoluminescence measurements. A wurtzite structure, in which Mn2+ replaces Zn2+, was obtained with a nanometric character. The photoluminescence of samples showed the characteristic Mn2+ 4T1–6A1 emission that was highly dependent on the doping level. The maximum luminescence efficiency through the ZnS excitation was found for a doping value of 1 mol%. The photoluminescence showed virtually no contribution from the host emission, which confirmed that samples were properly doped.