Features of ZnS-powder doping with a Mn impurity during synthesis and subsequent annealing

Luminescence, electron spin resonance, and X-ray diffraction (XRD) methods were used to investigate the features of ZnS-powder doped by Mn impurity during self-propagating high-temperature synthesis and subsequent annealing. The obtained powder consists of ZnS microcrystals with mainly hexagonal phase (80 $\pm$ 5)%. It was found, that after synthesis Mn presents not only in the form of non-uniformly distributed microscopic impurities in ZnS, but also in the form of Mn metal nanocrystals. Thermal annealing at 800$^\circ$C leads to the additional doping of ZnS from metallic Mn, to the redistribution of the embedded Mn in the volume of microcrystals, and to the ZnS oxidation. At the same time, the ratio between the cubic and hexagonal phases does not change. It was shown that annealing causes a decrease in the concentration of the defects responsible for the luminescence-excitation bands, which correspond to transitions from the ground to the excited states of the Mn$^{2+}$ ion. As a result of annealing, there is also a change in XRD coherent domain size. Simultaneously, the intensity of peaks in the luminescence-excitation spectrum with wavelengths of 375 and 395 nm was changed. The causes of these changes and the nature of the corresponding bands are discussed.