Mn²⁺-induced substitutional structural changes in ZnS nanoparticles as observed from positron annihilation studies

Zinc sulfide nanoparticles doped with different concentrations of manganese ions (Mn²⁺) were synthesized at various temperatures to investigate the effects of substitution and the associated defect evolution. Positron lifetime and Doppler broadening measurements were used as probes. The initial stage of defect recovery was dominated by the occupation of Zn²⁺ vacancies by Mn²⁺ ions, bringing in characteristic changes in the positron lifetimes, intensities and Doppler broadened lineshape parameters. Detailed analyses considering the presence of one and two types of defects were carried out to identify the type of defects which trap positrons at the different dopant concentrations. Electron paramagnetic resonance studies indicated increased Mn-Mn interaction and the formation of Mn clusters with further doping. The results are in striking contrast to those for nanorods, where vacancy recombination transformed their interior into regions free of defects.