Optical and Magnetic Properties of Manganese-Doped Zinc Sulfide Nanoclusters

We report the synthesis of fixed-size ZnS nanoclusters ~24 Å in diameter with varying manganese concentrations. Various samples of Zn_1-x Mn_xS, with x = 0, 0.02, 0.055, 0.09, and 0.13, have been prepared and characterized using X-ray diffraction, energy-dispersive analysis of X-rays, UV absorption, fluorescence emission and excitation, electron paramagnetic resonance (EPR), and magnetic susceptibility measurements. The manganese ions are found to substitute Zn randomly without giving rise to any clustering of Mn sites, as seen from EPR and magnetic susceptibility results. Our studies reveal that the band gap of the doped nanoclusters passes through a maximum as the manganese concentration is varied. Also, we observe orange emission from Mn²⁺ ions in the doped ZnS nanoclusters, apart from the blue emission characteristic of the ZnS defect states. The relative intensity of the orange emission compared with the blue varies with the manganese concentration in a nonmonotonic way. The inverse of susceptibility temperature plots can be plotted onto a universal curve by simple multiplicative constants, thus showing that the magnetic interactions between Mn²⁺ ions are weak.