Emission properties of Mn doped ZnO nanoparticles prepared by mechanochemical processing

Mechanochemical processing was reported to introduce lot of crystal defects which can significantly influence emission properties. Nevertheless, to the best of our knowledge, there are no reports on effect of mechanochemical processing on emission properties of transition metal ion doped ZnO. In this study, Zn1-xMnxO nanoparticles with different Mn content (x=0, 0.02, 0.04, 0.06, 0.08, and 0.1) were prepared by mechanochemical processing to study the effect of Mn doping and processing on emission properties. Confirmation of nanoparticles size and nanocrystalline nature of hexagonal wurtzite ZnO structure is carried out using transmission electron microscopy (TEM) and selected area electron diffraction (SAED), respectively. The samples were also characterized using Fluorescence Spectroscope before and after heat-treatment. The emission studies revealed that blue emission intensity is stronger compared to UV and green emission in contrast to the earlier reports, where other synthesis routes were employed for the ZnO nanoparticles' preparation. The blue emission originates from the zinc interstitial (Zn-i) and oxygen interstitial (O-i) defects, which indicate that the mechanochemical route resulted in more interstitial defects compared to oxygen substitution (O-zn) and oxygen vacancy (V-o) defects which otherwise would give green emission. Mn doping resulted in shifting of near-band-edge (NBE) emission and the reduction in the intensities of NBE, blue and green emissions. The initial red shift at lower Mn content could be due to s-d and p-d exchange interactions as well as band tailing effect where as the blue shift at higher Mn content can be attributed to the Burstein-Moss shift. The reduction in emission intensity could be due to non-radiative recombination processes promoted by Mn ions with increasing Mn content. (C) 2012 Elsevier B.V. All rights reserved.