Influence of reactant concentration on optical properties of ZnO nanoparticles

Zinc oxide (ZnO) nanoparticles have been prepared by wet chemical method from zinc acetate. Particle size was controlled by adjusting the reactant concentration. The size of nanoparticles was investigated using ultraviolet-visible absorption spectra and photoluminescence spectra. The present nanoparticles exhibit non-linear optical behaviour with blue shift of the wavelengths as the particle size decreases. Furthermore, yellow emission is observed in ambient air while it disappears in the presence of nitrogen gas and gets substituted by blue violet emissions. While the blue violet emissions are familiar and likely to be attributed to electronic transitions from localised states (e.g. shallow donor states on Zn interstitials 'Zn-i') or the conduction band edge to the valence band, the yellow emission in the absence of nitrogen remains unclear. Our results of the present investigation suggest that the bubbling with nitrogen should fill the oxygen vacancies, substitute the oxygen interstitials, passivate the dangling bonds and introduce shallow acceptor states, which allow electronic transitions with shorter wavelengths (i.e. blue violet emissions). In the absence of nitrogen, surface defects such as oxygen interstitials and Zn(OH)(2) and possibly other point defects become again active and induce deep acceptor states of similar to 1 eV above the valence band edge, which allow electronic transitions of longer wavelength (i.e. yellow emission). Our results are compared to several available experimental data and first principle calculations in order to support our claims and conclusions.