Probing the visible luminescence mechanism in ZnO nanoparticles by band edge modulation.

The visible luminescence mechanism of ZnO is an important but controversial problem. In this paper, we report the structural and optical properties of Mg-doped ZnO nanoparticles (approximately 3-4 nm) synthesized via the sol-gel method. X-ray diffraction (XRD) analysis and absorption spectra observations revealed that Mg ions replace Zn ions in the lattice. In the room temperature photoluminescence (PL) spectra, three emission bands, ultraviolet (UV), blue, and green, were observed. With increasing concentration of Mg, the near band edge (NBE) emission band progressively shifted to the higher energy side. The green emission in the visible emission band, however, presented an inconspicuous shift. The reason is probably that the bottom of the conduction band in ZnO is determined by the Zn 4s state, and the top of the valence band is determined by the O 2p state. Mg ions in ZnO substitute for zinc ions and enter a slightly distorted tetrahedral site, which causes the bottom of the ZnO conduction band to be shifted to higher energy and leaves the top of the valence band unchanged. This combined with the fact that the deep level position is insensitive to the shift of the band edge led us to conclude that the green emission originates from electronic transition between the deep defect level and the top of the valence band (or very shallow acceptor level).