Tunable Visible Photoluminescence from ZnO Thin Films through Mg-Doping and Annealing

Visible photoluminescence (PL) from ZnO has been found to be tunable in a wide range from blue to green and orange through chemical doping and annealing. Mg-doped, (Al, Li)-doped, and undoped ZnO thin films were deposited on glass substrates by a metal-organic decomposition method at temperatures around 600 °C. The films were annealed under different atmospheres, including air, oxygen, nitrogen, and hydrogen/nitrogen. X-ray diffraction analysis and field-emission scanning electron microscope observations revealed that the films consisted of large ZnO grains 50−100 nm in size. When the Mg-doped ZnO films were annealed in nitrogen or hydrogen/nitrogen, unusual blue or bluish-white PL, respectively, was observed in response to an ultraviolet light excitation. We confirmed the band-gap broadening (approximately 0.25 eV) of the Mg-doped ZnO films as compared to that of the undoped films through observation of the absorption edge. The blue-related PL therefore appeared to be caused by energetic shifts of the valence band and/or the conduction band of ZnO. Films annealed in the oxidizing atmospheres, on the other hand, showed yellow/orange PL. We ascribed this PL to electronic transitions between shallow and deep defect levels. Yellow PL was also observed in the (Al, Li)-doped ZnO films, suggesting that shallow donor/acceptor levels due to extrinsic defects also contributed to the yellow PL.