High quality ZnO single-crystal films were doped with copper by thermal diffusion, and their luminescent properties were studied by cathodoluminescence spectroscopy. Doping with copper increases the intensity of the green-emission band of the cathodoluminescence spectrum, whose peak, width, and shape at 78 and 300 K remain unchanged. At 4.2 K, a pronounced phonon structure with a phonon energy of 72 meV is detected in the cathodoluminescence green-emission band of the doped samples. In this case, the phonon peaks feature a triplet fine structure instead of the doublet one generally observed. This feature is attributed to radiative recombination of acceptor excitons that are localized at copper atoms and interact with each one of the subbands of the ZnO valence band. An analysis of the experimental data on the film cathodoluminescence and comparative studies of luminescence and electron spin resonance in single crystals allow one to conclude that the uncontrollable copper impurity typically existing in ZnO is responsible for green-emission luminescence in this material. (C) 2004 MAIK Nauka / Interperiodica.
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