Zinc oxide thin films have been grown via metalorganic vapor phase epitaxy at 450degreesC and 250 Torr total pressure on O-terminated areas and micro-regions of native oxide formed on GaN(0001) epilayers during exposure to the oxygen reactant. Analyses of the Ga3d core level spectra acquired from films grown for progressively longer times and comparisons of these data with both thermodynamic models of growth processes and associated atomic force micrographs revealed that the ZnO nucleated and grew via the Stranski-Krastanov mode. Considerations of (1) differences in surface energetics of the polar (0001) surfaces of ZnO and GaN and that of the Ga-based oxide as well as (2) the relatively low stress generated by the moderate lattice mismatches in the a-axis lattice parameters of these compounds supported the observed growth mode. The shifts in the position of the Ga3d core level with increasing deposition time and decreasing peak intensity were caused by surface charging and increasing sampling volumes of the Ga-based oxide as well as the growing ZnO layer. The island/ocean morphology of the Ga-based oxide controlled the morphology of the initial ZnO layer, which, in turn controlled the locations and the morphologies of the subsequently nucleated ZnO islands. Scanning electron microscopy of thicker ZnO films revealed a highly textured microstructure. (C) 2003 Elsevier B.V. All rights reserved.