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The results of comparative studies of the processes of high-temperature synthesis, luminescence and scintillation characteristics of ZnO films on M(100)- and A(110)-orientation sapphire substrates are presented. It is shown that the use of the magnetron deposition method makes it possible to form, against the background of a continuous film, ensembles of individual [001] ZnO microcrystals with pronounced X-ray luminescent properties. The X-ray luminescence kinetics is characterized by two components: a fast component with a decay time in the order of a nanosecond and a slow luminescence component. The study of the films by photoluminescence spectroscopy revealed the features of the near-band-edge luminescence spectra of the samples, in particular, the presence of various excitonic emission channels. Differences in the spectral parameters of the near-band-edge luminescence band in the case of optical and X-ray excitation are found and interpreted.