In this study, K-beta / K-alpha X-ray intensity ratios of zinc in pure zinc, undoped ZnO thin film and boron and fluorine-doped ZnO thin films have been investigated. These samples have been excited by 59.5 keV gamma-rays from a Am-241 annular radioactive source. K X-rays emitted by the samples have been counted using an Ultra-LEGe detector with a resolution of 150 eV at 5.9 keV. The K-beta / K-alpha X-ray intensity ratios of the doped ZnO thin films have been compared with that of the undoped ZnO thin film. The deviations between the results can be explained by delocalization and/or charge transfer phenomena causing change in valence electronic configuration of zinc.