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Virgin and Yb-implanted epitaxial ZnO films grown using atomic layer deposition (ALD) were investigated by X-ray absorption spectroscopy (XAS). XAS study revealed a strong polarization dependence of films determined by the orientation of the polarization vector of the synchrotron radiation to the sample surface. It also indicated that the implantation and subsequent annealing have an important influence on the native point defect complexes in the ZnO. Comparison of experimental spectra with the modelled ones, which are computed based on the linear combination of model spectra corresponding to the selected point defects and their complexes, confirmed the presence of donor-acceptor complexes (mVZn - nVO, m = 1,4; n = 1,2) in the samples under study. The mechanism of vacancy complexes formation is unclear as it takes place under non-equilibrium conditions, for which any theoretical method has not been well established. Exploring the 3 d → 4 f absorption, it was found that oxidation state of Yb in ZnO is 3+, which is consistent with the XPS findings and previously conducted Resonant Photoemission Spectroscopy (RPES) investigations. The inversion of the polarization dependence for samples with different Yb fluences visible in Yb M5 spectra can be associated with a tilt of the oxygen pseudo octahedra or/and with their distortion. The analysis of the presented data suggests that the donor-acceptor complexes are present both in as grown and implanted films and may influence their electrical properties. This suggestion was confirmed by previous Hall measurements showing that the resistivity of annealed ZnO:Yb film with a fluence of 5e15 ions/cm2 decreases by about one order compared to the one with a fluence of 5e14 ions/cm2.