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Depth-resolved cathodoluminescence spectroscopy (DRCLS) reveals the evolution of surface and near surface defects at polar surfaces with remote oxygen plasma (ROP) treatment. Furthermore, this evolution exhibits significant differences that depend on surface polarity. ROP decreased the predominant 2.5 eV defect emission related to oxygen vacancies on the O face, while creating a new 2.1 eV defect emission on the Zn face that increases with ROP time. The surface-located 2.1 eV emission correlates with carrier profiles from capacitance-voltage measurements and a shift of the E3 trap to higher binding energy from deep level transient spectroscopy (DLTS). This result suggests that ROP generates Zn vacancies on the Zn face which act as compensating acceptors at the surface and in the near surface region. Secondary ion mass spectrometry (SIMS) shows no polarity dependence due to impurities. We conclude that the near-surface deep level optical emissions and free carrier densities of ZnO depend strongly on the ROP modulation of native defects related to Zn or O vacancies.