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We used depth-resolved cathodoluminescence spectroscopy (DRCLS) to measure the nature and spatial distribution of native point defects at Zn- and O-polar ZnO interfaces with iridium oxide (IrOx) and their impact on Schottky barrier formation. IrOx and other metal oxides exhibit higher Schottky barriers than their pure metal counterparts, consistent with wider depletion regions and potentially useful for ohmic contacts to p-type semiconductors. DRCLS with I-V and 1/C2-V barrier height and carrier profile measurements showed high zinc vacancy VZn and CuZn defect densities that compensate free carrier densities, increase depletion widths, and form higher effective barriers than Ir/ZnO contacts. Zn-polar versus O-polar ZnO interfaces with IrOx exhibit 40% higher VZnþCuZn interface segregation and lower carrier densities within a wider depletion region, accounting for the significantly higher (0.89 vs. 0.67 eV) barrier heights. Both the depth of VZn density segregation and the Zn-deficient layer thickness measured microscopically match the depletion width and applied electric fields comparable to spontaneous polarization fields across similar layers displaying analogous defect segregation. These results account for the difference in polaritydependent segregation due to the electric field-driven diffusion of native defects near ZnO interfaces [ABSTRACT FROM AUTHOR]