RESUMEN
Oxygen vacancies (VO) influence many properties of ZnO in semiconductor devices, yet synthesis methods leave behind variable and unpredictable VO concentrations. Oxygen interstitials (Oi) move far more rapidly, so post-synthesis introduction of Oi to control the VO concentration would be desirable. Free surfaces offer such an introduction mechanism if they are free of poisoning foreign adsorbates. Here, isotopic exchange experiments between nonpolar ZnO(101[combining macron]0) and O2 gas, together with mesoscale modeling and first-principles calculations, point to an activation barrier for injection only 0.1-0.2 eV higher than for bulk site hopping. The modest barrier for hopping in turn enables diffusion lengths of tens to hundreds of nanometers only slightly above room temperature, which should facilitate defect engineering under very modest conditions. In addition, low hopping barriers coupled with statistical considerations lead to important qualitative manifestations in diffusion via an interstitialcy mechanism that does not occur for vacancies.