Recent theory has found that native defects such as the O vacancy V(O) and Zn interstitial Zn(I) have high formation energies in n-type ZnO and, thus, are not important donors, especially in comparison to impurities such as H. In contrast, we use both theory and experiment to show that, under N ambient, the complex Zn(I)-N(O) is a stronger candidate than H or any other known impurity for a 30 meV donor commonly found in bulk ZnO grown from the vapor phase. Since the Zn vacancy is also the dominant acceptor in such material, we must conclude that native defects are important donors and acceptors in ZnO.

We have used positron annihilation spectroscopy to study the introduction and recovery of point defects in electron-irradiated n-type ZnO. The irradiation ͑E el = 2 MeV, fluence 6 ϫ 10 17 cm −2 ͒ was performed at room temperature, and isochronal annealings were performed from 300 to 600 K. In addition, monochromatic illumination of the samples during low-temperature positron measurements was used in identification of the defects. We distinguish two kinds of vacancy defects: the Zn and O vacancies, which are either isolated or belong to defect complexes. In addition, we observe negative-ion-type defects, which are attributed to O interstitials or O antisites. The Zn vacancies and negative ions act as compensating centers and are introduced at a concentration ͓V Zn ͔Ӎc ion Ӎ 2 ϫ 10 16 cm −3 . The O vacancies are introduced at a 10-times-larger concentration ͓V O ͔Ӎ3 ϫ 10 17 cm −3 and are suggested to be isolated. The O vacancies are observed as neutral at low temperatures, and an ionization energy of 100 meV could be fitted with the help of temperature-dependent Hall data, thus indicating their deep donor character. The irradiation-induced defects fully recover after the annealing at 600 K, in good agreement with electrical measurements. The Zn vacancies recover in two separate stages, indicating that the Zn vacancies are parts of two different defect complexes. The O vacancies anneal simultaneously with the Zn vacancies at the later stage, with an activation energy of E V,O m = 1.8± 0.1 eV. The negative ions anneal out between the two annealing stages of the vacancies.

By combining results from positron annihilation and photoluminescence spectroscopy with data from Hall effect measurements, the characteristic deep level emission centered at ∼1.75 eV and exhibiting an activation energy of thermal quenching of 11.5 meV is associated with the zinc vacancy. Further, a strong indication that oxygen interstitials act as a dominating acceptor is derived from the analysis of charge carrier losses induced by electron irradiation with variable energy below and above the threshold for Zn-atom displacement. We also demonstrate that the commonly observed green emission is related to an extrinsic acceptorlike impurity, which may be readily passivated by oxygen vacancies.

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The dominant electrically active defect produced by 0.42 MeV electron irradiation in GaN is a 70 meV donor. Since only N-sublattice displacements can be produced at this energy, and since theory predicts that the N interstitial is a deep acceptor in n-type GaN, we argue that the 70 meV donor is most likely the isolated N vacancy. The background shallow donors, in the 24–26 meV range, actually decrease in concentration, probably due to interactions with mobile N interstitials that are produced by the irradiation. Thus, the recent assignment of a photoluminescence (PL) line as an exciton bound to a 25 meV N-vacancy donor is incompatible with our results. Moreover, we do not observe that PL line in our sample.