Photoluminescence spectroscopy has been used to study single crystalline ZnO samples systematically annealed in inert, Zn-rich and O-rich atmospheres. A striking correlation is observed between the choice of annealing ambient and the position of the deep band emission (DBE) often detected in ZnO. In particular, annealing in O2 results in a DBE at 2.35±0.05eV, whereas annealing in the presence of metallic Zn results in DBE at 2.53±0.05eV. The authors attribute the former band to zinc vacancy (VZn) related defects and the latter to oxygen vacancy (VO) related defects. Additional confirmation for the VO and VZn peak identification comes from the observation that the effect is reversible when O- and Zn-rich annealing conditions are switched. After annealing in the presence of ZnO powder, there is no indication for the VZn- or VO-related bands, but the authors observe a low intensity yellow luminescence band peaking at 2.17eV, probably related to Li, a common impurity in hydrothermally grown ZnO.

Single crystalline bulk and epitaxially grown gallium oxide (β–Ga2O3) was irradiated by 0.6 and 1.9 MeV protons to doses ranging from 5 × 109 to 6 × 1014 cm−2 in order to study the impact on charge carrier concentration and electrically active defects. Samples irradiated to doses at or above 2 × 1013 cm−2 showed a complete removal of free charge carriers in their as-irradiated state, whereas little or no influence was observed below doses of 6 × 1012 cm−2. From measurements at elevated temperatures, a thermally activated recovery process is seen for the charge carriers, where the activation energy for recovery follow a second-order kinetics with an activation energy of ∼1.2 eV. Combining the experimental results with hybrid functional calculations, we propose that the charge carrier removal can be explained by Fermi-level pinning far from the conduction band minimum (CBM) due to gallium interstitials (Gai), vacancies (VGa), and antisites (GaO), while migration and subsequent passivation of VGa via hydrogen-derived or VO defects may be responsible for the recovery. Following the recovery, deep level transient spectroscopy (DLTS) reveals generation of two deep levels, with energy positions around 0.75 and 1.4 eV below the CBM. Of these two levels, the latter is observed to disappear after the initial DLTS measurements, while the concentration of the former increases. We discuss candidate possibilities and suggest that the origins of these levels are more likely due to a defect complex than an isolated point defect.

Using a combination of deep level transient spectroscopy, secondary ion mass spectrometry, proton irradiation, and hybrid functional calculations, we identify two similar deep levels that are associated with Fe impurities and intrinsic defects in bulk crystals and molecular beam epitaxy and hydride vapor phase epitaxi-grown epilayers of β-Ga2O3. First, our results indicate that FeGa, and not an intrinsic defect, acts as the deep acceptor responsible for the often dominating E2 level at ∼0.78 eV below the conduction band minimum. Second, by provoking additional intrinsic defect generation via proton irradiation, we identified the emergence of a new level, labeled as E2*, having the ionization energy very close to that of E2, but exhibiting an order of magnitude larger capture cross section. Importantly, the properties of E2* are found to be consistent with its intrinsic origin. As such, contradictory opinions of a long standing literature debate on either extrinsic or intrinsic origin of the deep acceptor in question converge accounting for possible contributions from E2 and E2* in different experimental conditions.

Oxygen vacancy (VO) is a common native point defects that plays crucial roles in determining the physical and chemical properties of metal oxides such as ZnO. However, fundamental understanding of VO is still very sparse. Specifically, whether VO is mainly responsible for the n-type conductivity in ZnO has been still unsettled in the past fifty years. Here we report on a study of oxygen self-diffusion by conceiving and growing oxygen-isotope ZnO heterostructures with delicately-controlled chemical potential and Fermi level. The diffusion process is found to be predominantly mediated by VO. We further demonstrate that, in contrast to the general belief of their neutral attribute, the oxygen vacancies in ZnO are actually +2 charged and thus responsible for the unintentional n-type conductivity as well as the non-stoichiometry of ZnO. The methodology can be extended to study oxygen-related point defects and their energetics in other technologically important oxide materials.

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