Clustered vacancies in ZnO: chemical aspects and consequences on physical properties

The chemical nature of point defects, their segregation, cluster or complex formation in ZnO is an important area of investigation. The evolution of a defective state with MeV Ar ion irradiation fluence 1 × 1014 and 1 × 1016 ions cm−2 has been monitored here using x-ray photoelectron spectroscopy (XPS), photoluminescence (PL) and Raman spectroscopy. The XPS study shows the presence of oxygen vacancies (VO) in Ar irradiated ZnO. Zn(LMM) Auger spectra clearly identifies a transition involving metallic zinc in the irradiated samples. An intense PL emission from interstitial Zn (IZn)-related shallow donor bound excitons (DBX) is visible in the 10 K spectra for all samples. Although overall PL is largely reduced with irradiation disorder, DBX intensity is increased for the highest fluence irradiated sample. The Raman study indicates damage in both the zinc and oxygen sub-lattice by an energetic ion beam. Representative Raman modes from defect complexes involving VO, IZn and IO are visible after irradiation with intermediate fluence. A further increase of fluence shows, to some extent, a homogenization of disorder. A huge reduction of resistance is also noted for this sample. Certainly, high irradiation fluence induces a qualitative modification of the conventional (and highly resistive) grain boundary (GB) structure of granular ZnO. A low resistive path, involving IZn related shallow donors, across the GB can be presumed to explain resistance reduction. Open volumes (VZn and VO) agglomerate more and more with increasing irradiation fluence and are finally transformed to voids. The results as a whole have been elucidated with a model which emphasizes the possible evolution of a new defect microstructure that is distinctively different from the GB-related disorder. Based on the model, qualitative explanations of commonly observed radiation hardness, colouration and ferromagnetism in disordered ZnO have been put forward. A coherent scenario on disorder accumulation in ZnO has been presented, which we believe will guide further discussion on this topic.