Oxygen and zinc vacancies in as-grown ZnO single crystals

Oxygen and zinc vacancies are unambiguously shown to be formed in as-grown ZnO bulk crystals grown from melt without being subjected to irradiation, from electron paramagnetic resonance (EPR) and optically detected magnetic resonance (ODMR) studies. Concentrations of the defects in their paramagnetic charge states V-O(+) and V-Zn(-) are estimated to be similar to 2 x 10(14) cm(-3) and similar to 10(15) cm(-3), respectively. The V-Zn(-) defect is concluded to act as a deep acceptor and to exhibit large Jahn-Teller distortion by 0.8 eV. The energy level of the defect corresponding to the (2-/-) transition is E-v + 1.0 eV. The isolated Zn vacancy is found to be an important recombination centre and is concluded to be responsible for the red luminescence centred at around 1.6 eV. On the other hand, the oxygen vacancy seems to be less important in carrier recombination as it could be detected only in EPR but not in ODMR measurements. Neither isolated V-Zn(-) nor V-O(+) centres participate in the so-called 'green' emission. It is also shown that whereas the concentrations of both defects can be reduced by post-growth annealing, the Zn vacancy exhibits higher thermal stability. The important role of residual contaminants such as Li in the annealing process is underlined.