Hydrothermally grown n-type ZnO bulk samples have been implanted with protons and deuterium ions to fluences in the range of 8 × 1010 to 8 × 1011 cm−2. The implantations were performed at the temperature of 285 K, and the samples were then analyzed in-situ by deep level transient spectroscopy (DLTS) using a setup connected to the implanter beam line. The concentration of the so-called E4 center, having an apparent energy level at ∼0.57 eV below the conduction edge, is found to increase linearly with the ion fluence and the generation rate is proportional to the elastic energy deposition, as expected for a primary defect. Isothermal annealing of the E4 center at temperatures between 290 and 315 K reveals first-order kinetics with the activation energy of ∼0.6 eV. The annealing rate is strongly enhanced with increasing hydrogen fluence, and a model invoking migration of interstitial hydrogen and subsequent reaction with E4 exhibits close agreement with the experimental data. The rate of electron capture by E4 during the DLTS filling pulse depends on temperature, and it displays a thermal barrier of ∼0.15 eV. Most of these experimental results for E4 conform to the theoretically predicted properties of the oxygen vacancy (VO) and a tentative assignment of E4 to VO is made, corroborating previous suggestions in the literature. In particular, the 0.57 eV level is ascribed to the double donor state of VO.
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