Light-Induced Peroxide Formation in ZnO: Origin of Persistent Photoconductivity

The persistent photoconductivity (PPC) in ZnO has been a critical problem in opto-electrical devices employing ZnO such as ultraviolet sensors and thin film transistors for the transparent display. While the metastable state of oxygen vacancy (VO) is widely accepted as the microscopic origin of PPC, recent experiments on the influence of temperature and oxygen environments are at variance with the VO model. In this study, using the density-functional theory calculations, we propose a novel mechanism of PPC that involves the hydrogen-zinc vacancy defect complex (2H-VZn). We show that a substantial amount of 2H-VZn can exist during the growth process due to its low formation energy. The light absorption of 2H-VZn leads to the metastable state that is characterized by the formation of (peroxide) around the defect, leaving the free carriers in the conduction band. Furthermore, we estimate the lifetime of photo-electrons to be ~20 secs, which is similar to the experimental observation. Our model also explains the experimental results showing that PPC is enhanced (suppressed) in oxygen-rich (low-temperature) conditions. By revealing a convincing origin of PPC in ZnO, we expect that the present work will pave the way for optimizing optoelectronic properties of ZnO.