Energy-Transfer Efficiency in Eu-Doped ZnO Thin Films: The Effects of Oxidative Annealing on the Dynamics and the Intermediate Defect States

We have studied ultrafast dynamics in thin films of Eu-doped zinc oxide (ZnO), prepared by radio-frequency sputtering onto sapphire substrates. Following UV excitation of ZnO, a red emission is observed. Postdeposition annealing in an oxygen atmosphere improves the crystallinity and emission intensity of the films, which are highly sensitive to the dopant concentration. Transient-absorption spectroscopy shows that the excited semiconductor host transfers energy to rare-earth ions on a time scale of only a few picoseconds. The dynamics as a function of the probe wavelength change dramatically after annealing, with annealed films showing the fastest dynamics at much lower wavelengths. Our results show that annealing greatly affects the defect energy levels of the films and the dynamics of the trapped carriers. Unannealed films show dynamics consistent with energy transfer from O vacancies to the dopant, while energy transfer in annealed samples involves acceptor-type defects such as Zn vacancies as intermediates.