Abstract: This paper reports that the high-quality Co-doped ZnO single crystalline films have been grown on $a$-plane sapphire substrates by using molecular-beam epitaxy. The as-grown films show high resistivity and non-ferromagnetism at room temperature, while they become good conductive and ferromagnetic after annealing in the reducing atmosphere either in the presence or absence of Zn vapour. The x-ray absorption studies indicate that all Co ions in these samples actually substituted into the ZnO lattice without formatting any detectable secondary phase. Compared with weak ferromagnetism (0.16 $\mu _{\rm B}$/Co$^{2 + })$ in the Zn$_{0.95}$Co$_{0.05}$O single crystalline film with reducing annealing in the absence of Zn vapour, the films annealed in the reducing atmosphere with Zn vapour are found to have much stronger ferromagnetism (0.65 $\mu _{\rm B}$/Co$^{2 + })$ at room temperature. This experimental studies clearly indicate that Zn interstitials are more effective than oxygen vacancies to activate the high-temperature ferromagnetism in Co-doped ZnO films, and the corresponding ferromagnetic mechanism is discussed.

Key words: Co-doped ZnO, diluted magnetic semiconductors, x-ray absorption fine structure, single crystalline thin films