The donor efficiencies of Eu3+ ions and hydrogen atoms in ZnO crystalline films were investigated with reference to that of Ga3+ ions. It was found that Eu3+ ions acted as extrinsic donors in ZnO:Eu films, yielding a resistivity of 1.8 × 10−3 Ω cm at a doping level of 1 at. %. This value is comparable to one for intrinsic donors in undoped ZnO films. The conductivity was maintained as the deposition temperature was increased to 200 °C, and this is evidence for the contribution of extrinsic donors. Deposition of Ga-doped and Eu-doped ZnO films in an H2O gas flow produced oxyhydrogenated ZnO:(Ga, H) and ZnO:(Eu, H) films in which the Ga3+ and Eu3+ donors were deactivated by oxidization. Nevertheless, hydrogen donors contributed to electrical conduction yielding a resistivity of 1 × 10−2 Ω cm. Postannealing in an H2 gas ambient alleviated the excessive oxidization of the films and thereby reactivated the donor action of Ga3+ and Eu3+ ions, causing the resistivity to recover to 10−3 Ω cm for ZnO:(Ga, H) and 10−2 Ω cm for ZnO:(Eu, H). In contrast, vacuum annealing of ZnO:(Ga, H) and ZnO:(Eu, H) films increased resistivity through removal of hydrogen donors while not affecting the oxidized condition of the samples.

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