Influence of hydrogen introduction on structure and properties of ZnO thin films during sputtering and post-annealing

ZnO thin films were prepared in Ar and Ar + H₂ atmospheres by rf magnetron sputtering, and then they were annealed in vacuum and Ar + H₂ atmosphere, respectively. The structure and optical-electrical properties of the films were investigated by X-ray diffraction, transmittance spectra, and resistivity measurement, and their dependences on deposition atmosphere, annealing treatment, and aging were studied. The results showed that adding H₂ in deposition atmosphere improved the crystallinity of the films, decreased lattice constant, increased band gap, decreased the resistivity by the order of 10⁴ Ω cm, but exhibited poor conductive stability with aging. After Ar + H₂ and vacuum annealing, crystallinity of the films deposited in Ar and Ar + H₂ was further improved; their resistivity was decreased by the order of 10⁵ and 10¹ Ω cm, respectively, and exhibited high conductive stability with aging. We suggest that the formed main defect is V_O and H_i when H₂ is introduced during deposition, which decreases the resistivity but cannot improve the conductive stability; hydrogen would remove negatively charged oxygen species near grain boundaries during Ar + H₂ annealing to decrease the resistivity, and grain boundaries are passivated by formation of a number of V_O-H complex (H_O) to improve the conductive stability at the same time. Under vacuum annealing, the hydrogen that is introduced non-intentionally from deposition chamber maybe plays an important role; it exists as H_O in the films to improve the conductive stability of the films.