The formation mechanism and stability of p-type N-doped Zn-rich ZnO films
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Abstract
Nitrogen-doped Zn-rich ZnO films [ZnO:(Zn, N)] were deposited on quartz substrates using a radio-frequency (RF) magnetron sputtering and ion implantation technique. Hall-effect measurements confirmed that a p-type ZnO:(Zn, N) film with a hole concentration of ~1016 cm−3, which exhibits significantly higher stability than p-type ZnO:N film prepared under non-Zn-rich conditions, is obtained by optimized post-annealing condition. With the help of X-ray photoelectron spectroscopy, Auger electron spectroscopy, Raman spectroscopy (Raman), ultraviolet and visible spectrophotometer and first-principles calculations, it is found that a certain concentration of zinc interstitial (Zni) donor defects which easily bond to substitutional nitrogen (NO) to form defect complexes (denoted as Zni@NO) were observed in the p-type ZnO:(Zn, N) film. Further theoretical and experimental investigations indicate that the relatively stable p-type conductivity of ZnO:(Zn, N) film is attributed to the formation of passive complex (Zni–2NO), which can form an impurity band (IBM) above the valence band maximum, resulting in a decrease in the acceptor ionization energy and an improvement in the stability of p-type ZnO:(Zn, N) film. This p-type formation mechanism is consistent with donor–acceptor co-doping method. Nevertheless, the p-type performance of the ZnO:(Zn, N) film would still gradually decline over time. The remaining interstitial nitrogen atoms (Ni) in p-type film is easy trapped by the acceptor NO to form a dual-donor defect (N2)O, which is one of possible important factors for the eventual instability of p-type ZnO:(Zn, N) films.
Keywords
Acceptor Energy LevelNotes
Acknowledgments
The authors gratefully acknowledge support from the National Natural Science Foundation of China (Grant Nos. 51472038 and 51502030), and the Nature Science Foundation of Chongqing City (KJ1500319).
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