ZnO is a wide band gap, naturally n-type semiconductor with great promise for optoelectronic applications; the main obstacle yet to be overcome is p-type doping. Nitrogen, the most promising candidate currently being pursued as a dopant, has been predicted to preferentially incorporate into the ZnO lattice in the form of a N-2 molecule at an O site when a plasma source is used, leading to compensation rather than p-type doping. We demonstrate this to be incorrect by using N K-edge x-ray absorption spectra and comparing them with first-principles calculations showing that nitrogen, in fact, incorporates substitutionally at O sites where it is expected to act as an acceptor. We also detect the formation of molecular nitrogen upon annealing. These results suggest that effective p-type doping of ZnO with N may be possible only for low-temperature growth processes.
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