Substitutional diatomic molecules NO, NC, CO, N2, and O2: Their vibrational frequencies and effects on p doping of ZnO

First-principles calculations show that AB defects substituting on an O site in ZnO where A, B=N, O, or C are an important class of defects whose physical properties cannot be described by the usual split interstitials but rather by substitutional diatomic molecules. The molecular natures of the (AB)O defects are reflected in their vibrational frequencies which are redshifted from those of the corresponding free molecules but only by about 10%. These calculated results agree with the frequency range recently observed by IR measurement on N-doped ZnO. Moreover, most (AB)O defects are donors in p-type samples. The (NC)O and (N2)O defects have sufficiently low energies to convert substituional NO acceptors into donors, thereby hindering the efforts of doping ZnO p type.