Stable p-type doping of ZnO has been a major technical barrier for the application of ZnO in optoelectronic devices. While p-type conductivity for nitrogen-doped ZnO has been repeatedly reported, its origin remains mysterious. Here, using first-principles calculation, we predict that an ammonia molecule could counterintuitively assume a Zn site and form a substitutional defect, (NH3)(Zn). By comparing with other molecular dopants (N-2 and NO) on the Zn site and N on the O site (NO), we found that (NH3)(Zn) is thermodynamically the most stable defect under O-rich conditions. The stability is attributed to the formation of a strong dative bond of the ammonia molecule with a neighbouring O atom. The (NH3)(Zn) defect is neutral regardless of the Fermi level of the system, but it can capture a H donor forming (NH4)(Zn), which becomes an acceptor. Experimental evidence for the existence of this Zn-site N acceptor is provided based on a comparison of calculated and measured N 1s X-ray photoelectron spectra. Accurately calculating the (0/-) transition level for this and other N-based acceptors has been hindered by the theoretical method used. Experimental studies are called for to clarify its (0/-) transition level.
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