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P mono-doped and (P, N) co-doped ZnO are investigated by the first-principlescalculations. It is found that substitutive P defect forms a deep acceptorlevel at O site (PO) and it behaves as a donor at Zn site (PZn), whileinterstitial P (Pi) is amphoteric. Under equilibrium conditions, these defectscontribute little to the p-type conductivity of ZnO samples since the formationenergy of PZn is much lower than that of Pi or PO when EF is below mid-gap (aprerequisite p-type condition). Zinc vacancies (VZn) and PZn-2VZn complex aredemonstrated to be shallow acceptors with ionization energies around 100 meV,but they are easily compensated by PZn defect. Fortunately, PZn-4NO complexesmay have lower formation energy than that of PZn under Zn rich condition byproper choices of P and N sources. In addition, the neutral PZn-3NO passivedefects may form an impurity band right above the valence band maximum of ZnOas in earlier reported (Ga,N) or (Zr,N) doped ZnO. This significantly reducesthe acceptor level of PZn-4NO complexes, and helps improving the p-typeconductivity in ZnO.

The origin of p-type conduction in (P, N) co-doped ZnO