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

TL;DR

This study uses first-principles calculations to analyze how phosphorus and nitrogen co-doping influence p-type conductivity in ZnO, revealing defect behaviors and conditions that enhance hole conduction.

Contribution

It identifies specific defect complexes and conditions that can improve p-type doping efficiency in ZnO through co-doping strategies.

Findings

P substitutive defects form deep acceptor or donor levels.

Zn vacancies and PZn-2VZn are shallow acceptors but easily compensated.

PZn-4NO complexes can lower formation energy and improve p-type conductivity.

Abstract

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