ZnO has been a subject of intense research in the optoelectronics community owing to its wide bandgap (3.3eV) and large exciton binding energy (60meV). However, difficulty in doping it p-type posts a hindrance in fabricating ZnO-based devices. In order to make p-type ZnO films, phosphorus implantation, using plasma immersion ion-implantation technique (2kV, 900W, 10μs pulse width) for 30 seconds, was performed on ZnO thin film deposited by RF Magnetron Sputtering (Sample A). The implanted samples were subsequently rapid thermal annealed at 700°C and 1000°C (Samples B and C) in oxygen environment for 30 seconds. Low temperature (8K) photoluminescence spectra reveal dominant donor-bound exciton (D°X) peak at 3.36eV for samples A and B. However, for Sample B the peaks around 3.31eV and 3.22eV corresponding to the free electron-acceptor (FA) and donor to acceptor pair peaks (DAP) are also observed. A dominant peak around 3.35eV, corresponding to acceptor bound exciton (A°X) peak, is detected for Sample C along with the presence of FA and DAP peaks around 3.31eV and 3.22eV. Moreover, the deep level peak around 2.5eV is higher for Sample B which may be due to implantation and acceptor related defects. However, for Sample C, the deep level peaks are very weak compared to the near band edge peaks confirming that these peaks are mainly due to intrinsic defects and not related to acceptors. These results clearly show us a promising way to achieve p-type ZnO films using phosphorus doping. © 2013 SPIE.