ZnO (002) films of thickness 0.5 μm were grown on c-plane sapphire substrates by Pulsed Laser Deposition technique at 400°C in oxygen ambient of 75 mTorr and implanted with 8x1014 cm-2 dose of phosphorus ions of energy 50 keV (Sample A) followed by Rapid Thermal Annealing in Ar (Sample B) and oxygen atmospheres (Sample C) at 750°C (30 seconds). AFM images depicted root-mean-square roughness for Sample A (10.072 nm), B (9.314 nm) and C (4.9 nm). Room-temperature Hall study revealed n-type conductivity with carrier concentrations of 9.69x1019cm-3, 1.36x1020 cm-3, 4x1018 cm-3 and Hall mobility of 0.727 cm2/V-s, 12.44 cm2/V-s, 54.3 cm2/V-s for Sample A, B and C respectively. Possible reasons might be the formation of vacancy clusters by implantation for Sample A, production of oxygen vacancies with agglomeration of vacancy clusters and without further aggregation of vacancy clusters with higher annealing temperature for Sample B and C respectively. Dominance of donor-bound exciton peaks were found to be at 3.295 eV, 3.284 eV, 3.281 eV and 3.272 eV for unimplanted sample, Sample A, B and C respectively from roomtemperature photoluminescence study. © 2011 Copyright Society of Photo-Optical Instrumentation Engineers (SPIE).