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 ZnObased devices. In an attempt to make it p-type we have studied Li-implanted (Energy=40keV, dose=5x1013cm-2) <002> ZnO films grown over <001> sapphire substrates by Pulsed Laser Deposition technique at 400°C (sample A). The samples were subsequently subjected to Rapid Thermal Annealing at 650° and 750°C (samples B and C) for 30 seconds. Room temperature Photoluminescence study of as-deposited sample reveal consistent Donor-bound exciton (D0X) peak at 3.3eV, which shifts to 3.298eV, 3.298eV, and 3.289eV for samples A, B and C respectively. This data validates the n-type conductivity of the samples with a carrier concentration and Hall mobility of 8.68x1019cm-3, 1.13x10 19cm-3 and 2.9x1020cm-3 and 2.14cm2/V-sec, 35.2cm2/V-sec, 16.9cm2/V-sec for samples A, B and C respectively. The reduced energy of D0X peak is probably due to strain variations occurred during the various processing steps. While the higher carrier concentration in sample C can be attributed to aggregated vacancy clusters at high temperature annealing. Since Li acts as an acceptor for ZnO, so a free electron-acceptor (FA) peak at 3.227eV, 3.217eV and 3.225eV in samples A, B and C is evident. A third peak at 3.128eV may be due to the donor-acceptor pair, a reason for a lower energy FA peak for sample B. © 2011 Copyright Society of Photo-Optical Instrumentation Engineers (SPIE).