We performed a comparative study of the plasma generated from AlN targets under sub-ps vs ns UV (λ=248 nm) excimer laser pulses. Optical emission and time-of-flight spectra recorded in cases of samples irradiated with ns laser pulses showed the presence of Al lines, which became prevalent after the first laser pulse was incident on the target. These observations are congruent with the metallization of AlN targets inside each crater under multipulse ns laser action at laser fluences above the ablation threshold, observed by visual inspection and optical microscopy. Metallization was not observed when working with sub-ps laser pulses. Moreover, our studies confirmed the predominant presence of AlN positive molecular ions in the plasma generated in front of AlN targets submitted to sub-ps multipulse laser irradiation. The optical emission data are in good agreement with time-of-flight mass analysis. We emphasize that all investigations support the experimental evidence reported by György etal [E. György etal, J. Appl. Phys. 90, 456 (2001)], according to which thin films obtained by pulsed laser deposition with ns laser pulses contain a significant amount of metallic Al, while only AlN is detected in films obtained with sub-ps laser pulses. Measurements of the velocity and kinetic energy distributions of AlN+ indicate that in the case of ns-laser ablation the ions are emitted with thermal energy, while in the case of sub-ps-laser ablation a bimodal distribution exists and has thermal (1 eV) and hyperthermal (10 eV) energy components. This points to different plasma formation mechanisms for the two cases. © 2003 American Institute of Physics.