Time‐ and space‐resolved emission and laser‐induced fluorescence spectroscopic measurements were performed to investigate vaporization and plasma formation resulting from excimer laser irradiation of titanium targets in a low‐pressure nitrogen atmosphere. Measurement series have been done by varying the laser intensity from the vaporization threshold at 25 MW cm−2up to values of about 500 MW cm−2typically applied in pulsed laser deposition processing of titanium nitride films. Thus, the transition from thermal evaporation to the high‐density plasma formation process, leading to the production of reactive species and high‐energy ions, was evidenced. An interesting result for the comprehension of the reactive deposition process was the observation of a quantity of dissociated and ionized nitrogen, which is transported with the plasma front in the direction of the substrate. ©1995 American Institute of Physics.