We investigated laser-induced deposition processes on BK7 substrates under the influence of pulsed Q-switched Nd:YAG laser radiation, starting from small toluene partial pressures in a background vacuum environment. The composition and structure of the deposit was analyzed using microscopic methods like Nomarski DIC, dark-field and white-light interference microscopy, TEM, EDX and XPS. We found a distinct threshold for deposition built-up dependant on the partial pressure of toluene (0.2 J/cm2 at 0.1 mbar, 0.8 J/cm2 at 0.01 mbar toluene). The deposits strictly followed the spherical geometry of the laser spot. No deposit accumulated on MgF2 AR coated BK7 samples even at high toluene partial pressures. The onset of deposit was accompanied by periodic surface ripples formation. EDX and XPS analysis showed a carbon-like layer which strongly absorbed the 1 μm laser radiation. The typical number of shots applied was 50 000. In addition, long term lifetime tests of more than 5 Mio. shots per site were run.© (2005) COPYRIGHT SPIE--The International Society for Optical Engineering. Downloading of the abstract is permitted for personal use only.