New mechanistic details regarding aluminum deposition by ArF excimer laser photodecomposition of trimethylaluminum (TMA) adsorbed on aluminum covered SiO 2/Si substrates have been obtained using a time-of-flight quadrupole mass spectrometer. CH3 radicals and Al-(CH3)n (n = 1,2,3) species are efficiently photoejected from the surface with up to 0.22 eV of translational energy. Experiments at various TMA dosing levels reveal differences in desorbed fragment translational energy presumably associated with variations in surface site binding energy. No direct evidence is found for desorption of A1 from the surface indicating that A1 is more tightly bound than methyl-aluminum fragments. By carefully monitoring changes in fragment translational energy as an A1 deposit forms on the clean SiO2/Si substrate, we examine how the surface influences the onset of A1 growth. No evidence of ethane or methane desorption from the sample surface is found implying that radical recombination and hydrogen abstraction are primarily secondary gas phase reactions which are not surface initiated.