IR laser ablation of doped poly(methyl methacrylate)

We investigate the TEA CO2 laser ablation of films of poly(methyl methacrylate), PMMA, with average MW 2.5, 120 and 996 kDa doped with photosensitive compounds iodo-naphthalene (NapI) and iodo-phenanthrene (PhenI) by examining the induced morphological and physicochemical modifications. The films casted on CaF2 substrates were irradiated with a pulsed CO2 laser (10P(20) line at 10.59 μm) in resonance with vibrational modes of PMMA and of the dopants at fluences up to 6 J/cm2. Laser induced fluorescence probing of photoproducts in a pump and probe configuration is carried out at 266 nm. Formation of naphthalene (NapH) and phenanthrene (PhenH) is observed in NapI and PhenI doped PMMA, respectively, with relatively higher yields in high MW polymer, in similarity with results obtained previously upon irradiation in the UV at 248 nm. Above threshold, formation of photoproducts is nearly complete after 200 ms. As established via optical microscopy, bubbles are formed in the irradiated areas with sizes that depend on polymer MW and filaments are observed to be ejected out of the irradiated volume in the samples made with high MW polymer. The implications of these results for the mechanisms of polymer IR laser ablation are discussed and compared with UV range studies.