Dependence of ultraviolet nanosecond laser polymer ablation on polymer molecular weight: Poly(methyl methacrylate) at 248nm

Abstract

We rely on a methodology demonstrated previously for assessing the temperature evolution and polymer viscosity changes in the 248nm irradiation of poly(methyl methacrylate)s (PMMAs) with molecular weights (Mw) ranging from 2.5to996kDa. Briefly, this methodology [G. Bounos et al., J. Appl. Phys. 98, 084317 (2005)] relies on monitoring the formation of aryl products in the irradiation of polymer doped with iodonaphthalene or iodophenanthrene. The results demonstrate that higher temperatures are attained with increasing Mw. The surface temperatures at the corresponding ablation thresholds are estimated to be ∼850–900K for Mw⩾120kDa vs ∼600K for 2.5kDa PMMA. In addition, for all Mw’s, melting is demonstrated (viscosity values of ≈101Pas), but it lasts longer for high Mw PMMAs. We ascribe these differences to the fact that low Mw PMMAs dissociate efficiently to desorbing monomers/oligomers, thereby resulting in more efficient energy removal. Even so, the ablation threshold of the high Mw PMMAs is attained at higher fluences. This can be ascribed to the higher fraction of bonds that is required to be broken, and also plausibly to the higher gaseous product pressures that must be attained, for material ejection to be effected. The results are overall well accounted by the bulk photothermal model.