Journal of Physical Chemistry B, Vol.105, No.13, 2518-2524, 2001
Laser-induced nanometer-nanosecond expansion and contraction dynamics of poly(methyl methacrylate) film studied by time-resolved interferometry
The expansion and contraction behavior of a neat poly(methyl methacrylate) film is induced by 248 nm excimer laser exitation and directly measured by nanosecond interferometry. Above the ablation threshold (1400 mJ/cm(2)), the film expands during the excitation laser pulse, and after 25% expansion of the thickness, it undergoes fragmentation. Below the threshold, the expansion rate is still high (a few nm/ns), and permanent swelling is observed after transient expansion and succeeding contraction. By decreasing the laser fluence below 800 mJ/cm(2), permanent swelling was not observed, and at a few tens of mJ/cm(2), novel oscillatory expansion and contraction behavior was successfully detected. The expansion amplitude as a function of laser fluence indicates that the polymer film undergoes phase transition from glass to rubber upon excitation with a fluence higher than 450 mJ/cm(2). In the glass state, the interpenetrating structure of the polymer film and associated free volume distribution may be changed upon irradiation and photochemical degradation should be involved. A dynamic view of these polymer properties explains well the unique expansion and contraction behavior. Furthermore, these laser-induced morphological changes are compared with those of polymer films doped with aromatic molecules and considered in general.