Pulsed laser deposition vs. matrix assisted pulsed laser evaporation for growth of biodegradable polymer thin films

Thin films of poly (lactide-co-glycolide) (PLGA), a biodegradable polymer, were deposited on Si wafers by both conventional pulsed laser deposition (PLD) and matrix assisted pulsed laser evaporation ( MAPLE) using chloroform (CHCl3) as a matrix solvent. This research represents an initial study to investigate the deposition characteristics of each technique at comparable conditions to gain insight into the transport and degradation mechanisms of each approach. The deposited materials were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), proton nuclear magnetic resonance (H-1 NMR), and gel permeation chromatography (GPC) with refractive index (RI) detection. While FTIR and NMR results do not show a measurable departure from the native, in sharp contrast GPC results show a significant change (up to 95%) in molecular weight for both deposition methods. This result makes it clear that it is possible to overlook substantial degradation when incomplete chemical analysis is conducted. Optical transmission measurements of the starting MAPLE targets yielded laser penetration depths on the order of 0.362 cm and 0.209 cm for pure CHCl3 and 1 wt.% PLGA in CHCl3, respectively. Straightforward application of the Beer-Lambert law for laser energy deposition predicts a negligible temperature rise of less than 1 K at the target surface, which is in clear contradiction with ablation rates of 1.85 mu m/pulse experimentally measured for polymer loaded samples. With an ablation process of this magnitude, the material ejection is likely due to contributions of nonlinear or non-homogeneous laser light absorption rather than evaporation. Severe non-uniformity of the final surface morphologies of the MAPLE films, similar to solvent wicking artifacts found in spin casting supports the spallation scenario in MAPLE.