Laser induced chemical and physical modifications of polymer films: dependence on the irradiation wavelength

Polymers with photolabile groups absorbing in the mid UV (around 300 nm) were irradiated with excimer-lasers (248 and 308 nm). Irradiation with 248 nm (KrF laser) corresponds to an excitation of the photostable phenyl system whereas the XeCl laser (308 nm) excites the labile triazeno groups (–NN–N). Thin polymer films (0.1–3 μm) were coated onto quartz or glass and irradiated below and above the threshold of ablation. The films were subsequently analyzed with various surface analysis techniques. Below the threshold of ablation the main feature at both irradiation wavelengths was the reduction of the absorption maximum at about 330 nm and an increase of the surface oxygen content (X-ray photoelectron spectroscopy) and therefore the surface polarity (contact angle). The surface remained smooth with no detectable micro-structures (scanning electron microscopy). Above the ablation threshold the absorbance at 330 nm decreased dramatically and the color of the film changed. For 248 nm irradiation the surface was darkened and a carbonization (XPS) with microstructures (SEM) was detected. The surface became non-polar in agreement with surface carbonization. In the case of 308 nm irradiation the surface remained smooth and no change of the chemical composition or surface polarity was detected, suggesting a photochemically induced layer by layer ablation process.