Swelling and modification of silicone surface by F2 laser irradiation

The surface of silicone rubber swelled and was modified by 157-nm F₂ laser irradiation at a laser fluence less than the ablation threshold. The irradiated surface swelled to a height of approximately 3 m. Fourier-transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy showed that the irradiated surface was modified to SiO₂. 193-nm ArF laser irradiation of the silicone rubber induced the surface to swell, but not to modify to SiO₂. The IR peaks of end groups of silicone were observed in the FT-IR spectra of the surface. From these results, it is concluded that the main chains (Si-O) of silicone were photodissociated and generation of low molecular weight silicones caused the swelling. In addition, it was observed that methane and carbon dioxide were released from silicone rubber when each laser beam irradiated it. These gases were generated by photodissociation of the side chains (Si-CH₃) of silicone. An F₂ laser beam can photodissociate the Si-CH₃ bonds and the Si-O bonds of silicone and O₂ effectively even at a laser fluence less than the ablation threshold, resulting in the modification to SiO₂ and the swelling. PACS 61.80.Ba; 61.82.Pv; 82.50.Hp