The modification of polydimethylsiloxane (PDMS) by narrow band 254 nm excimer radiation under a nitrogen atmosphere was characterized by contact angle goniometry, attenuated total reflectance infrared spectroscopy, atomic force and scanning electron microscopy. UV irradiation results in the formation of the carboxylic acids that influences the wettability of the surface. Continued exposure results in the formation of an inorganic surface (SiOx(1 < x < 2)) which hinders the ability to continually increase the wettability. The continuity of this inorganic layer is disrupted by the formation of surface cracks. These results have implications in the fabrication and chemical modi. cation of microfluidic or micro-electro-mechanical systems. (c) 2008 Elsevier B.V. All rights reserved.