Abstract
Specular x-ray reflectivity probes morphological changes in a crosslinkable coumarin photoalignment polymer film resulting from ultraviolet irradiation. An ordered surface layer with density oscillations compatible with planar side-chain alignment is obtained before irradiation. The ordering is enhanced in the early stages of crosslinking. This is attributed to the photoinduced increase of mobility of the side-chains resulting from the creation of free volume by the crosslinking process. The expansion of the thin film confirms that free volume is created. The surface ordering decreases with prolonged ultraviolet irradiation because of increased material viscosity resulting from a high crosslinked density. The implications of surface ordering on liquid crystal photoalignment are discussed.