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Vacuum ultraviolet (VUV) transmission spectra show a clear polarizationeffect in pi electronic transition in spin coated atactic polystyrene (aPS)films of thickness below 4Rg, where Rg (~20.4nm) is the radius of gyration ofthe polymer. This transition associated with pendant benzene rings inpolystyrene. The polarization effect clearly indicates pendant benzene ringalignment on a macroscopic scale. Study of core electron (1s) transitionthrough near edge x-ray absorption fine structure (NEXAFS) spectroscopyconfirms the ordering and shows that the rings are oriented towardsout-of-plane direction with a tilt angle ~63 degree with the sample plane,which is consistent with the observed in-plane (sample surface) VUVpolarization. These results indicate the transition of a common polymer, likepolystyrene, inherently disordered in the bulk, to an orientationally orderedphase under a certain degree of confinement.

Confinement Induced Polarization effects in Valence and Inner-shell Spectra of Atactic Polystyrene