Spatial and temporal dependence of diffusion in polystyrene thin films on silicon and carbon surfaces

The strong inhibition of chain diffusion in thin polystyrene (PS) films has been observed near an attractive silicon surface, and diffusion remains inhibited out to distances of several radii of gyration from the surface. The present study seeks to determine the time dependence of the diffusion coefficient, and to examine the effect of a carbon surface on this diffusion. The sputter-deposited carbon surface may serve as a model for carbon-black particles employed in nanocomposites, which have recently been observed to reduce diffusion throughout a nanocomposite layer. The experiments employed a thin (approximately 15 nm) deuterated polystyrene (dPS) marker layer sandwiched between two normal PS layers. Deuterium profiles were monitored in the annealed samples by secondary ion mass spectrometry. Strong segregation was observed at the silicon surface, but was inhibited at the carbon surface, allowing the diffusion behaviour to be studied in the latter case over longer annealing times. A finite-element computer program was developed to fit the observed diffusion profiles. The variation of the diffusion coefficient with depth is shown to be consistent with previous results, and diffusion is comparable at both the carbon and silicon surfaces. The diffusion coefficient decreases roughly in proportion to t^-1/2, and is discussed in the context of reptation theory.