Gradient in refractive index reveals denser near free surface region in thin polymer films

A gradient in refractive index that is linear in magnitude with depth into the film is used to fit ellipsometric data for thin polymer films of poly(methyl methacrylate) (PMMA), polystyrene (PS), and poly(2-vinyl pyridine) (P2VP). We find that the linear gradient model fits provide more physically realistic refractive index values for thin films compared with the commonly used homogeneous Cauchy layer model, addressing recent reports of physically unrealistic density increases. Counter to common expectations of a simple free volume correlation between density and dynamics, we find that the direction of refractive index (density) gradient indicates a higher density near the free surface, which we rationalize based on the observed faster free surface dynamics needed to create vapor deposited stable glasses with optimized denser molecular packings. The magnitude of refractive index gradient is observed to be three times larger for PMMA than for PS films, while P2VP films exhibit a more muted response possibly reflective of a decoupling in free surface and substrate dynamics in systems with strong interfacial interactions.