Comparing refractive index and density changes with decreasing film thickness in thin supported films across different polymers

Density changes in thin polymer films have long been considered as a possible explanation for shifts in the thickness-dependent glass transition temperature Tg(h) in such nanoconfined systems, given that the glass transition is fundamentally associated with packing frustration during material densification on cooling. We use ellipsometry to compare the temperature-dependent refractive index with decreasing thickness n(h) for supported films of poly(2-vinyl pyridine) (P2VP), poly(methyl methacrylate) (PMMA), and polystyrene (PS), as these polymers have different silica substrate interactions. We observe similar n(h) trends for all three polymers, with near equivalence of P2VP and PS, characterized by a large apparent increase in refractive index for h ≤ 40 nm–65 nm depending on the polymer. Possible sources of molecular dipole orientation within the film are tested by varying molecular weight, polydispersity, chain conformation, and substrate chemistry. Such film inhomogeneities associated with non-uniform polarizability would invalidate the use of homogeneous layer approximations inherent in most thin film analysis methods, which we believe likely explains recent reports of large unphysical increases in film density with decreasing thickness by a variety of different experimental techniques.