Structural Transitions in Asymmetric Poly(styrene)-block-Poly(lactide) Thin Films Induced by Solvent Vapor Exposure

Successive structural transitions in thin films of asymmetric poly(styrene)-block-poly(lactide) (PS–PLA) block copolymer samples upon exposure to tetrahydrofuran (THF) vapors have been monitored using atomic force microscopy (AFM) and both in situ and ex situ grazing incidence small-angle X-ray scattering (GISAXS). A direct link was established between the structure in the swollen state and the morphology formed in the dried state post solvent evaporation. This was related to the high incompatibility between the constituting blocks of the copolymer that thwarted the system from reaching the homogeneous disordered state in the swollen state under the specific conditions utilized in this study. Upon rapid solvent removal, the morphologies formed in the swollen state were trapped due the fast evaporation kinetics. This work provides a better understanding of the mechanisms associated with block copolymer thin film morphology changes induced by solvent vapor annealing.