Hydrodynamic-flow-driven phase evolution in a polymer blend film modified by diblock copolymers

We have studied surface-directed phase separation in thin films of deuterated polystyrene and poly(bromostyrene) (with 22.7% of monomers brominated) using He-3 nuclear reaction analysis, dynamic secondary ion mass spectroscopy and atomic force microscopy combined with preferential dissolution. The crossover from competing to neutral surfaces of the critical blend film (cast onto Au) was commenced: polyisoprene-polystyrene diblock copolymers were added and segregated to both surfaces reducing in a tuneable manner the effective interactions. Two main stages of phase evolution are characterised by i) the growth of two surface layers and by ii) the transition from the four-layer to the final bilayer morphology. For increasing copolymer content the kinetics of the first stage is hardly affected but the amplitude of composition oscillations is reduced indicating more fragmented inner layers. As a result, a faster mass flow to the surfaces and an earlier completion of the second stage were observed. The hydrodynamic flow mechanism, driving both stages, is evidenced by nearly linear growth of the surface layer and by mass flow channels extending from the surface layer into the bulk. The final bilayer structure, formed even for the surfaces covered by strongly overlapped copolymers, is indicative of long-range (antisymmetric) surface forces.