In situ GISAXS study of a Si-containing block copolymer under solvent vapor annealing: Effects of molecular weight and solvent vapor composition

Citation

Bai, W.; Yager, K.G.; Ross, C.A. "In situ GISAXS study of a Si-containing block copolymer under solvent vapor annealing: Effects of molecular weight and solvent vapor composition" Polymer 2016, 101 176–183.
doi: 10.1016/j.polymer.2016.08.055

Summary

We study the assembly of block-copolymers during exposure to solvent vapor, using in-situ GISAXS measurements.

Abstract

The room-temperature solvent vapor annealing of polystyrene-b-polydimethylsiloxane (PS-b-PDMS) block copolymer films was studied in situ by grazing incidence small-angle X-ray scattering. Films of cylinder-forming PS-b-PDMS with molecular weight 16 kg/mol and 12.2 kg/mol, annealed under vapors of toluene:heptane with varying composition, exhibited swelling-ratio-dependent evolution of microdomain spacing and orientation. In a vapor made from a toluene:heptane 5:1 volumetric ratio liquid mixture, or from pure toluene, cylindrical microdomains reoriented from majority out-of-plane to in-plane during annealing, while drying led to shrinkage along the film normal and a large distortion of the hexagonal lattice of in-plane cylinders. Annealing under vapor from a toluene:heptane 1:5 volumetric ratio liquid produced a non-bulk lamellar structure in the 16 kg/mol PS-b-PDMS.