Self-Assembled Phases of Block Copolymer Blend Thin Films

The patterns formed by self-assembled thin films of blended cylindrical and lamellar polystyrene-b-poly(methyl methacrylate) block copolymers can be either a spatially uniform, single type of nanostructure or separate, coexisting regions of cylinders and lamellae, depending on fractional composition and molecular weight ratio of the blend constituents. In blends of block copolymers with different molecular weights, the morphology of the smaller molecular weight component more strongly dictates the resulting pattern. Although molecular scale chain mixing distorts microdomain characteristic length scales from those of the pure components, even coexisting morphologies exhibit the same domain spacing. We quantitatively account for the phase behavior of thin-film blends of cylinders and lamellae using a physical, thermodynamic model balancing the energy of chain distortions with the entropy of mixing.