Transition between tetragonal and hexagonal pattern in binary blends of ABC block copolymers with different chain length

Abstract The thin film morphology of binary blends of triblock copolymers (poly(isoprene - block - styrene - block - (2-vinylpyridine)) ISP after solvent vapor annealing (SVA) was investigated using AFM, GISAXS and TEM. Although bulk samples of binary ISP blends exhibit tetragonal pattern, thin films led either to tetragonal pattern or hexagonal pattern, depending on the annealing time. These transitions were attributed to the formation of non-synchronized wetting layers of I and P, leading to a variation of the inner composition in I and P during SVA. Surprisingly, the hexagonal morphology exhibited centered hexagons of I and surrounding hexagons of P, which is not predicted nor observed for neat block copolymer samples. Although the system must adopt the lowest P/S interface, our results suggest that the effect of chain length with marked difference in the studied blends is playing a major role. Particularly, the presence of long chains of I favors the formation of I domains with bigger size, in order to keep their conformation entropy loss as small as possible.