Direct Visualization of Order-Order Transitions in Silicon-Containing Block Copolymers by Electron Tomography

Here, we aim to comprehend the mechanism of the order-order transition (OOT) from nonequilibrium, metastable phase to equilibrium phase. Polystyrene-block-polydimethylsiloxane (PS-PDMS) block copolymer (BCP) bulks with metastable cylinder (C) and double gyroid (G) phases can be obtained from lamellae (L) forming PS-PDMS by simply tuning the selectivity of casting solvent. The recovery of the intrinsic L phase can be achieved by thermal annealing through OOT. Time-resolved small-angle X-ray scattering (SAXS) experiments are carried out to reveal the variation of the structural evolution in reciprocal space during annealing. The structural evolution in real space is directly visualized by using electron tomography (i.e., 3D transmission electron microscopy (TEM)). As a result, combining the time-resolved scattering experiments and the morphological observations from electron tomography offers new insights into the phase behaviors of the OOT of BCPs.