Phase behavior of symmetric diblock copolymers under 3D soft confinement

Abstract

The phase behavior of symmetric diblock copolymers under three-dimensional (3D) soft confinement is investigated using self-consistent field theory. Soft confinement is realized in binary blends composed of AB diblock copolymers and C homopolymers, where the copolymers self-assemble to form a droplet embedded in a homopolymer matrix. The phase behavior of the confined block copolymers is regulated by the degree of confinement and the selectivity of the homopolymers, resulting in a rich variety of novel structures. When the C homopolymers are neutral to the A- and B-blocks, stacked lamellae (SL) are formed where the number of layers increases with the droplet volume, resulting in a morphological transition sequence from Janus particles to square SL. When the C homopolymers are strongly selective for the B-blocks, a series of non-lamellar morphologies, including onion-, hamburger-, cross-, ring-, and cookie-like structures, are observed. A detailed free energy analysis reveals a first-order reversible transformation between SL and onion-like (OL) structures when the selectivity of the homopolymers is changed. Our results provide a comprehensive understanding of how various factors, such as the copolymer concentration, homopolymer chain length, degree of confinement, and homopolymer selectivity, affect the self-assembled structures of diblock copolymers under soft 3D confinement.