Leveraging tunability of copolymer gradients during polymer synthesis to advance understanding of polymer self-assembly in confined geometries

Self-assembly of polymer materials provides a cost-effective route to preparation of materials with well-defined nanostructures (1-100 nm). Due to their ability to self-assemble, block copolymers are a particularly useful and important class of materials utilized in a wide range of applications including photonic crystals, ion conducting membranes, microfluidics, drug delivery, sensors, and nanoporous membranes, and templates for the organization of nanodots and nanowires. However, relationships between block copolymer chemistry, architecture, and thermodynamics are critical for understanding self-assembly behavior towards designing materials with target properties. This research investigated the impact of incorporation of a gradient copolymer within the block copolymer architecture for enabling additional control over self-assembly behavior in polymer thin films and how these polymer thin films can be leveraged to fabricate porous thin polymer films. Block and and block-gradient copolymers were synthesized with controlled molecular size and gradient structure and their thin film structures evaluated using atomic force microscopy towards understanding relationships between the macromolecular structure and formed morphologies in thin films.