Highly Tunable Self-Assembled Nanostructures from a Poly(2-vinylpyridine-b-dimethylsiloxane) Block Copolymer

An extraordinarily large degree of tunability in geometry and dimension is demonstrated in films of a self-assembled block copolymer. A poly(2-vinylpyridine-b-dimethylsiloxane) block copolymer with highly incompatible blocks was spun-cast on patterned substrates and treated with various solvent vapors. The degree of selective swelling in the poly(2-vinylpyridine) matrix block could be controlled over an extensive range, leading to the formation of various microdomain morphologies such as spheres, cylinders, hexagonally perforated lamellae, and lamellae from the same block copolymer. The systematic control of swelling ratio and the choice of solvent vapors offer the unusual ability to control the width of very well-ordered linear features within a range between 6 and 31 nm. This methodology is particularly useful for nanolithography based on directed self-assembly in that a single block copolymer film can form microdomains with a broad range of geometries and sizes without the need to change molecular weight or volume fraction.