Combining polymer synthesis with self-assembly of block copolymers

Polymer self-assembly is one of the most promising nanopatterning techniques due to its advantages of low cost and high versatility. The key challenge of conventional strategy is its very limited ability to control over chemistry during or after self-assembly in order to alter the nanostructures from its thermodynamic equilibrium state. In this talk, we will demonstrate our recent development of in-film photopolymerization technique for synthesizing polymers within an self-assembled film. The vapor phase monomer is first introduced to swell a photoinitiator-containing block copolymer film, which can be subsequently converted to polymers upon UV irradiation. The synthesized homopolymers blend with BCP films, which alter the thin film nanostructures by changing the underlying polymer composition. As these altered nanostructures are locally near equilibrium, common annealing techniques such as shear aligning can be combined to improve the degree of ordering. With successful integrating polymer chemistry with assembly physics, the in-film polymerization method provides an exciting platform for on-demand manipulation of polymer functionality as well as opening up a new area for radical polymerizations within such geometrically confined, swollen films.