Synthesis and thin-film self-assembly of radical-containing diblock copolymers

Electronically active block polymers based on pi-conjugated macromolecules have been investigated for applications where nanostructured electrodes are of prime import; however, controlling the nanoscale order of these materials has proven challenging. Here, we demonstrate that diblock copolymers that utilize a non-conjugated radical polymer moiety as the electronically active block assemble into ordered thin-film nanostructures. Specifically, the diblock copolymer polydimethylsiloxane-b-poly(2,2,6,6-tetramethylpiperidinyloxy methacrylate) (PDMS-PTMA) was synthesized via atom transfer radical polymerization to generate polymers with readily controlled molecular properties. Importantly, solvent annealing of the PDMS-PTMA thin films led to well-defined nanostructures with domain spacings of the order of similar to 30-40 nm.