Air–Liquid Interfacial Self-Assembly of Conjugated Block Copolymers into Ordered Nanowire Arrays

The ability to control the molecular packing and nanoscale morphology of conjugated polymers is important for many of their applications. Here, we report the fabrication of well-ordered nanoarrays of conjugated polymers, based on the self-assembly of conjugated block copolymers at the air-liquid interface. We demonstrate that the self-assembly of poly(3-hexylthiophene)-block-poly(ethylene glycol) (P3HT-b-PEG) at the air-water interface leads to large-area free-standing films of well-aligned P3HT nanowires. Block copolymers with high P3HT contents (82-91%) formed well-ordered nanoarrays at the interface. The fluidic nature of the interface, block copolymer architecture, and rigid nature of P3HT were necessary for the formation of well-ordered nanostructures. The free-standing films formed at the interface can be readily transferred to arbitrary solid substrates. The P3HT-b-PEG films are integrated in field-effect transistors and show orders of magnitude higher charge carrier mobility than spin-cast films, demonstrating that the air-liquid interfacial self-assembly is an effective thin film fabrication tool for conjugated block copolymers.