Surface engineering using Kumada catalyst-transfer polycondensation (KCTP): preparation and structuring of poly(3-hexylthiophene)-based graft copolymer brushes.

Poly(4-vinylpyridine)-block-poly(4-iodo-styrene), P4VP-b-PS(I), block copolymers obtained by iodination of readily available P4VP-b-PS block copolymers strongly adhere to variety of polar substrates including Si wafers, glasses, or metal oxide surfaces by a polar P4VP block, forming polymer brushes of moderately stretched PS(I) chains. Kumada catalyst-transfer polycondensation (KCTP) from the P4VP-b-PS(I) brushes results into planar brushes of the graft copolymer in which relatively short ( approximately 10 nm) poly(3-hexylthiophene), P3HT, grafts emanate from the surface-tethered PS(I) chains. Grafting of the P3HT leads to significant stretching of the PS(I) backbone as a result of increased excluded volume interactions. Specific adsorption of the P4VP block to polar surfaces was utilized in this work to pattern the P4VP(25)-b-PS(I)(350) brush. The microscopically structured P4VP(25)-b-PS(I)(350) brush was converted into the respectively patterned P4VP-PS(I)-g-P3HT one using KCTP. We also demonstrated that KCTP from functional block copolymers is an attractive option for nanostructuring with polymer brushes. P4VP(75)-b-PS(I)(313) micelles obtained in selective solvent for the PS(I) block form a quasi-ordered hexagonal array on Si wafer. The P4VP(75)-b-PS(I)(313) monolayer preserves the characteristic quasi-regular arrangement of the micelles even after extensive rinsing with various solvents. Although the grafting of P3HT from the nanopatterned P4VP(75)-b-PS(I)(313) brush destroys the initial order, the particulate morphology in the resulting film is preserved. We believe that the developed method to structured brushes of conductive polymers can be further exploited in novel stimuli-responsive materials, optoectronic devices, and sensors.