High Surface Area Poly(3-hexylthiophenes) Thin Films from Cleavable Graft Copolymers

A strategy for the fabrication of high surface area poly(3-hexylthiophene) thin films by removal of nanoscale domains formed from graft copolymers is presented. This approach relies on the synthesis and characterization of cleavable graft copolymers based on regioregular poly(3-hexylthiophene) (rr-P3HT) main chain and sacrificial poly(styrene) side chains. An alkoxyamine initiator based on 2,2,6,6tetramethylpiperidine-N-oxyl (TEMPO) was incorporated at the 3-position of the functionalized thienyl repeat unit, 2, via a cleavable trityl ether linker. Grignard metathesis (GRIM) copolymerization of 2 and 2,5-dibromo-3-hexylthiophene afforded regioregular P3HT with randomly incorporated alkoxyamine groups. Polymerization of styrene from the P3HT backbone for different time periods afforded graft copolymers with controllable sacrificial chain lengths. These materials were characterized using an array of techniques such as H and C NMR spectroscopy and size exclusion chromatography (SEC). An approach to obtain nanoporous P3HT thin films by cleavage of the trityl ether linker followed by complete removal of poly(styrene) is reported with the as-cast graft copolymer thin films displaying an irregular microphase-separated structure with an average domain size ∼30 nm as determined by grazing incidence small-angle X-ray scattering (GISAXS) measurements. Significantly, this length scale was conserved after removal of the sacrificial component which allows this strategy to have potential application in diverse fields such as organic photovoltaics.