Surface‐Initiated Living Self‐Assembly of Polythiophene‐Based Conjugated Block Copolymer into Erect Micellar Brushes

Abstract Nanostructured conjugated polymers are of widespread interest due to their broad applications in organic optoelectronic devices, biomedical sensors and other fields. However, the alignment of conjugated nanostructures perpendicular to a surface remains a critical challenge. Herein, we report a facile method to directly self‐assemble a poly(3‐(2‐ethylhexyl)thiophene), P3EHT‐based block copolymer into densely aligned micellar brushes through surface‐initiated living crystallization‐driven self‐assembly. The presence of an ethyl pendant on the side group intrinsically moderates the crystallization rate of the polythiophene main chains, and hence favors the controlled living growth of long conjugated fibers and the subsequent fabrication of conjugated micellar brushes. The corona of the micellar brush can be further decorated with platinum nanoparticles, which enables the formation of erect nanoarrays with heights up to 2700 nm in the dried state. This also renders the micellar brush catalytically active toward hydrogen evolution reaction, which shows a low overpotential of 27 mV at 10 mA cm −2 . Notably, the P3EHT‐based micellar brush can simultaneously grow with polyferrocenyldimethylsilane, PFS‐based micellar brush on the same surface without any significant interference between the two systems. Thus, these two micellar brushes can be patterned through site‐selective immobilization of two types of seeds followed by independent living self‐assembly.