Liquid crystalline moiety-assisted perpendicular orientation of cylindrical domains within P4VP-b-PMA(Az) films with high aspect ratio

Block copolymer (BCP) films with perpendicularly aligned cylindrical domains of high aspect ratio have important applications in diverse fields. However, an aspect ratio of the cylinders as high as 200 has rarely been reported so far. Here we demonstrate an efficient route to the formation of normally aligned P4VP cylinders with high aspect ratio surrounded by a matrix of azobenzene-containing block (PMA(Az)) via hierarchical self-assembly. A crisscross structure, consisting of parallelly aligned liquid crystalline (LC) layers and normally aligned self-assembly domains, is expected to assist the formation of well-defined nanostructures. The LC layers in the cylindrical films self-assemble to form smectic phase after solvent annealing, as confirmed by WAXD and UV-vis spectra. We found that the aspect ratio of the vertical P4VP cylinders is up to 200 and the film thickness reaches 6 μm. P4VP is a functional polymer, making this P4VP-b-PMA(Az) film more suitable for advanced filters, multi-nanochannels, nanolithography, and high-density storage media, etc.