Wet Brush Homopolymers as “Smart Solvents” for Rapid, Large Period Block Copolymer Thin Film Self-Assembly


Doerk, G.S.; Li, R.; Fukuto, M.; Yager, K.G. "Wet Brush Homopolymers as “Smart Solvents” for Rapid, Large Period Block Copolymer Thin Film Self-Assembly" Macromolecules 2020, 53 1098–1113.
doi: 10.1021/acs.macromol.9b02296


We demonstrate how blending of homopolymer chains into a block copolymer allows one to induce structure formation in otherwise intractable high molecular-weight materials.


The spontaneous formation of periodic nanopatterns through the self-assembly of block copolymer (BCP) thin films offers an enticing path to engineer functional material properties over large areas, but the prohibitively slow ordering of ultrahigh molecular weight BCPs that generate large pattern periods (>100 nm) severely restricts the design space in which BCPs may be used. Here, we demonstrate that blending lamellae-forming polystyrene-block-poly(methyl methacrylate) diblock copolymers with very low molecular weight polystyrene and poly(methyl methacrylate) homopolymers can reduce by an order-of-magnitude the times required to form ordered large period patterns through solvent vapor annealing. Using in situ grazing-incidence small-angle X-ray scattering and ex situ electron microscopy, we show that the added homopolymer plasticizers act as a “smart solvent”: They increase the mobility of the long BCP chains by amplifying the dilution effect during solvent vapor annealing but segregate to like domains during subsequent thermal annealing to produce high-quality patterns with periods that may exceed 200 nm, which are readily transferred to other materials. The dramatic impact of homopolymer plasticizers may help extend the use of BCPs into new areas, particularly for visible light photonic applications that demand larger period nanopatterns.