Block Copolymer Assembly on Nanoscale Patterns of Polymer Brushes Formed by Electrohydrodynamic Jet Printing

Fundamental understanding of the self-assembly of domains in block copolymers (BCPs) and capabilities in control of these processes are important for their use as nanoscale templates in various applications. This paper focuses on the self-assembly of spin-cast and printed poly(styrene-<i>block</i>-methyl methacrylate) BCPs on patterned surface wetting layers formed by electrohydrodynamic jet printing of random copolymer brushes. Here, end-grafted brushes that present groups of styrene and methyl methacrylate in geometries with nanoscale resolution deterministically define the morphologies of BCP nanostructures. The materials and methods can also be integrated with lithographically defined templates for directed self-assembly of BCPs at multiple length scales. The results provide not only engineering routes to controlled formation of complex patterns but also vehicles for experimental and simulation studies of the effects of chemical transitions on the processes of self-assembly. In particular, we show that the methodology developed here provides the means to explore exotic phenomena displayed by the wetting behavior of BCPs, where 3-D soft confinement, chain elasticity, interfacial energies, and substrate’s surface energy cooperate to yield nonclassical wetting behavior