Hierarchical, Self-Assembled Metasurfaces via Exposure-Controlled Reflow of Block Copolymer-Derived Nanopatterns.

Nanopatterning for the fabrication of optical metasurfaces entails a need for high-resolution approaches like electron beam lithography that cannot be readily scaled beyond prototyping demonstrations. Block copolymer thin film self-assembly offers an attractive alternative for producing periodic nanopatterns across large areas, yet the pattern feature sizes are fixed by the polymer molecular weight and composition. Here, a general strategy is reported which overcomes the limitation of the fixed feature size by treating the copolymer thin film as a hierarchical resist, in which the nanoscale pattern motif is defined by self-assembly. Feature sizes can then be tuned by thermal reflow controlled locally by irradiative cross-linking or chemical alteration using lithographic ultraviolet light or electron beam exposure. Using blends of polystyrene--poly(methylmethacrylate) (PS--PMMA) with PS and PMMA homopolymers, we demonstrate both self-assembled PS grating and hexagonal hole patterns; exposure-controlled reflow is then used to reduce the hole diameter by as much as 50% or increase the PS grating linewidth by more than 180%. Transferring these nanopatterns, or their inverse obtained by a lift-off approach, into silicon yields structural colors that may be prescriptively controlled based on the nanoscale feature size. Furthermore, patterned exposure enables area-selective feature size control, yielding uniform structural color patterns across centimeter square areas. Electron beam lithography is also used to show that the lithographic resolution of this selective-area control can be extended to the nanoscale dimensions of the self-assembled features. The exposure-controlled reflow approach demonstrated here takes a pivotal step toward fabricating complex, hierarchical optical metasurfaces using scalable self-assembly methods.