Proximity Injection of Plasticizing Molecules to Self-Assembling Polymers for Large-Area, Ultrafast Nanopatterning in the Sub-10-nm Regime

While the uses of block copolymers (BCPs) with a high Flory–Huggins interaction parameter (χ) are advantageous for the improvement of resolution and line edge fluctuations of self-assembled nanoscale patterns, their slow chain diffusion results in a prolonged assembly time. Although solvent vapor annealing has shown great effectiveness in promoting the self-assembly of such BCPs, a practical methodology to achieve a uniform swelling level in wafer-scale BCP thin films has not been reported. Here, we show that a solvent-swollen polymer gel pad can be used as a highly controllable vapor source for the rapid, large-area (>200 mm in diameter) formation of sub-10-nm patterns from a high-χ BCP. The proximal injection of solvent vapors to BCP films and the systematic control of the swelling levels and temperatures can significantly boost the self-assembly kinetics, realizing the formation of well-aligned sub-10-nm half-pitch patterns within 1 min of self-assembly. Moreover, we show that the gel pad can be used for the shear-induced alignment of BCP microdomains in an extremely short time of ∼5 s as well as for the generation of three-dimensional crossed-wire nanostructures with controlled alignment angles.