Rapid Assembly of Block Copolymer Thin Films via Accelerating the Swelling Process During Solvent Annealing

Block copolymer (BCP) lithography is widely regarded as a promising next-generation nanolithography technique. However, achieving rapid assembly with defect-free morphology remains a significant challenge for its practical application. In this study, we presented a facile and efficient solvent annealing method for fabricating well-ordered BCP thin films within minutes on both flat and topographically patterned substrates. By accelerating the swelling process, rapid film swelling was observed within just 10 s of annealing, leading to well-ordered morphologies in 1~3 min. Furthermore, we systematically investigated the influence of swelling ratio (SR) on film morphology by precisely tuning solvent vapor pressure. For cylinder-forming poly(styrene-block-2-vinylpyridine) (PS-b-P2VP) films, we identified three distinct SR-dependent ordering regimes: (I) Excessive SR led to a disordered morphology; (II) near-optimal SR balanced long-range and short-range orders, and a slight increase in SR enhanced the long-range order but introduced short-range defects. (III) Insufficient SR failed to provide adequate chain mobility, limiting long-range order development. These findings highlight the critical role of SR in controlling defect density in nanopatterned surfaces. Long-range-ordered BCP nanopatterns can only be achieved under optimal SR conditions that ensure sufficient chain mobility. We believe this rapid annealing strategy, which is also applicable to other solvent-based annealing systems for BCP films, may contribute to next-generation nanolithography for microfabrication.