Chemically tailored block copolymers for highly reliable sub-10-nm patterns by directed self-assembly

Abstract While block copolymer (BCP) lithography is theoretically capable of printing features smaller than 10 nm, developing practical BCPs for this purpose remains challenging. Herein, we report the creation of a chemically tailored, highly reliable, and practically applicable block copolymer and sub-10-nm line patterns by directed self-assembly. Polystyrene- block -[poly(glycidyl methacrylate)- random -poly(methyl methacrylate)] (PS- b -(PGMA- r -PMMA) or PS- b -PGM), which is based on PS- b -PMMA with an appropriate amount of introduced PGMA (10–33 mol%) is quantitatively post-functionalized with thiols. The use of 2,2,2-trifluoroethanethiol leads to polymers (PS- b -PG F Ms) with Flory–Huggins interaction parameters ( χ ) that are 3.5–4.6-times higher than that of PS- b -PMMA and well-defined higher-order structures with domain spacings of less than 20 nm. This study leads to the smallest perpendicular lamellar domain size of 12.3 nm. Furthermore, thin-film lamellar domain alignment and vertical orientation are highly reliably and reproducibly obtained by directed self-assembly to yield line patterns that correspond to a 7.6 nm half-pitch size.