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Title
Japanese:Sequence-Encoded Perpendicular Orientation in High-Chi Triblock Copolymer Thin Films via Central Hydrophobic Block Placement 
English:Sequence-Encoded Perpendicular Orientation in High-Chi Triblock Copolymer Thin Films via Central Hydrophobic Block Placement 
Author
Japanese: 上原綾太, 前川伸祐, 瀬下武広, Ryutaro Sugawara, Takahiro Dazai, Kazufumi Sato, 高橋陸, 畠山歓, Yuta Nabae, 早川晃鏡.  
English: Ryota Uehara, Shinsuke Maekawa, Takehiro Seshimo, Ryutaro Sugawara, Takahiro Dazai, Kazufumi Sato, Riku Takahashi, Kan Hatakeyama, Yuta Nabae, Teruaki Hayakawa.  
Language English 
Journal/Book name
Japanese:Macromolecules 
English:Macromolecules 
Volume, Number, Page Vol. 59    No. 11    pp. 6266-6273
Published date June 2026 
Publisher
Japanese:American Chemical Society 
English:American Chemical Society 
Conference name
Japanese: 
English: 
Conference site
Japanese: 
English: 
Official URL https://doi.org/10.1021/acs.macromol.6c00175
 
DOI https://doi.org/10.1021/acs.macromol.6c00175
Abstract Block copolymer lithography is a promising technique for nanoscale patterning in semiconductor manufacturing, where perpendicular domain orientation is essential. This study elucidates the influence of hydrophobic block position within triblock copolymers on the formation of well-ordered perpendicular orientation. Triblock copolymers with hydrophobic blocks precisely positioned at the middle and terminal are synthesized via living anionic polymerization and efficient thiol-epoxy reactions. Atomic force microscopy (AFM) reveals that perpendicular microdomain orientation is achieved only when the low-surface-energy block is placed centrally, where chain connectivity frustrates complete surface segregation and thereby stabilizes a perpendicular lamellar orientation. Further analyses via cross-sectional scanning electron microscopy (SEM) and grazing incidence small-angle X-ray scattering (GI-SAXS) demonstrate the perpendicular orientation across the entire film. These findings provide design guidelines for high-ﾏ� block copolymers enabling perpendicular orientation for nanolithography.

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