Bottlebrush Copolymer as Surface Neutralizer for Vertical Alignment of Block Copolymer Nanodomains in Thin Films

Ki Hyun Kim, Mincheol Kim, Junsoo Moon, June Huh, Joona Bang

Research output: Contribution to journalArticlepeer-review

16 Citations (Scopus)


Herein we designed bottlebrush copolymers for use as a neutral additive to block copolymer (BCP) thin films in which they are segregated to the interfaces via architectural effects and produce nonpreferential interfaces to induce perpendicular orientation of BCP microdomains. Two BCP systems were employed, a conventional poly(styrene-b-methyl methacrylate) (PS-b-PMMA) with relatively low χ and similar surface energies between blocks, and a high χ poly(styrene-b-methacrylic acid) (PS-b-PMAA) with distinct surface energies. The bottlebrushes, with either short side-chains of PS-r-PMMA or PS-r-PMAA random copolymers, were synthesized via ring-opening metathesis polymerization (ROMP). Remarkably, it was observed that the top and bottom interfaces of both BCP films were enriched with bottlebrush copolymers, regardless of the surface energy difference between blocks, hence, vertically oriented microdomains were achieved for both BCP systems. This can be attributed to the screening of polymer interactions by a good solvent during the spin-casting process, allowing architectural effects to play a role in surface segregation of bottlebrush copolymers, as confirmed by contact angle measurements and time-of-flight secondary ion mass spectroscopy (TOF-SIMS). We believe that this concept can be further extended to various applications that require polymer films with functional surfaces.

Original languageEnglish
Pages (from-to)346-353
Number of pages8
JournalACS Macro Letters
Issue number3
Publication statusPublished - 2021 Mar 16

Bibliographical note

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© 2021 American Chemical Society. All rights reserved.

ASJC Scopus subject areas

  • Organic Chemistry
  • Polymers and Plastics
  • Inorganic Chemistry
  • Materials Chemistry


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