Control of the Orientation of Symmetric Poly(styrene)-block-poly(d,l-lactide) Block Copolymers Using Statistical Copolymers of Dissimilar Composition
Abstract
The interactions of block copolymers with surfaces can be controlled by coating those surfaces with appropriate statistical copolymers. Usually, a statistical copolymer comprised of monomer units identical to those of the block copolymer is used; that is, typically a poly(styrene)-stat-poly(methyl methacrylate) (PS-stat-PMMA) is used to direct the alignment of poly(styrene)-block-poly(methyl methacrylate) (PS-block-PMMA), and poly(styrene)-stat-poly(2-vinylpyridine) (PS-stat-P2VP) has been used for poly(styrene)-block-poly(2-vinylpyridine) (PS-block-P2VP). Reports of controlling the orientation of block copolymers with statistical copolymers with a dissimilar composition are limited. Here, we demonstrate that this method can be further extended to show that PS-stat-PMMA can be used to control the wetting properties of poly(styrene)-block-poly(D,L-lactide) (PS-block-PDLA). Surfaces were modified with a series of cross-linked PS-stat-PMMA-stat-glycidyl methacrylate terpolymers, and the surface chemistries and energies were assessed using angle-dependent X-ray photoelectron spectroscopy and the two-liquid harmonic method, respectively. From these experiments, an expected neutral compositional window was identified for symmetrical PS-block-PDLA. Moreover, high-resolution SEM, AD-XPS, and grazing-incidence SAXS measurements were used to evaluate the morphology of PS-block-PDLA as a function of the surface composition of the underlying cross-linked copolymer films, and the neutral composition was found to range from 32 to 38 mol % of PS, in the bulk polymer. Ultimately, we demonstrated the determination of nonpreferential surface compositions that allow the self-assembly of lamellae with sizes in the sub-10 nm regime that are oriented perpendicular to the substrate. These findings have important implications for the use of PS-block-PDLA block copolymers in directed self-assembly, most specifically in advanced lithographic processes.
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PS-b-PDMS, PS-b-P2VP, and PS-b-PLA are capable of self-assembling into sub-10 nm domain sizes.
“Some other BCPs that are capable of self-assembling into sub-10 nm domain sizes include PS-b-PDMS [125], PS-b-P2VP [126], and PS-b-PLA [118].”
From Block Copolymers: Synthesis, Self-Assembly, and Applications (2017) · cites this paper as [118]
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Block Copolymers: Synthesis, Self-Assembly, and Applications
Feng, H., Lu, X., Wang, W., Kang, N.-G., & Mays, J. (2017) · Polymers · doi:10.3390/polym9100494 · Cited by 467 · see citing works
“Some other BCPs that are capable of self-assembling into sub-10 nm domain sizes include PS-b-PDMS [125], PS-b-P2VP [126], and PS-b-PLA [118].”
Background
- Authors
- Keen, I., Yu, A., Cheng, H.-H., Jack, K. S., Nicholson, T. M., Whittaker, A. K., & Blakey, I.
- Affiliations
- The University of Queensland (AU)
- Corresponding author
- Whittaker, Andrew K.
- Blakey, Idriss
- Venue
- Langmuir
- Publisher
- American Chemical Society (ACS)
- Published
- 2012-10-30
- Volume
- 28
- Issue
- 45
- Pages
- 15876-15888
- ISSN
- 0743-7463 (ISSN-L)
- 1520-5827
- OpenAlex
- W2020022786
- Cited by
- 56
- References
- 78
- Citations by year
- 2024: 2 · 2023: 1 · 2022: 3 · 2021: 4 · 2020: 2 · 2019: 6 · 2018: 3 · 2017: 7 · 2016: 5 · 2015: 10 · 2014: 9 · 2013: 4
- FWCI
- 3.38
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Langmuir (publishedVersion)
- PubMed (publishedVersion)
- Topics
- Physical Sciences › Materials Science › Materials Chemistry › Block Copolymer Self-Assembly
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Materials Science › Surfaces, Coatings and Films › Polymer Surface Interaction Studies
- Keywords
- random copolymers, surface modification, wettability, glycidyl methacrylate, surface composition, lamellar self-assembly, directed self-assembly, lithography, surface energy
- MeSH terms
- Polyesters, Polystyrenes, Molecular Structure
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