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Bottlebrush Block Copolymer Assembly in Ultraconfined Films: Effect of Substrate Selectivity

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Download Hi-Res ImageDownload to MS-PowerPointCite This:Macromolecules 2021, 54, 5, 2079-2089
    Article

    Bottlebrush Block Copolymer Assembly in Ultraconfined Films: Effect of Substrate Selectivity
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    • Yaron Aviv
      Yaron Aviv
      Institute of Chemistry and the Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 9190401, Israel
      More by Yaron Aviv
    • Esra Altay
      Esra Altay
      Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260-3000, United States
      More by Esra Altay
    • Ofer Burg
      Ofer Burg
      Institute of Chemistry and the Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 9190401, Israel
      More by Ofer Burg
    • Marcus Müller*
      Marcus Müller
      Institute for Theoretical Physics, Georg-August-University Göttingen, Friedrich-Hund-Platz 1, Göttingen 37077, Germany
      *Email: [email protected]
      More by Marcus Müller
      Orcidhttp://orcid.org/0000-0002-7472-973X
    • Javid Rzayev*
      Javid Rzayev
      Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260-3000, United States
      *Email: [email protected]
      More by Javid Rzayev
      Orcidhttp://orcid.org/0000-0002-9280-1811
    • Roy Shenhar*
      Roy Shenhar
      Institute of Chemistry and the Center for Nanoscience and Nanotechnology, The Hebrew University of Jerusalem, Jerusalem 9190401, Israel
      *Email: [email protected]
      More by Roy Shenhar
      Orcidhttp://orcid.org/0000-0002-0631-1542
    Other Access OptionsSupporting Information (1)

    Macromolecules

    Cite this: Macromolecules 2021, 54, 5, 2079–2089
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.0c02057
    Published February 18, 2021
    Copyright © 2021 American Chemical Society
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    Abstract

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    Abstract Image

    Ultraconfined block copolymer films present nonbulk structures that are highly sensitive to film thickness and are strongly influenced by the wetting properties of the substrate. Here, we describe the self-assembly of bottlebrush block copolymers with varying side-chain lengths on different types of substrates. Our results show a pronounced influence of the nature of the substrate on the self-assembled morphology and the surface patterns that evolve during solvent–vapor annealing. In particular, we observe by experiments and simulations a transient, substrate-driven morphology of cylinder-like structures obtained in films of doubly symmetric (i.e., the backbone and side chains) bottlebrush block copolymers despite the general tendency of these polymers to form lamellar structures. The insights gained from this study highlight the ability to use the substrate chemistry for inducing the formation of unique morphologies in bottlebrush block copolymer films.

    Copyright © 2021 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.macromol.0c02057.

    • GPC curves and NMR spectra of the BBCPs; AFM thickness profile across a scratch in the film of BBCPsym assembled on the PS brush; determination of surface energies of the substrates; assessment of SiOx selectivity toward PS and PLA; and circularity analysis of the PS domains as they appear in the SEM images of BBCPPLA maj films annealed on SiOx and the PLA brush (PDF)

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    Cited By

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    This article is cited by 10 publications.

    1. Xuchen Gan, Hong-Gyu Seong, Mingqiu Hu, Zhan Chen, Todd Emrick, Thomas P. Russell. Crystallization of Bottlebrush Statistical Copolymers of Polystyrene and Poly(ethylene oxide). Macromolecules 2024, 57 (15) , 7306-7314. https://doi.org/10.1021/acs.macromol.4c01159
    2. Benjamin R. Magruder, David C. Morse, Christopher J. Ellison, Kevin D. Dorfman. Boundary Frustration in Double-Gyroid Thin Films. ACS Macro Letters 2024, 13 (4) , 382-388. https://doi.org/10.1021/acsmacrolett.4c00026
    3. Yong-Guen Yu, Joo Hwan Ko, Jong Hyun An, Beom-Goo Kang, Young Min Song, Jae-Suk Lee. Self-assembly of POSS–Polystyrene Bottlebrush Block Copolymers on an Angle-Robust Selective Absorber for Enhancing the Purity of Reflective Structural Color. ACS Applied Materials & Interfaces 2022, 14 (39) , 44753-44761. https://doi.org/10.1021/acsami.2c11194
    4. Mingqiu Hu, Xindi Li, Javid Rzayev, Thomas P. Russell. Hydrolysis-Induced Self-Assembly of High-χ–Low-N Bottlebrush Copolymers. Macromolecules 2021, 54 (24) , 11449-11458. https://doi.org/10.1021/acs.macromol.1c02061
    5. Yaron Aviv, Esra Altay, Javid Rzayev, Roy Shenhar. Assembly of Bottlebrush Block Copolymers and Nanoparticles in Ultrathin Films: Effect of Substrate–Copolymer Interaction on the Nanocomposite Morphology. Macromolecules 2021, 54 (13) , 6247-6256. https://doi.org/10.1021/acs.macromol.1c00459
    6. Zhi Zhao, Xiaotong Zheng, Yurong Li, Xuan Yao, Haibin Wang, Xiaoyan Song. Convert Polymer Self‐Assembly Nanostructures into Target Functional Materials: An Art of Embattling Molecules. Advanced Functional Materials 2024, 133 https://doi.org/10.1002/adfm.202409050
    7. Yingying Guo. Effect of Film Thickness on the Self-Assembly of CBABC Symmetric Pentablock Terpolymer Melts under 1D Confinement: A Dissipative Particle Dynamic Study. Materials 2023, 16 (21) , 6862. https://doi.org/10.3390/ma16216862
    8. Yingying Guo, Linqing Bai. Dissipative Particle Dynamics Simulation for the Self-Assembly of Symmetric Pentablock Terpolymers Melts under 1D Confinements. Polymers 2023, 15 (19) , 3982. https://doi.org/10.3390/polym15193982
    9. Ling-Ying Shi, Zhixiong Fei, Qian Wang, Lin Weng, Chenxiao Yin, Jinrui Sun, Zhihao Shen. Selective solvent vapor induced self-assembly of silicon-containing bottlebrush block copolymer thin films to generate mesoporous silicon oxide patterns. Polymer 2023, 277 , 125952. https://doi.org/10.1016/j.polymer.2023.125952
    10. Sousa Javan Nikkhah, Maria Sammalkorpi. Single core and multicore aggregates from a polymer mixture: A dissipative particle dynamics study. Journal of Colloid and Interface Science 2023, 635 , 231-241. https://doi.org/10.1016/j.jcis.2022.12.119
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    Macromolecules

    Cite this: Macromolecules 2021, 54, 5, 2079–2089
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.0c02057
    Published February 18, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

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