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Dispersity-Driven Stabilization of Coexisting Morphologies in Asymmetric Diblock Copolymer Thin Films

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    Dispersity-Driven Stabilization of Coexisting Morphologies in Asymmetric Diblock Copolymer Thin Films
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    • Jyoti P. Mahalik
      Jyoti P. Mahalik
      Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      Department of Mathematics, University of Tennessee, Knoxville, Tennessee 37916, United States
      Department of Polymer Science and Engineering, University of Massachusetts, Amherst, Massachusetts 01002, United States
      More by Jyoti P. Mahalik
      Orcidhttp://orcid.org/0000-0003-4448-4126
    • Wei Li
      Wei Li
      Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      Computational Sciences and Engineering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, Tennessee 37916, United States
      More by Wei Li
    • Andrei T. Savici
      Andrei T. Savici
      Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      More by Andrei T. Savici
    • Steven Hahn
      Steven Hahn
      Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      More by Steven Hahn
    • Hans Lauter
      Hans Lauter
      Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      More by Hans Lauter
    • Haile Ambaye
      Haile Ambaye
      Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      More by Haile Ambaye
    • Bobby G. Sumpter
      Bobby G. Sumpter
      Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      Computational Sciences and Engineering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
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      Orcidhttp://orcid.org/0000-0001-6341-0355
    • Valeria Lauter*
      Valeria Lauter
      Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      *Email: [email protected]
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    • Rajeev Kumar*
      Rajeev Kumar
      Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      Computational Sciences and Engineering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
      *Email: [email protected]
      More by Rajeev Kumar
      Orcidhttp://orcid.org/0000-0001-9494-3488
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    Macromolecules

    Cite this: Macromolecules 2021, 54, 1, 450–459
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    https://doi.org/10.1021/acs.macromol.0c01722
    Published December 15, 2020
    Copyright © 2020 American Chemical Society
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    Abstract

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    Despite decades of research, characterization of the effects of polymer chain dispersity on the structural properties of block copolymer thin films remains challenging. We present an integrated experimental and modeling approach to characterize the morphology of thin films containing asymmetric diblock copolymers. Specifically, we used synergistic neutron reflectivity (NR) and self-consistent field theory (SCFT)-based modeling to realize unexpected morphology of thin films containing asymmetric copolymers. Using NR, a highly stable and reproducible mixed phase of coexisting cylinders and lamellar domains was discovered in asymmetric poly(deuterated-styrene-b-n butyl methacrylate) (dPS-PBMA) copolymer thin films containing 34% volume fraction of dPS. SCFT reveals how to obtain such a thermodynamically stable morphology in the presence of disperse majority block and asymmetric interactions of polymer species with surfaces. Stabilization of the coexisting domains is a consequence of the depth segregation based on chain-length distribution. The asymmetric chains microphase-separate into cylindrical domains close to the substrate and near-symmetric chains form lamellar domains at the air interface. In the absence of dispersity, the coexistence of cylindrical and lamellar domains is thermodynamically unstable because of the absence of depth segregation. Overall, such an effect of dispersity on diblock copolymer thin-film morphology reveals a unique and powerful strategy to create coexisting nanoscale domains and tailor properties of thin films.

    Copyright © 2020 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.0c01722.

    • SCFT model parameter determination for thin films containing monodisperse dPS-PBMA copolymers; effect of different parameters on the morphology of monodisperse dPS-PBMA thin film; Effect of different parameters on the polydisperse dPS-PBMA thin film; effects of Đ on the free energy of the competing morphologies in the thin film; molecular weight distribution as a function of Đ (PDF)

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    Cited By

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    This article is cited by 4 publications.

    1. Panagiotis Christakopoulos, Hanyu Wang, Peter V. Bonnesen, Jong K. Keum, Yangyang Wang, Kunlun Hong, Bradley S. Lokitz, Mathieu Doucet, James F. Browning, Rigoberto C. Advincula, Rajeev Kumar. Characterizing Hygroscopic Films of Polyzwitterions in Electric Fields Using Neutron and X-ray Reflectometries: Electrostriction or Mass Loss?. ACS Applied Materials & Interfaces 2024, 16 (36) , 48307-48319. https://doi.org/10.1021/acsami.4c09938
    2. Jia-Wen Hong, Yi-Qing Jian, Yin-Ping Liao, Hsiang-Ho Hung, Tzu-Yen Huang, Andrew Nelson, I-Yu Tsao, Chun-Ming Wu, Ya-Sen Sun. Distributions of Deuterated Polystyrene Chains in Perforated Layers of Blend Films of a Symmetric Polystyrene-block-poly(methyl methacrylate). Langmuir 2021, 37 (44) , 13046-13058. https://doi.org/10.1021/acs.langmuir.1c02132
    3. Brian Qu, Panagiotis Christakopoulos, Hanyu Wang, Jong Keum, Polyxeni P Angelopoulou, Peter V Bonnesen, Kunlun Hong, Mathieu Doucet, James F Browning, Miguel Fuentes-Cabrera, Rajeev Kumar. Learning continuous scattering length density profiles from neutron reflectivities using convolutional neural networks *. Machine Learning: Science and Technology 2024, 5 (4) , 045065. https://doi.org/10.1088/2632-2153/ad9809
    4. Dustin Eby, Mikolaj Jakowski, Valeria Lauter, Mathieu Doucet, Panchapakesan Ganesh, Miguel Fuentes-Cabrera, Rajeev Kumar. Extraction of interaction parameters from specular neutron reflectivity in thin films of diblock copolymers: an “inverse problem”. Nanoscale 2023, 15 (16) , 7280-7291. https://doi.org/10.1039/D2NR07173H
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    Macromolecules

    Cite this: Macromolecules 2021, 54, 1, 450–459
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.macromol.0c01722
    Published December 15, 2020
    Copyright © 2020 American Chemical Society
    Request reuse permissions

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