Engineering Self-Assembled Domain Asymmetry in Solvent Vapor Annealed Block Copolymer–Homopolymer Blend Films

Doerk, Gregory S.; Kulkarni, Ashish A.; Li, Ruipeng

doi:10.1021/acs.macromol.3c01652

Title: Engineering Self-Assembled Domain Asymmetry in Solvent Vapor Annealed Block Copolymer–Homopolymer Blend Films

Journal Article · Wed Dec 20 00:00:00 EST 2023 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.3c01652· OSTI ID:2267565

^[1];

^[1]; Li, Ruipeng ^[2]

Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Thin-film block copolymer (BCP) self-assembly is a powerful approach to generate highly uniform nanopatterns across large areas, yet the symmetries of these nanopatterns are constrained by the relative volume occupied by each polymer block. Here, we present a conceptually new approach to circumvent this limitation by combining homopolymer (HP) blending with solvent vapor annealing (SVA), demonstrated here for ternary blends of a near-symmetric BCP with athermal, low molar mass HPs. Screening of BCP–HP interactions by a weakly selective solvent promotes entropically driven delocalization of HP throughout both blocks and enables assembly of metastable lamellae for volume fractions as high as 0.78. Subsequent brief thermal annealing induces HPs to withdraw to their enthalpically favored domains, sharpening domain interfaces on a time scale much shorter than pattern coarsening. This renders lamellar nanopatterns with tunable widths that can be transferred to other materials with high fidelity. Furthermore, the persistence of the metastable asymmetric lamellae upon thermal annealing is sensitive to film confinement, as they are preserved in submonolayer films but transition to horizontal cylinders in films more than one monolayer thick. SVA using a strongly selective solvent results in assembled morphologies aligned closely with expectations based on the total polymer blend composition, underscoring the key role of BCP–HP interactions in dictating domain asymmetry. Overall, this work details important principles for using SVA to mediate BCP–HP interactions in thin films, thereby presenting opportunities to engineer pathways for the assembly of well-ordered nanopatterns with designer feature asymmetry for lithographic or nanotexturing applications.

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Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2267565

Report Number(s):: BNL-225129-2023-JAAM

Journal Information:: Macromolecules, Vol. 57, Issue 1; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Engineering Self-Assembled Domain Asymmetry in Solvent Vapor Annealed Block Copolymer–Homopolymer Blend Films

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