Assembling Vertical Block Copolymer Nanopores via Solvent Vapor Annealing on Homopolymer-Functionalized Substrates

Bellini, Beatrice; Willard, Jasmine R.; Cetindag, Semih; Tsai, Esther R.; Li, Ruipeng; Kisslinger, Kim; Kumar, Sanat K.; Doerk, Gregory S.

doi:10.1021/acsami.4c05715

Assembling Vertical Block Copolymer Nanopores via Solvent Vapor Annealing on Homopolymer-Functionalized Substrates

Journal Article · Wed Jun 26 00:00:00 EDT 2024 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.4c05715· OSTI ID:2382648

Bellini, Beatrice ^[1]; Willard, Jasmine R. ^[2]; Cetindag, Semih ^[3]; Tsai, Esther R. ^[3]; Li, Ruipeng ^[4]; Kisslinger, Kim ^[3]; ^[5]; ^[3]

Columbia Univ., New York, NY (United States); Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Alfred Univ., NY (United States)
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)
Columbia Univ., New York, NY (United States)

Utilizing the self-assembly of block copolymers with large Flory–Huggins interaction parameters (χ) for nanofabrication is a formidable challenge due to the attendant large surface energy differences between the blocks. This work reports a robust protocol for the fabrication of thin films with highly ordered cylindrical nanopore arrays via the self-assembly of an asymmetric poly(styrene-block-4-vinylpyridine) (PS-b-P4VP) diblock copolymer blended with a P4VP homopolymer. The desired vertical domain orientation is achieved at the air–polymer interface by controlled solvent vapor annealing (SVA) using acetone, a solvent with weak selectivity for PS over P4VP, and at the substrate interface by functionalization using a hydroxy-terminated poly(2-vinylpyridine) (P2VP-OH) homopolymer brush. In contrast, the vertical cylinder orientation is unstable during acetone SVA on substrates functionalized using hydroxy-terminated poly(methyl methacrylate) (PMMA-OH). Although PMMA exhibits more balanced interfacial energies between PS and P4VP than P2VP in the dry state, it is also swollen more selectively by acetone. We hypothesize that the nearly balanced solvent swelling of the three polymers (P2VP, P4VP, and PS) stabilizes the vertical cylinder orientation, while unbalanced swelling (PMMA > P4VP and PS) does not. Here we further characterize pore formation by addition of a P4VP homopolymer and its postassembly extraction using ethanol, revealing a narrow window of pore size tunability. Notably, minimal differences in nanopore morphologies are observed for P4VP volume fractions as high as 0.1, regardless of the P4VP molar mass. However, further increasing the P4VP volume fraction results in domain reorientation or macrophase separation when its molar mass is less than or greater than the P4VP block molar mass, respectively. Using a P4VP homopolymer that is nearly equal in length to the P4VP block enables the fabrication of well-ordered arrays of vertical, through-film nanopores with high aspect ratios (>10), small periods (<23 nm), and diameters less than 10 nm.

View Accepted Manuscript (DOE)

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:: 2382648

Report Number(s):: BNL--225754-2024-JAAM

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 27 Vol. 16; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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