Solvent Processing and Ionic Liquid-Enabled Long-Range Vertical Ordering in Block Copolymer Films with Enhanced Film Stability

Masud, Ali; Wu, Wenjie; Singh, Maninderjeet; Tonny, Wafa; Ammar, Ali; Sharma, Kshitij; Strzalka, Joseph W.; Terlier, Tanguy; Douglas, Jack F.; Karim, Alamgir

doi:10.1021/acs.macromol.1c01305

Title: Solvent Processing and Ionic Liquid-Enabled Long-Range Vertical Ordering in Block Copolymer Films with Enhanced Film Stability

Journal Article · 17 September 2021 · Macromolecules

DOI: https://doi.org/10.1021/acs.macromol.1c01305 · OSTI ID:1840574

^[1]; Wu, Wenjie ^[1];

^[1]; Tonny, Wafa ^[1]; Ammar, Ali ^[1]; Sharma, Kshitij ^[1];

^[2]; Terlier, Tanguy ^[3];

^[4];

^[1]

Univ. of Houston, TX (United States)
Argonne National Lab. (ANL), Lemont, IL (United States)
Rice Univ., Houston, TX (United States)
National Inst. of Standards and Technology (NIST), Gaithersburg, MD (United States)

Rapid and reliable processing methods for forming ordered block copolymer (BCP) materials with low defect density in a thin film geometry are required for many nanotechnology applications. Vertically aligned BCP structures, in particular, have applications ranging from nanolithography for electronics and photonics to nanoporous membranes for water remediation and novel batteries for flexible electronics. However, the attainment of nearly complete vertical orientational order of the BCP ordered phase remains challenging. Solvent-based techniques, such as direct immersion annealing (DIA) and solvent vapor annealing (SVA), have immense potential for these applications of BCP films, as it allows for tuning of their thermodynamic, structural, and chain mobility driven kinetic properties. We first demonstrate that DIA, using a judicious choice of binary solvent mixtures along with a relatively hydrophobic ionic liquid (IL), induces the rapid vertical ordering in polystyrene-b-polymethylmethacrylate (PS-PMMA) block copolymer in lamellar films. The IL establishes synergy to the binary solvent mixture of toluene and heptane to 1 create a near-neutral solvent environment for attaining the vertical microstructure of the BCP. Next, we show that IL can suppress the de-wetting of the PS-PMMA films to achieve long-range order using SVA in cylindrical films for long annealing times. Both vertical and horizontal morphology is attained in these films by selecting different solvent environments. Furthermore, attaining enhanced vertical and horizontal BCP structure with long-range defect-free order by tuning solvent quality and using additives like IL can render them useful for many nanotech applications.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1840574

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 18 Vol. 54; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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