Solvent-Induced Swelling Behaviors of Microphase-Separated Polystyrene-block-Poly(ethylene oxide) Thin Films Investigated Using In Situ Spectroscopic Ellipsometry and Single-Molecule Fluorescence Microscopy

Coceancigh, Herman; Xue, Lianjie; Nagasaka, Shinobu; Higgins, Daniel A.; Ito, Takashi

doi:10.1021/acs.jpcb.2c05025

Solvent-Induced Swelling Behaviors of Microphase-Separated Polystyrene-block-Poly(ethylene oxide) Thin Films Investigated Using In Situ Spectroscopic Ellipsometry and Single-Molecule Fluorescence Microscopy

Journal Article · Tue Oct 11 04:00:00 EDT 2022 · Journal of Physical Chemistry. B

DOI:https://doi.org/10.1021/acs.jpcb.2c05025· OSTI ID:1895417

Coceancigh, Herman ^[1]; ^[2]; Nagasaka, Shinobu ^[2]; ^[2]; ^[2]

Kansas State Univ., Manhattan, KS (United States); Kansas State University
Kansas State Univ., Manhattan, KS (United States)

Block copolymers have attracted considerable interest in the fields of nanoscience and nanotechnology, because these polymers afford well-defined nanostructures via self-assembly. An in-depth understanding of solvent effects on the physicochemical properties of these microdomains is crucial for their preparation and utilization. Herein, we employed in situ spectroscopic ellipsometry and single-molecule fluorescence techniques to gain detailed insights into microdomain properties in polystyrene-block-poly(ethylene oxide) (PS-b-PEO) films exposed to ethanol- and water-saturated N₂. We observed a quick increase and a subsequent gradual decrease in the ellipsometric thickness of PS-b-PEO films upon exposure to ethanol-saturated N₂. This observation was unexpected because ethanol-saturated N₂ induced negligible thickness change for PS and PEO homopolymer films. The similarity in maximum thickness gain observed under ethanol- and water-saturated N₂ implied the swelling of PEO microdomains. Ethanol vapor permeation through the PEO microdomains was supported by the red-shift of the ensemble and single-molecule fluorescence emission of Nile red in PS-b-PEO films. Single-molecule tracking data showed the initial enhancement and subsequent reduction of the diffusion of hydrophilic sulforhodamine B molecules in PS-b-PEO films upon exposure to ethanol-saturated N₂, consistent with the spectroscopic ellipsometry results. Furthermore, the higher ethanol susceptibility of the PEO microdomains was attributable to their amorphous nature, as shown by FTIR data.

View Accepted Manuscript (DOE)

Research Organization:: Kansas State Univ., Manhattan, KS (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0002362

OSTI ID:: 1895417

Journal Information:: Journal of Physical Chemistry. B, Journal Name: Journal of Physical Chemistry. B Journal Issue: 41 Vol. 126; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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