Effect of deprotection extent on swelling and dissolution regimes of thin polymer films

Ashwin Rao, Shuhui Kang, Bryan D. Vogt, Vivek M. Prabhu, Eric K. Lin, Wen Li Wu, M. Muthukumar

Research output: Contribution to journalArticle

17 Scopus citations

Abstract

The response of unentangled polymer thin films to aqueous hydroxide solutions is measured as a function of increasing weakly acidic methacrylic acid comonomer content produced by an in situ reaction-diffusion process. Quartz crystal microbalance with energy dissipation and Fourier transform infrared spectroscopy measurements are used to identify four regimes: (I) nonswelling, (II) quasiequilibrium swelling, (III) swelling coupled with partial film dissolution, and (IV) film dissolution. These regimes result from chemical heterogeneity in local composition of the polymer film. The acid-catalyzed deprotection of a hydrophobic group to the methacrylic acid tends to increase the hydrophilic domain size within the film. This nanoscale structure swells in aqueous base by ionization of the methacrylic acid groups. The swollen film stability, however, is determined by the hydrophobic matrix that can act as physical cross-links to prevent dissolution of the polyelectrolyte chains. These observations challenge current models of photoresist film dissolution that do not include the effects of swelling and partial film dissolution on image quality.

Original languageEnglish (US)
Pages (from-to)10009-10015
Number of pages7
JournalLangmuir
Volume22
Issue number24
DOIs
Publication statusPublished - Nov 21 2006

    Fingerprint

All Science Journal Classification (ASJC) codes

  • Materials Science(all)
  • Condensed Matter Physics
  • Surfaces and Interfaces
  • Spectroscopy
  • Electrochemistry

Cite this

Rao, A., Kang, S., Vogt, B. D., Prabhu, V. M., Lin, E. K., Wu, W. L., & Muthukumar, M. (2006). Effect of deprotection extent on swelling and dissolution regimes of thin polymer films. Langmuir, 22(24), 10009-10015. https://doi.org/10.1021/la061773p