Glass transition in thin supported polystyrene films probed by temperature-modulated ellipsometry in vacuum

Phys Rev E Stat Nonlin Soft Matter Phys. 2012 Aug;86(2 Pt 1):021501. doi: 10.1103/PhysRevE.86.021501. Epub 2012 Aug 7.

Abstract

Glass transition in thin (1-200 nm thick) spin-cast polystyrene films on silicon surfaces is probed by ellipsometry in a controlled vacuum environment. A temperature-modulated modification of the method is used alongside a traditional linear temperature scan. A clear glass transition is detected in films with thicknesses as low as 1-2 nm. The glass transition temperature (T(g)) shows no substantial dependence on thickness for coatings greater than 20 nm. Thinner films demonstrate moderate T(g) depression achieving 18 K for thicknesses 4-7 nm. Less than 4 nm thick samples are excluded from the T(g) comparison due to significant thickness nonuniformity (surface roughness). The transition in 10-20 nm thick films demonstrates excessive broadening. For some samples, the broadened transition is clearly resolved into two separate transitions. The thickness dependence of the glass transition can be well described by a simple 2-layer model. It is also shown that T(g) depression in 5 nm thick films is not sensitive to a wide range of experimental factors including molecular weight characteristics of the polymer, specifications of solvent used for spin casting, substrate composition, and pretreatment of the substrate surface.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Glass / chemistry*
  • Nitrogen / chemistry
  • Oxidation-Reduction
  • Phase Transition*
  • Polystyrenes / chemistry*
  • Surface Properties
  • Temperature*
  • Vacuum

Substances

  • Polystyrenes
  • Nitrogen