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Multi-scale dynamics at the glassy silica surface.

Huy A Nguyen1, Can Liao1, Alison Wallum1

  • 1Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.

The Journal of Chemical Physics
|November 10, 2019
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Summary
This summary is machine-generated.

Glassy silica films exhibit dynamic motions below the glass transition temperature. Clusters of silica glass-forming units (GFUs) hop and merge, while Si-O-Si bridges flip, influencing the material

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Area of Science:

  • Materials Science
  • Condensed Matter Physics
  • Surface Science

Background:

  • Silica-based glass is ubiquitous, yet its dynamics below the glass transition temperature remain debated.
  • Understanding these dynamics is crucial for applications ranging from insulation to microelectronics.

Purpose of the Study:

  • To investigate and classify atomic-scale motions in glassy silica films at room temperature.
  • To elucidate the nature of dynamics occurring well below the glass transition temperature (Tg).

Main Methods:

  • Fabrication of thin glassy silica films via Si(100) surface oxidation (0.5–1.5 nm thickness).
  • In situ scanning tunneling microscopy (STM) for imaging and classifying motions at room temperature.
  • Electronic structure calculations to assign observed vibrational fine structures.

Main Results:

  • Observed two distinct dynamic phenomena: cluster hopping and Si-O-Si bridge flipping.
  • Glass-forming units (GFUs) form clusters that exhibit cooperative hopping, merging (aging), and splitting (rejuvenation) on minute timescales.
  • Si-O-Si bridges within clusters flip on second timescales, creating a vibrational fine structure.
  • Calculated barrier heights for hopping align with thermodynamic predictions of configurational entropy.

Conclusions:

  • The study reveals distinct configurational and vibrational dynamics in silica glass below Tg.
  • Observed dynamics, including cluster hopping and GFU flipping, are consistent with thermodynamic models of the glass transition.
  • Both vibrational and configurational entropy contribute significantly to the dynamics on a per-GFU basis.