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High-density stable glasses formed on soft substrates

Nature Materials (2024)Cite this article

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Abstract

Enabled by surface-mediated equilibration, physical vapour deposition can create high-density stable glasses comparable with liquid-quenched glasses aged for millions of years. Deposition is often performed at various rates and temperatures on rigid substrates to control the glass properties. Here we demonstrate that on soft, rubbery substrates, surface-mediated equilibration is enhanced up to 170 nm away from the interface, forming stable glasses with densities up to 2.5% higher than liquid-quenched glasses within 2.5 h of deposition. Gaining similar properties on rigid substrates would require 10 million times slower deposition, taking ~3,000 years. Controlling the modulus of the rubbery substrate provides control over the glass structure and density at constant deposition conditions. These results underscore the significance of substrate elasticity in manipulating the properties of the mobile surface layer and thus the glass structure and properties, allowing access to deeper states of the energy landscape without prohibitively slow deposition rates.

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Fig. 1: Surface morphology and thermodynamic stability of TPD glasses deposited on 5 nm PDMS and silicon substrates.
Fig. 2: Structural anisotropy of TPD glasses deposited on 5 nm PDMS and silicon substrates.
Fig. 3: Layering peak amplitude of TPD glasses as a function of film thickness.
Fig. 4: Effect of PDMS modulus on the structure and stability of TPD SGs.

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Data availability

All data supporting the findings in this study are available within the Article and its Supplementary Information, or from the corresponding author on reasonable request. Source data are provided with this paper. They are also available via Figshare at https://doi.org/10.6084/m9.figshare.25000454.

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Acknowledgements

We thank M. D. Ediger for insightful discussions. We acknowledge financial support from the National Science Foundation (NSF) Materials Research Science and Engineering Centers (MRSEC) under grant DMR-1720530. Support during manuscript revisions and final editing was provided by Wisconsin MRSEC grant DMR-2309000. We acknowledge the use of the Dual Source and Environmental X-ray Scattering facility operated by the Laboratory for Research on the Structure of Matter at the University of Pennsylvania supported by NSF through DMR-2309043. This research used the 12-ID (SMI) beamline of the National Synchrotron Light Source II, a US Department of Energy (DOE) Office of Science User Facility, operated for the DOE Office of Science by Brookhaven National Laboratory under contract no. DE-SC0012704. P.L. acknowledges postdoctoral fellowship funding from the School of Arts and Sciences of the University of Pennsylvania. C.Y.C. acknowledges support from the NSF Graduate Research Fellowship Program (NSF GRFP, DGE-1845298).

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Authors and Affiliations

  1. Department of Chemistry, University of Pennsylvania, Philadelphia, PA, USA

    Peng Luo, Shivajee Govind, Richard B. Stephens, Dong Hyup Kim, Cindy Y. Chen, Truc Nguyen & Zahra Fakhraai

  2. Department of Chemistry, State University of New York Cortland, Cortland, NY, USA

    Sarah E. Wolf

  3. School of Chemical and Biological Engineering, Seoul National University, Seoul, Republic of Korea

    Dong Hyup Kim

  4. National Synchrotron Light Source II (NSLS-II), Brookhaven National Laboratory, Upton, NY, USA

    Patryk Wąsik & Mikhail Zhernenkov

  5. Department of Mechanical Engineering and Applied Mechanics, University of Pennsylvania, Philadelphia, PA, USA

    Brandon Mcclimon

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Contributions

Z.F. directed the project. P.L. performed the sample preparations and AFM, SE and in-house GIWAXS measurements with the help of S.G. and T.N. P.L., S.E.W., D.H.K., R.B.S., C.Y.C., M.Z. and P.W. performed the synchrotron GIWAXS measurements. P.L., S.E.W. and P.W. analysed the GIWAXS data. B.M. performed the AFM indentation experiments. P.L. and Z.F. wrote the paper with help from all authors.

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Correspondence to Zahra Fakhraai.

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Nature Materials thanks Camille Bishop, Connie Roth and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.

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Luo, P., Wolf, S.E., Govind, S. et al. High-density stable glasses formed on soft substrates. Nat. Mater. (2024). https://doi.org/10.1038/s41563-024-01828-w

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