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Ultrastable monodisperse polymer glass formed by physical vapour deposition


Stable glasses prepared by vapour deposition are an analogue of glassy materials aged for geological timescales. The ability to prepare such materials allows the study of near-ideal glassy systems. We report the preparation and characterization of stable glasses of polymers prepared by physical vapour deposition. By controlling the substrate temperature, deposition rate and polydispersity, we prepared and characterized a variety of stable polymer glasses. These materials display the kinetic stability, low fictive temperatures and high-density characteristic of stable glasses. Extrapolation of the measured transformation times between the stable and normal glass provides estimates of the relaxation times of the equilibrium supercooled liquid at temperatures as much as 30 K below the glass transition temperature. These results demonstrate that polymer stable glasses are an exciting and powerful tool in the study of ultrastable glass and disordered materials in general.

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Fig. 1: Thickness change versus temperature for the initial and subsequent heating and cooling cycles of various kinetically stable glasses.
Fig. 2: MALDI-TOF data for polymers in different phases of stable glass production.
Fig. 3
Fig. 4: Estimating relaxation times for stable glass films of PS.

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Data availability

The datasets generated during and/or analysed during the current study are available in the UW Dataverse repository at Source data are provided with this paper.


  1. Ediger, M. D. Perspective: highly stable vapor-deposited glasses. J. Chem. Phys. 147, 210901 (2017).

    Article  CAS  Google Scholar 

  2. Swallen, S. F. et al. Organic glasses with exceptional thermodynamic and kinetic stability. Science 315, 353–356 (2007).

    Article  CAS  Google Scholar 

  3. Dalal, S. S. & Ediger, M. D. Influence of substrate temperature on the transformation front velocities that determine thermal stability of vapor-deposited glasses. J. Phys. Chem. B 119, 3875–3882 (2015).

    Article  CAS  Google Scholar 

  4. Ediger, M. D., de Pablo, J. J. & Yu, L. Anisotropic vapor-deposited glasses: hybrid organic solids. Acc. Chem. Res. 52, 407–414 (2019).

    Article  CAS  Google Scholar 

  5. Lyubimov, I. et al. Orientational anisotropy in simulated vapor-deposited molecular glasses. J. Chem. Phys. 143, 094502 (2015).

    Article  Google Scholar 

  6. Bagchi, K. et al. Origin of anisotropic molecular packing in vapor-deposited Alq3 glasses. J. Phys. Chem. Lett. 10, 164–170 (2019).

    Article  CAS  Google Scholar 

  7. Lin, P.-H., Lyubimov, I., Yu, L., Ediger, M. D. & de Pablo, J. J. Molecular modeling of vapor-deposited polymer glasses. J. Chem. Phys. 140, 204504 (2014).

    Article  Google Scholar 

  8. Svorcik, V., Rybka, V., Efimenko, K. & Hnatowicz, V. Deposition of polystyrene films by vacuum evaporation. J. Mat. Sci. Lett. 16, 1564–1566 (1997).

    Article  CAS  Google Scholar 

  9. Zhang, J., Con, C. & Cui, B. Electron beam lithography on irregular surfaces using an evaporated resist. ACS Nano 8, 3483–3489 (2014).

    Article  CAS  Google Scholar 

  10. Wubbenhorst, M., Kasina, A., Capponi, S., Vanroy, B. & Napolitano, S. Ultrathin polymer films by single molecule deposition. J. Non-Cryst. Sol. 407, 270–276 (2015).

    Article  CAS  Google Scholar 

  11. Guo, Y. et al. Ultrastable nanostructured polymer glasses. Nat. Mater. 11, 337–343 (2012).

    Article  CAS  Google Scholar 

  12. Yoon, H., Koh, Y. P., Simon, S. L. & McKenna, G. B. An ultrastable polymeric glass: amorphous fluoropolymer with extreme fictive temperature reduction by vacuum pyrolysis. Macromolecules 50, 4562–4574 (2017).

    Article  CAS  Google Scholar 

  13. Chai, Y., Raegen, A. N., Zhu, S. & Forrest, J. A. Crystallization of low molecular weight atactic polystyrene. Soft Matter 14, 6883–6891 (2018).

    Article  CAS  Google Scholar 

  14. Dalal, S. S., Fakhraai, Z. & Ediger, M. D. High-throughput ellipsometric characterization of vapor-deposited indomethacin glasses. J. Phys. Chem. B 117, 15415–15425 (2013).

    Article  CAS  Google Scholar 

  15. Yang, Z., Fujii, Y., Lee, F. K., Lam, C. H. & Tsui, O. K. C. Glass transition dynamics and surface layer mobility in unentangled polystyrene films. Science 328, 1676–1679 (2010).

    Article  CAS  Google Scholar 

  16. Zhu, S., Chai, Y. & Forrest, J. A. Evaporative purification to produce highly monodisperse polymers: application to polystyrene for n = 3–13 and quantification of Tg from oligomer to polymer. Phys. Rev. Mat 1, 025605 (2017).

    Google Scholar 

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The authors acknowledge discussions with M. Ediger and Z. Fakhraai. Financial support from Natural Sciences and Research Council of Canada is gratefully acknowledged. Research at Perimeter Institute is supported by the Government of Canada through Industry Canada and by the Province of Ontario through the Ministry of Economic Development and Innovation. J.A.F. thanks the ESPCI for funding through the Paris Sciences Chair program.

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Authors and Affiliations



A.N.R. performed experiments, data analysis and contributed to the writing and editing of the manuscript. J.Y. and Q.Z. performed experiments, data analysis and contributed to the editing of the manuscript. J.A.F. conceived the experiments, contributed to data analysis, wrote the draft manuscript and contributed to the editing of the manuscript.

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Correspondence to James A. Forrest.

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Supplementary information

Supplementary Information

Supplementary Figs. 1–7, methods and discussion.

Source data

Source Data Fig. 1

Thickness versus temperature data used in Fig. 1.

Source Data Fig. 2

Histogram data from MALDI

Source Data Fig. 3

Density data for TgTf.

Source Data Fig. 4

Transformation kinetics data.

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Raegen, A.N., Yin, J., Zhou, Q. et al. Ultrastable monodisperse polymer glass formed by physical vapour deposition. Nat. Mater. 19, 1110–1113 (2020).

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