Small Molecule Diffusion in Polymer Ultra-Thin Films


The influence of film thickness and polymer molecular weight on the diffusion coefficient of water in poly(methyl methacrylate) thin films supported on gold coated surfaces has been studied using vapor sorption experiments via quartz crystal microbalance (QCM) methods. Diffusion coefficients for films ranging in thickness from approximately 1 μm to 50 nm were determined. It is observed that the diffusion coefficient of water in PMMA on weakly interacting substrates is a strong function of film thickness, and that the diffusion coefficient decreases drastically as film thickness is reduced below a critical thickness value. Furthermore, it is found that polymer molecular weight also appears to play an important role in determining the diffusion behavior of such polymer thin film systems.

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  1. 1.

    Perry, M.L.; Fuller, T.F., J. Electrochem. Soc., 149(7), S59-S67 (2002).

    CAS  Article  Google Scholar 

  2. 2.

    Future trends in microelectronics (editors: Serge Luryi, Jimmy Xu, Alex Zaslavsky) John Wiley & Sonds: New York (1999).

    Google Scholar 

  3. 3.

    Chrisey, D. B.; Pique, A.; McGill, R. A.; Horwitz, J. S.; Ringeisen, B. R.; Bubb, D. M.; Wu, P. K., Chem. Rev., 103(2), 553-576 (2003).

    CAS  Article  Google Scholar 

  4. 4.

    Koros, W.J.; Zimmerman, C.M. “Transport and barrier properties,” from Comprehensive Desk Reference of Polymer Characterization (Brady, R.F. editor) 680-690 (2003).

  5. 5.

    Ellison, C.J.; Torkelson, J.M., Nature Mater., 21, 695-700 (2003).

    Article  Google Scholar 

  6. 6.

    W. Hubbell, H. Brandt, Z. Munir, J. Polym. Sci., Part B: Polym. Phys., 13, 493 (1975).

    CAS  Google Scholar 

  7. 7.

    E. Sacher, J. Susko, J. Appl. Polym. Sci., 26, 679 (1981).

    CAS  Article  Google Scholar 

  8. 8.

    S. Numata, K. Fujisaki, N. Kinjo, Polymer, 28, 2282 (1987).

    CAS  Article  Google Scholar 

  9. 9.

    G. Sykes, A. Clair, J. Appl. Polym. Sci., 32, 3725 (1986).

    Article  Google Scholar 

  10. 10.

    D. Yang, W.J. Koros, H. Hopfenberg, V. Stannett, J. Appl. Polym. Sci., 30,1035 (1985).

    CAS  Article  Google Scholar 

  11. 11.

    D. Yang, W. J. Koros, H. Hopfenberg, V. Stannet, J. Appl. Polym. Sci., 31,1619 (1986).

    CAS  Article  Google Scholar 

  12. 12.

    K. Okamoto, N. Tanihara, H. Watanabe, K. Tanaka, H. Kita, A. Nakamura, Y. Kusuki, K. Nakagawa, J. Polym. Sci., Part B: Polym. Phys., 30,1223-1231 (1992).

    CAS  Article  Google Scholar 

  13. 13.

    K. Ichikawa, T. Mori, H. Kitano, M. Fukuda, A. Mochizuki, M. Tanaka, J. Polym. Sci., Part B: Polym. Phys., 39, 2175-2182 (2001).

    CAS  Article  Google Scholar 

  14. 14.

    M. Ree, S. Swanson, W. Volksen, Polymer, 34, 1423 (1993).

    CAS  Article  Google Scholar 

  15. 15.

    J. Jou, R. Huang, P. Huang, W. Shen, J. Appl. Polym. Sci., 43, 857-875 (1991).

    CAS  Article  Google Scholar 

  16. 16.

    J. Jou, P. Huang, Polymer, 33, 1218-1222 (1992).

    CAS  Article  Google Scholar 

  17. 17.

    C.M. Berger, C.L. Henderson, Polymer, 44, 2101-2108 (2003).

    CAS  Article  Google Scholar 

  18. 18.

    C. Lu, A. Czanderna, Applications of Piezoelectric Quartz Crystal Microbalances, (New York:Elsevier, 1984, chapter 2).

    Google Scholar 

  19. 19.

    H. Han, J. Seo, M. Ree, S. Pyo, C. Gryte, Polymer, 39(13), 2963-2972 (1998).

    CAS  Article  Google Scholar 

  20. 20.

    S. Despond, E. Espuche, A. Domard , J. Polym. Sci., Part B: Polym. Phys., 39, 3114 (2001).

    CAS  Article  Google Scholar 

  21. 21.

    J. Seo, K. Cho, H. Han, Polym. Degrad. Stab., 74, 133 (2001).

    CAS  Article  Google Scholar 

  22. 22.

    K. Mueller, W. J. Koros, Y. Wang, C. G. Willson, Proc. SPIE, 3049, 871 (1997).

  23. 23.

    A.L. Hines, R.N. Maddox, Mass Transfer: Fundamentals and Applications, (Englewood Cliffs:Prentice-Hall, 1985, chapter 4).

  24. 24.

    J.comyn, Polymer Permeability, (New York:Elsevier; 1985) p. 7, 345-350.

    Google Scholar 

  25. 25.

    W. Vieth, Diffusion In and Through Polymers: Principles and Applications, (New York:Hanser; 1991) p. 19–47.

    Google Scholar 

  26. 26.

    Singh, L.; Henderson, C.L.; Ludovice, P.J., Proceedings of SPIE-The International Society for Optical Engineering, 5753(Pt. 2, Advances in Resist Technology and Processing XXII), pp. 1202-1211, (2005).

  27. 27.

    McCaig, M.S.; Paul, D.R.; Barlow, J.W., Polymer, 41(2), 639-648 (1999).

    Article  Google Scholar 

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Ordaz, I., Singh, L., Ludovice, P. et al. Small Molecule Diffusion in Polymer Ultra-Thin Films. MRS Online Proceedings Library 899, 505 (2005).

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