Jpn. J. Appl. Phys. 43 (2004) pp. 4363-4367  |Previous Article| |Next Article|  |Table of Contents|
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Pulse Radiolysis Study on Proton and Charge Transfer Reactions in Solid Poly(methyl methacrylate)

Atsuro Nakano, Kazumasa Okamoto, Takahiro Kozawa and Seiichi Tagawa

(Received January 26, 2004; accepted March 25, 2004; published July 7, 2004)

Poly(methyl methacrylate) (PMMA) is a good matrix for a case study aimed at understanding reaction mechanisms of electron beam, X-ray and EUV resists. Radiation-induced reactions and proton dynamics of solid PMMA were studied under room temperature by pulse radiolysis. PMMA samples were doped with pyrene (Py), crystal violet lactone (CVL) or an anion scavenger to observe charge and proton transfer reactions in the solid matrix. The time-dependent behavior of ionic radicals was observed with the time resolution of 10 ns. The electron transfer from PMMA anion radicals to the anion scavenger or Py was observed in the time range of several hundred nanoseconds. The dynamics of protons generated in irradiated PMMA was traced using CVL. The growth of optical absorbance attributed to proton adducts of CVL was observed in the time range of several hundreds minutes. Protons derived from PMMA cation radicals have a long lifetime and migrated in the solid PMMA matrix.

URL: http://jjap.jsap.jp/link?JJAP/43/4363/
DOI: 10.1143/JJAP.43.4363
KEYWORDS:PMMA, resist, crystal violet lactone, proton transfer, charge transfer

References | Citing Articles (19)

1. A. R. Shultz: J. Polym. Sci. 35 (1959) 369.
2. A. Todd: J. Polym. Sci. 42 (1960) 223.
3. C. David, D. Fuld and G. Geuskens: Makromol. Chem. 139 (1970) 269.
4. C. David, F. D. Bie and G. Geuskens: Makromol. Chem. 176 (1975) 3493.
5. S. K. Ho and S. Siegel: J. Chem. Phys. 50 (1969) 1142[AIP Scitation].
6. M. Ogasawara, M. Tanaka and H. Yoshida: J. Phys. Chem. 91 (1987) 937[CrossRef].
7. M. Szadkowska-Nicze, M. Kiszka and J. Mayer: J. Polym. Sci. Part A 35 (1997) 299.
8. M. Szadkowska-Nicze and J. Mayer: J. Polym. Sci. Part A 36 (1998) 1209.
9. M. Szadkowska-Nicze and J. Mayer: J. Polym. Sci. Part A 39 (2001) 4110.
10. M. Szadkowska-Nicze and J. Mayer: Res. Chem. Intermed. 27 (2001) 823.
11. G. Geuskens and C. David: Makromol. Chem. 165 (1973) 273.
12. A. Torikai, H. Kato and Z. Kuri: J. Polym. Sci., Polym. Chem. Ed. 14 (1976) 1065.
13. A. Torikai and H. Mishina: J. Polym. Sci., Polym. Chem. Ed. 19 (1981) 2297.
14. T. Ichikawa and H. Yoshida: J. Polym. Sci. Part A 28 (1990) 1185.
15. M. Tanaka, H. Yoshida and T. Ichikawa: Polym. J. 22 (1990) 835.
16. T. Ichikawa, K. Oyama, T. Kondho and H. Yoshida: J. Polym. Sci. Part A 32 (1994) 2487.
17. T. Kozawa, A. Saeki, A. Nakano, Y. Yoshida and S. Tagawa: J. Vac. Sci. Technol. B 21 (2003) 3149[AIP Scitation].
18. S. Tagawa, S. Nagahara, T. Iwamoto, M. Wakita, T. Kozawa, Y. Yamamoto, D. Werst and A. D. Trifunac: Proc. SPIE 3999 (2000) 204[AIP Scitation].
19. H. Tachikawa, H. Yoshida and M. Ogasawara: Radiat. Phys. Chem. 37 (1991) 107.
20. S. Nagahara, Y. Yamashita, T. Taguchi, T. Kozawa, Y. Yoshida and S. Tagawa: Jpn. J. Appl. Phys. 35 (1996) 6491[JSAP].
21. K. Kobayashi, S. Tagawa, S. Daff, I. Sagami and T. Shimizu: J. Biol. Chem. 276 (2001) 39864.
22. S. Arai, A. Kira and M. Imamura: J. Phys. Chem. 81 (1977) 110[CrossRef].
23. S. Tsuji, T. Kozawa, Y. Yamamoto and S. Tagawa: J. Photopolym. Sci. Technol. 13 (2000) 733.
24. V. K. Milinchuk and V. I. Tupikov: Organic Radiation Chemistry Handbook (Ellis Horwood Limited, Chichester, 1989) p. 50.
25. Y. Kaneko and D. C. Neckers: J. Phys. Chem. A 102 (1998) 5356[CrossRef].
26. J. Brandrup and E. H. Immergut: Polymer Handbook Second Edition (John Wiley & Sons, New York, 1974) p. III-148.
27. L. C. E. Struik: Polymer 28 (1987) 1869.
28. M. Christoff and T. D. Z. Atvars: Macromolecules 32 (1999) 6093.