Low temperature chemical vapour deposition of ruthenium and ruthenium dioxide on polymer surfaces

Abstract

Thin films of ruthenium or ruthenium dioxide can be prepared on polymer films supported on aluminium disks by chemical vapour deposition (CVD) from the volatile precursor ruthenium tetroxide, RuO₄, by using hydrogen as reducing carrier gas. On very thin (ca. 0.7 µm) spin-cast polymer films on aluminium, ruthenium metal was deposited under mild conditions. These ruthenium films were crystalline when formed on polyurethane or poly(methyl methacrylate) but mostly amorphous when formed on polystyrene or poly(ether/ester)polyurethane block copolymers. On thicker polymer films (ca. 75 µm), the films formed were composed primarily of RuO₂ with lesser amounts of ruthenium metal. The films were characterized by using XPS, Auger, XANES, XRD and SEM techniques.

References

1. M. L. Green, M. E. Gross, L. E. Papa, K. J. Schnoes and D. Brasen, J. Electrochem. Soc., 1985, 132, 2677; J. C. Viguie and J. J. Spitz, J. Electrochem. Soc., 1975, 122, 585.
2. M. Wittmer, J. Vac. Sci. Technol. A, 1984, 2, 273; L. Krusin-Elbaum, M. Wittmer and D. S. Yee, Appl. Phys. Lett., 1987, 50, 1879; E. Kolawa, F. C. T. So, E. T. S. Pan and M. A. Nicolet, Appl. Phys. Lett., 1987, 50, 854; L. Krusin-Elbaum and M. Wittmer, J. Electrochem. Soc., 1988, 135, 2610.
3. J. Lee, S. Min and S. H. Choh, Jpn. J. Appl. Phys., 1994, 33, 7080; Q. X. Jia and W. A. Anderson, Appl. Phys. Lett., 1990, 57, 304.
4. Q. X. Jia, Z. Q. Shi, K. L. Jiao and W. A. Anderson, Thin Solid Films, 1991, 196, 29; I. K. Yoo and S. B. Desu, Phys. Status Solidi A, 1992, 133, 565; J. N. Crosby and R. S. Hanley, US Pat., 4250210, 1981.
5. T. Takagi, I. Oizuki, I. Kobayashi and M. Okada, Jpn. J. Appl. Phys., 1995, 34, 4104; G. R. Bai, A. Wang, C. M. Foster and J. Vetrone, Thin Solid Films, 1997, 310, 75.
6. J. Si and S. B. Desu, J. Mater. Res., 1993, 8, 2644; P. C. Liao, S. Y. Mar, W. S. Ho, Y. S. Huang and K. K. Tiong, Thin Solid Films, 1996, 287, 74; W. C. Shin and S. G. Yoon, J. Electrochem. Soc., 1997, 144, 1055.
7. Z. Yuan, R. J. Puddephatt and M. Sayer, Chem. Mater., 1993, 5, 908.
8. Y. Senzaki, F. B. McCormick and W. L. Gladfelter, Chem. Mater., 1992, 4, 747; Y. Senzaki, W. L. Gladfelter and F. B. McCormick, Chem. Mater., 1993, 5, 1715.
9. E. P. Boyd, D. R. Ketchum, H. Deng and S. G. Shore, Chem. Mater., 1997, 9, 1154.
10. Y. Koda, J. Chem. Soc., Chem. Commun., 1986, 1347.
11. D. J. Pedder, Electrical Components, Science and Technology, Gordon and Breach Ltd., New York, 1976, vol. 2; R. G. Vadimsky, R. P. Frankenthal and D. E. Thompson, J. Electrochem. Soc., 1979, 126, 2017.
12. S. Serghini-Monim, P. R. Norton and R. J. Puddephatt, J. Phys. Chem. B, 1997, 101, 7808; S. Serghini-Monim, P. R. Norton, R. J. Puddephatt, K. D. Pollard and J. R. Rasmussen, J. Phys. Chem. B, 1998, 102, 1450.
13. R. Vitali and E. Montani, Polymer, 1980, 21, 1220; J. S. Trent, J. I. Scheinbeim and P. R. Couchman, J. Polym. Sci. Polym. Lett., 1981, 19, 315; P. Gaylarde and I. Sarkany, Science, 1968, 161, 1157; J. S. Trent, J. I. Scheinbeim and P. R. Couchman, Macromolecules, 1983, 16, 589.
14. W. P. Griffith, The Chemistry of the Rarer Platinum Metals (Os, Ru, Ir and Rh), Wiley-Interscience, New York, 1967; D. G. Lee, Oxidation—Techniques and Applications in Organic Synthesis, ed. R. L. Augustine, Marcel Dekker, New York, 1969; D. G. Lee and M. van den Engh, Oxidation in Organic Chemistry, ed. W. S. Trahanovsky, Academic Press, New York, 1973.
15. K. S. Kim and N. J. Winograd, J. Catal., 1974, 35, 66; G. E. Muilenburg, Handbook of X-Ray Photoelectron Spectroscopy, Perkin-Elmer, Eden Prairie, MN, USA, 1979; L. C. Feldman and J. W. Mayer, Fundamentals of Surface and Thin Film Analysis, North Holland, New York, 1986; A. Iembo, F. Fuso, E. Arimondo, C. Ciofi, G. Pennelli, G. M. Curro, F. Neri and M. Allegrini, J. Mater. Res., 1997, 12, 1433.
16. Y. J. Kim, Y. Gao and S. A. Chambers, Appl. Surf. Sci., 1997, 120, 250; J. F. Moulder, W. F. Stickle, P. W. Sobol and K. D. Bonben, Handbook of X-Ray Photoelectron Spectroscopy, ed. J. Chastain, Perkin-Elmer, New York, 1992.
17. L. E. Davis, Handbook of Auger Electron Spectroscopy, Perkin-Elmer, Eden Prairie, MN, USA, 1978.
18. V. Svorcik, V. Rybka, V. Hnatowicz, L. Bacakova, V. Lisa and F. Kocourek, J. Mater. Chem., 1995, 5, 27; M. Collaud, S. Nowak, O. M. Kuttel, P. Groning and L. Schlapbach, Appl. Surf. Sci., 1993, 72, 19; J. E. Klemberg-Sapieha, O. M. Kuttel, L. Martinu and M. R. Wertheimer, J. Vac. Sci. Technol. A, 1991, 9, 29.
19. J. E. Muller, O. Jepsen and J. W. Wilkins, Solid State Commun., 1982, 42, 365.
20. T. K. Sham, Phys. Rev. B: Condens. Matter, 1985, 31, 1888.
21. M. Brown, R. S. Peierls and E. A. Stern, Phys. Rev. B: Condens. Matter, 1977, 15, 738.
22. D. B. Rogers, R. D. Shannon, A. W. Sleight and J. L. Gillson, Inorg. Chem., 1969, 4, 841.
23. Powder Diffraction Data, file card #6.663 (Ruthenium); card #21.1172 (Ruthenium dioxide), JCPDS, Pennsylvania, 1976.