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Metallurgical factors influencing the corrosion of aluminum, Al-Cu, and Al-Si alloy thin films in dilute hydrofluoric solution

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Abstract

The corrosion behavior of sputter-deposited Al, Al-Cu, and Al-Si alloy thin films in dilute hydrofluoric (HF) acid solution was investigated. These materials maintain a thin aluminum oxide film in dilute HF solutions and, consequently, are susceptible to localized corrosion. Pit densities increase for the alloys with Cu and, to a lesser extent, Si additions. Open circuit potentials (OCP) are more positive for such alloys relative to the OCP of pure Al. Metastable pits in Al-Cu alloys are formed in Cu-depleted zones at grain boundaries which are galvanically coupled to adjacent θ-Al2Cu precipitates. Metastable pits in Al-Si alloys are formed in the Al matrix which is galvanically coupled to adjacent elemental Si nodules. θ-Al2Cu has different electrochemical characteristics than Al, even though both maintain a thin Al oxide in dilute HF solutions. θ-Al2Cu has a more positive OCP than pure Al and facilitates cathodic reactions at enhanced rates relative to pure Al. Hence, its presence raises the potential of the adjacent pure Al grain boundary to potentials which increase the probability of metastable pitting. Evidence is also presented which suggests that metastable pit growth may be cathode limited. A new hypothesis describing one mechanism by which θ-Al2Cu supports cathodic electron transfer re-actions is discussed.

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References

  1. S. Thomas and H.M. Berg:IEEE Transactions on Components,Hybrides, and Manufacturing Technology (CHMT-10), 1987, pp. 252–57.

  2. S. Mayumi, I. Murozono, H. Nanatsue, and S. Ueda:J. Electrochem. Soc, 1990, vol. 137 (6), pp. 1861–67.

    Article  CAS  Google Scholar 

  3. J. Zahavi, M. Rotel, H.C. Huang, and P. Totta:International Corrosion Congress, Toronto, ON, Canada, 1984, pp. 311–16.

  4. J.R. Scully, R.P. Frankenthal, K.J. Hanson, D.J. Siconolfi, and J.D. Sinclair:J. Electrochem., 1990, vol. 137 (5), pp. 1365–73.

    Article  CAS  Google Scholar 

  5. J.L. Murray and A.J. McAlister:Bull. Alloy Phase Diagrams, 1984, vol. 5 (1), pp. 74–84.

    Article  CAS  Google Scholar 

  6. J. Fleming: Microelectronics Device Development Laboratories, Sandia National Laboratories, July 1990, private communication.

  7. J.O. McCaldin and H. Sankur:Appl. Phys. Lett., 1971, vol. 19 (12), pp. 524–27.

    Article  CAS  Google Scholar 

  8. A.P. Bond, G.F. Boiling, H.A. Domian, and H. Biloni:J. Electrochem., 1966, vol. 113, p. 773.

    Article  Google Scholar 

  9. H. Bohni and H.H. Uhlig:J. Electrochem., 1969, vol. 116, p. 906.

    Article  Google Scholar 

  10. M. Pourbaix:Atlas of Electrochemical Equilibria in Aqueous Solutions, NACE, Houston, TX, 1974, pp. 168–76.

    Google Scholar 

  11. J.W. Schultze: inPassivity of Metals, R.P. Frankenthal and J. Kruger, eds., The Electrochemical Soc, Inc., Princeton, NJ, 1978, p. 82.

    Google Scholar 

  12. J.R. Galvele and S.M. de De Micheli:Corros. Sci., 1970, vol. 10, p. 795.

    Article  CAS  Google Scholar 

  13. R. Holliger and H. Bohni: inComputer Aided Acquisition and Analysis of Corrosion Data, M.W. Kendig, U. Bertocci, and J.E. Strutt, eds., The Electrochemical Society Proceedings Series, Pennington, NJ, 1985, vol. 85–3, p. 200.

    Google Scholar 

  14. A.K. Covington and J.M. Thain:J. Chem. Ed., 1972, vol. 49 (8), p. 554.

    Article  CAS  Google Scholar 

  15. M. Salomen and B.K. Stevenson:J. Chem. Eng. Data, 1974, vol. 19 (1), p. 42.

    Article  Google Scholar 

  16. H.N. Farrer and F.J.C. Rossotti:J. Inorg. Nucl. Chem., 1965, vol. 26, p. 1959.

    Article  Google Scholar 

  17. W.J. Hamer and Y.-C. Wu:J. Research Nat. Bureau Standards-A. Physics and Chemistry, 1970, vol. 74A (6), p. 761.

    Article  Google Scholar 

  18. ASTM Standard G-3, ASTM Annual Book of Standards, ASTM, Philadelphia, PA, 1990, vol. 03.02, p. 60.

  19. H.P. Hack, P.J. Moran, and J.R. Scully:The Measurement and Correction of Electrolyte Resistance in Electrochemical Tests, L.L. Scribner and S.R. Taylor, eds., ASTM STP 1056, ASTM, Philadelphia, PA, 1989, pp. 5–26.

    Google Scholar 

  20. S.J. Ketcham and F.H. Haynie:Corrosion, 1963, vol. 19, pp. 242t-246t.

    Article  CAS  Google Scholar 

  21. J.W. Evancho and J.T. Staley:Metall. Trans., 1974, vol. 5, pp. 43–47.

    Article  CAS  Google Scholar 

  22. M.J. Carr and A.D. Romig, Jr.:Proc. 44th EMSA Meeting, San Francisco Press, San Francisco, CA, 1988, pp. 916–17.

    Google Scholar 

  23. A.D. Romig, Jr.: Sandia Report SAND82-2938, Sandia National Laboratories, Albuquerque, NM, Mar. 1983.

  24. A.D. Romig, Jr.:Characterization of Interfacial Chemistry by Analytical Electron Microscopy, Defect and Diffusion Forum, Trans Tech Publications, Aedermanns-dorf, Switzerland, 1988, vol. 59, pp. 179–96.

    Google Scholar 

  25. A.D. Romig, Jr., S.J. Plimpton, R.L. Mykelbust, and D.E. Newbury:Microbeam Analysis—1990, San Francisco Press, San Francisco, CA, 1991, pp. 275–80.

    Google Scholar 

  26. Kratos XSAM 800 commercial software package, Kratos Limited Analytical Instruments, Manchester, United Kingdom.

  27. D.R. Frear, J.E. Sanchez, A.D. Romig, Jr., and J.W. Morris, Jr.:Metall. Trans. A, 1990, vol. 21A, pp. 2449–58.

    Article  CAS  Google Scholar 

  28. H.B. Aaron and H.I. Aaronson:Acta Metall., 1968, vol. 16, p. 789.

    Article  CAS  Google Scholar 

  29. J. Kruger and K. Rhyne:Nucl. Chem. Waste Management, 1982, vol. 3, p. 205.

    Article  CAS  Google Scholar 

  30. Y. Murty, T. Kattamis, and O. Devereux:Corrosion, June 1975, vol. 31 (6),

  31. B. Mazurkiewicz and A. Piotrowski:Corros. Sci., 1983, vol. 23 (7), pp. 697–707.

    Article  CAS  Google Scholar 

  32. R.H. Brown, W.L. Fink, and M.S. Hunter:Trans. AIME, 1941, vol. 143, p. 115.

    Google Scholar 

  33. ASM Metals Handbook on Corrosion, ASM, Metals Park, OH, 1987, vol. 13, p. 584.

  34. J.R. Scully: inCritical Factors in Localized Corrosion, G.S. Frankel and R.C. Newman, eds., The Electrochemical Society, Pennington, NJ, 1992, vol. 92–9, pp. 144–56.

    Google Scholar 

  35. K.J. Vetter and H.H. Streblow:Localized Corrosion, NACE-3,, R.W. Staehle, B.F. Brown, J. Kruger, and A. Agrawal, eds., NACE, Houston, TX, 1974, pp. 240–60.

    Google Scholar 

  36. G.S. Frankel:Corros. Sci., 1990, vol. 30 (12), pp. 1203–18.

    Article  CAS  Google Scholar 

  37. G.S. Frankel, L. Stockert, F. Hunkeler, and H. Bohni:Corros. J., 1987, vol. 43 (7), pp. 429–36.

    Article  CAS  Google Scholar 

  38. D.E. Peebles and J.R. Scully: Sandia National Laboratories, Albuquerque, NM, unpublished research, 1990.

  39. G.E. McGuire, G.K. Schweitzer, and T.A. Carlson:Inorg. Chem., 1973, vol. 12, p. 2450.

    Article  CAS  Google Scholar 

  40. P.E. Larson:J. Electron Spectroscopy Rel. Phenom., 1974, vol. 4, p. 213.

    Article  CAS  Google Scholar 

  41. N.S. McIntyre and M.G. Cook:Anal. Chem., 1975, vol. 47, p. 2208.

    Article  CAS  Google Scholar 

  42. L.C. Feldman and J.W. Mayer:Fundamentals of Surface and Thin Film Analysis, North-Holland, NY, 1986, p. 125.

  43. J.A. Richardson and G.C. Wood:J. Electrochem. Soc, 1973, vol. 120, p. 193.

    Article  CAS  Google Scholar 

  44. F. Mansfeld and H. Shih:J. Electrochem. Soc, 1988, vol. 135, p. 1171.

    Article  CAS  Google Scholar 

  45. J.R. Scully: “Characterization of the Corrosion of Al Thin Films Using Electrochemical Impedance Methods,” ASTM STP1188 on EIS-Analysis and Interpretation, J.R. Scully, D. Silverman, and M. Kendig, eds., ASTM, Philadelphia, PA, in press.

  46. Introduction to Ceramics: W.D. Kingery, H.K. Bowen, and D.R. Uhlmann, eds., John Wiley and Son, New York, NY, 1976, p. 903.

    Google Scholar 

  47. G.D. Davis, W.C. Moshier, J.S. Ahearn, H.F. Hough, and G.O. Gote:J. Vac. Sci. Technol. A, 1987, vol. 5 (4), p. 1152.

    Article  CAS  Google Scholar 

  48. H. Hladky and J.L. Dawson:Corros. Sci., 1981, vol. 21 (4), pp. 317–22.

    Article  CAS  Google Scholar 

  49. H. Hladky and J.L. Dawson:Corros. Sci., 1982, vol. 22 (3), pp. 231–37.

    Article  CAS  Google Scholar 

  50. J. Painot and J. Augustynski:Electrochim. Acta, 1975, vol. 20, p. 747.

    Article  CAS  Google Scholar 

  51. F. Hunkeler and H. Bohni:Corrosion, 1981, vol. 37, p. 645.

    Article  CAS  Google Scholar 

  52. J.W. Schultz and L. Elfenthal:J. Electroanal. Chem., 1986, vol. 204, pp. 153–71.

    Article  Google Scholar 

  53. K. Shimamura, K. Miura, A. Kawashima, K. Asami, and K. Hashimoto:Proc. Symp. on Corrosion and Electrochemical Catalysis on Metallic Glasses, Proc. Electrochem. Soc, The Electrochemical Society, Pennington, NJ, 1988, vol. 88–1, p. 232.

    Google Scholar 

  54. T.N. Taylor and J.A. Martin:J. Vac. Sci. Tech., 1991, vol. A9, pp. 1840–46.

    Article  Google Scholar 

  55. H.H. Strehblow and C.J. Doherty:J. Electrochem. Soc, 1978, vol. 125 (1), pp. 30–33.

    Article  CAS  Google Scholar 

  56. W.D. Mackintosh, F. Brown, and H.H. Plattner:J. Electrochem. Soc, 1974, vol. 121 (10), pp. 1281–86.

    Article  CAS  Google Scholar 

  57. H.H. Streblow, C.M. Melliar-Smith, and W.M. Augustyniak:J. Electrochem. Soc, 1978, vol. 125 (6), pp. 915–19.

    Article  Google Scholar 

  58. G.C. Farlow, P.S. Sklad, C.W. White, and C.J. McHargue:J. Mater. Res., 1990, vol. 5 (7), p. 1502.

    Article  CAS  Google Scholar 

  59. B. Abies, P. Sheng, M.D. Courts, and Y. Arie:Adv. Phys., 1975, vol. 24 (3), p. 407.

    Article  Google Scholar 

  60. J.W. Schultze and U. Stimming:Z. Phys. Chem., 1985, vol. 98, p. 285.

    Article  Google Scholar 

  61. J.W. Schultze and M.M. Haga:Z. Phys. Chem., 1977, vol. 104, p. 73.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Department of Materials Science and Engineering, University of Virginia, 22903, Charlottes ville, VA

    J. R. Scully (Assistant Professor of Materials Science) & C. R. Hills

  2. Sandia National Laboratories, 87185, Albuquerque, NM

    D. E. Peebles (Technical Staff Senior Member, Organization 1830), A. D. Romig (Department Head, Organization 1830) & D. R. Frear (Technical Staff Member, Organization 1820)

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  1. J. R. Scully
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  2. D. E. Peebles
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  4. D. R. Frear
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  5. C. R. Hills
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Scully, J.R., Peebles, D.E., Romig, A.D. et al. Metallurgical factors influencing the corrosion of aluminum, Al-Cu, and Al-Si alloy thin films in dilute hydrofluoric solution. Metall Trans A 23, 2641–2655 (1992). https://doi.org/10.1007/BF02658068

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