Analysis and Interpretation of Scanning Tunneling Microscopy Images in an Electrochemical Environment: Copper on AU(111)

  • W. Haiss
  • J. K. Sass
  • D. Lackey
  • M. van Heel


The electrochemical deposition of a copper monolayer on Au(111) has been studied by STM in H2SO4 and Na2SO4 solutions. Three different superstructures, which are attributed to the adsorption of either HSO 4 , SO 4 2− or both anions, have been observed for the full monolayer. Evidence for the expected epitaxial (1 × 1) overlayer was also obtained at very negative potentials, by avoiding bulk copper growth. A novel STM data analysis by multivariate statistical procedures is shown to provide detailed information, which is not evident in the raw data. The need for a better understanding of the tunneling and imaging mechanisms in an electrochemical environment is emphasized.


Scanning Tunneling Microscopy Multivariate Statistical Analysis Desorption Peak Scan Tunneling Microscopy Image Electrochemical Environment 
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  1. 1.
    J. K. Gimzewski and J. K. Sass, Fundamental aspects of scanning tunneling microscopy in polar solvents, in.. “Proc. ICTP Conf. Cond. Matt. Phys. Aspects of Electrochem.,” M. P. Tosi and A. A. Kornyshev, eds., World Scientific, New Jersey, 303–326 (1991).Google Scholar
  2. 2.
    See for example: J. OM. Bockris and A. K. N. Reddy,“Modem Electrochemistry,” Plenum Press, New York (1977).Google Scholar
  3. 3.
    R. N. Barnett, U. Landmann and A. Nitzan, Primary events following electron injection into water and adsorbed water layers, J. Chem. Phys. 93: 6535–6542 (1990).CrossRefGoogle Scholar
  4. 4.
    J. K. Sass and J. K. Gimzewski, Solvent dynamical effects in scanning tunneling microscopy with a polar liquid in the gap, J. Electroanal. Chem. 308: 333–337 (1991).CrossRefGoogle Scholar
  5. 5.
    K. L. Sebastian and G. Doyen, Electrochemical scanning tunneling microscopy: Does the orientational polarisation of the liquid play any role?, Surf. Sci.,in press.Google Scholar
  6. 6.
    K. Bange, B. Straehler, J. K. Sass and R. Parsons, The interaction of Br with Ag(110): Comparison of electrochemical and gas-phase adsorption measurements, J. Electroanal. Chem. 229: 87–98 (1987).CrossRefGoogle Scholar
  7. 7.
    J. K. Sass, J. Schott and D. Lackey, Prospects for the direct determination of the dielectric constantof water in the double layer using model adsorption experiments in UHV: Coadsorption of Cs and H2O on Cu(110), J. Electroanal. Chem. 283, 441–448 (1990).CrossRefGoogle Scholar
  8. 8.
    D. M. Kolb, The initial stages of metal deposition: An atomistic view, Schering Lecture Publications, 2:1–35, Schering Research Foundation, Berlin (1991).Google Scholar
  9. 9.
    O. M. Magnussen, J. Hotlos, R. J. Nichols, D. M. Kolb and R. J. Behm, Atomic structure of Cu adlayers on Au(100) and Au(111) electrodes observed by in situ scanning tunneling microscopy, Phys. Rev. Lett. 64: 2929–2932 (1990).CrossRefGoogle Scholar
  10. 10.
    T. Hachiya, H. Honbo and K. Itaya, Detailed underpotential deposition of copper on gold(111) in aqueous solutions, J. Electroanal. Chem. 315: 275–291 (1991).CrossRefGoogle Scholar
  11. 11.
    S. Manne, P. K. Hansma, J. Massie, V. Elings and A. A. Gerwith, Atomic resolution electrochemistry with the atomic force microscope: Copper deposition on gold surfaces, Science 251: 183–186 (1991).CrossRefGoogle Scholar
  12. 12.
    M. van Heel, Classification of very large electron microscopical image data sets, Optik 82: 14–126 (1989).Google Scholar
  13. 13.
    E. J. Boekema and M. van Heel, Molecular shape of lumbricus terrestris erythrocruorin studied by electron microscopy and image analysis, Biochim. Biophys. Acta 957: 370–379 (1989).CrossRefGoogle Scholar
  14. 14.
    L. Borland and M. van Heel, Classification of image data in conjugate representation spaces, J. Opt. Soc. Am. A 7: 601–610 (1990).CrossRefGoogle Scholar
  15. 15.
    K. H. Besocke, An easily operable scanning tunneling microscope, Surf Sci. 181: 145–153 (1987).CrossRefGoogle Scholar
  16. 16.
    W. Haiss, D. Lackey, J. K. Sass and K. H. Besocke, Atomic resolution scanning tunneling microscopy images of Au(111) surfaces in air and polar organic solvents, J. Chem. Phys. 95: 2193–2196 (1991).CrossRefGoogle Scholar
  17. 17.
    W. Haiss, D. Lackey, J. K. Sass, H. Meyer and R. J. Nichols, A determination of copper overlayer structures on Au(l11) in the presence of electrolyte additives, Chem. Phys. Lett. 200: 343–349 (1992).CrossRefGoogle Scholar
  18. 18.
    J. V. Barth, H. Brune, G. Ertl and R. J. Behm, Scanning tunneling microscopy observations on the reconstructed Au(111) surface: Atomic structure, long-range superstructure, rotational domains, and surface defects, Phys. Rev. B 42, 9307–9318 (1990).CrossRefGoogle Scholar
  19. 19.
    X. Gao, A. Hamelin and M. J. Weaver, Atomic relaxation at ordered electrode surfaces probed by scanning tunneling microscopy: Au(111) in aqueous solution compared to ultrahigh-vacuum environments, J. Chem. Phys. 95: 6993–6996 (1991).CrossRefGoogle Scholar
  20. 20.
    N. J. Tao and S. M. Lindsay, Observations of the 22 x J3 reconstruction of Au(111) under aqueous solutions using scanning tunneling microscopy, J. Appl. Phys. 70: 5141–5143 (1991).CrossRefGoogle Scholar
  21. 21.
    P. Zelenay, L. M. Rice-Jackson, A. Wieckowski and J. Gawlowski, Radioactive labeling study of isulfate adsorption on copper adatoms deposited on the gold electrode in neutral media, Surf. Sci. 256: 253–263 (1991).CrossRefGoogle Scholar
  22. 22.
    STM-images of C,molecules adsorbed in UHV on gold and copper surfaces are currently being analyzed by the MSA method and the preliminary results are very encouraging; J. K. Gimzcwski, R. Schlittler, M. van Heel and J. K. Sass, to be published.Google Scholar
  23. 23.
    O. M. Magnussen, J. Hageböck, J. Hotlos and R. J. Behm, In situ scanning tunnelling microscopy observations of a disorder-order transition in hydrogensulfate adlayers on Au(111), Faraday Discuss., 94:154–163 (1992).Google Scholar

Copyright information

© Springer Science+Business Media New York 1994

Authors and Affiliations

  • W. Haiss
    • 1
  • J. K. Sass
    • 1
  • D. Lackey
    • 1
  • M. van Heel
    • 1
  1. 1.Fritz-Haber-Institut der MPGBerlinGermany

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