Abstract
The electronic properties of nanoclusters of transition (Ni, Co, Cr) and noble (Au, Cu) metals deposited on the surface of highly oriented pyrolytic graphite (HOPG) are studied using the method of X-ray photoelectron spectroscopy. The laws of variation of a change ΔE b in the binding energies of core-level electrons in the initial (ΔE i) and final (ΔE f) states of atoms in nanoclusters, the intrinsic widths γ of photoelectron lines, and their singularity indices α as functions of the metal cluster size d are determined. A qualitative difference in behavior of the ΔE i(d) and α(d) values in metals of the two groups (Ni, Cr versus Co, Cu) is found. The values of the final-state energy (ΔE f < 0) and the line width (Δγ > 0) in the clusters of all metals studied vary in a similar manner. It is shown that a significant contribution to E i is due to a transfer of the valence-shell electrons at the cluster-substrate interface, which is caused by the contact potential difference. The value of an uncompensated charge per nanocluster is determined as a function of the cluster size and the number of atoms in the cluster. The behavior of ΔE f(d) is controlled by the Coulomb energy of a charged cluster and by a decrease in the efficiency of electron screening, which is different in the metals studied. The broadening of photoelectron lines is determined by a spread of the cluster sizes and by lower electron screening in the final Fermi system. An asymmetry of the core-level electron spectra of nanoclusters can be explained using notions about the electron-hole pair excitation near the Fermi level. The effect of the structure of the density of electron states in the d band of transition metals on the asymmetry of photoelectron lines is considered and it is concluded that this structure near the Fermi level qualitatively changes with a decrease in the nanocluster size. The obtained results indicate that the behavior of the electron subsystem of clusters of the d-metals in a size range of 2–10 nm under consideration is close to the behavior of a normal Fermi system.
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References
W. P. Halperin, Rev. Mod. Phys. 58, 533 (1986).
S. H. M. Persson, L. Olofsson, and L. Gunnarsson, Appl. Phys. Lett. 74, 2546 (1999).
V. Yu. Irkhin and Yu. P. Irkhin, Electronic Structure, Correlation Effects, and Physical Properties of d- and f-Metals and Their Compounds (Ural Branch of the Russian Academy of Sciences, Yekaterinburg, Russia, 2004; Cambridge International Science, Cambridge, 2007).
D. P. Woodruff and T. A. Delchar, Modern Techniques of Surface Science (Cambridge University Press, Cambridge, 1986; Mir, Moscow, 1989).
G. Wertheim, in Electron and Ion Spectroscopy of Solids, Ed. by L. Fiermans, J. Vennik, and W. Dekeyser (Plenum, New York, 1978; Mir, Moscow, 1981).
V. V. Nemoshkalenko and V. G. Aleshin, Electron Spectroscopy of Crystals (Naukova Dumka, Kiev, 1976; Plenum, New York, 1979).
T. L. Barr, Modern ESCA: The Principles and Practice of X-ray Photoelectron Spectroscopy (CRC Press, Boca Raton, Florida, United States, 1994), p. 300.
D. Briggs and M. P. Seah, Practical Surface Analysis by Auger and X-ray Photoelectron Microscopy (Wiley, New York, 1983; Mir, Moscow, 1987).
W. F. Egelhoff, Jr., Surf. Sci. Rep. 6, 253 (1987).
G. K. Wertheim, Phys. Rev. B: Condens. Matter 36, 9559 (1987).
X. Ch. Lai, M. A. Pushkin, and V. I. Troyan, Surf. Interface Anal. 36, 1199 (2004).
I. Jirka, Surf. Sci. 232, 307 (1990).
Y. Wu, E. Garfunkel, and T. E. Madey, J. Vac. Sci. Technol., A 14, 1662 (1996).
D.-Q. Yang and E. Sacher, Appl. Surf. Sci. 195, 187 (2002).
S. Zafeiratos and S. Kennou, Surf. Sci. 443, 238 (1999).
M. G. Mason, Phys. Rev. B: Condens. Matter 27, 748 (1983).
M. K. Bahl, S. C. Tsai, and Y. W. Chung, Phys. Rev. B: Condens. Matter 21, 1344 (1980).
B. Richter, H. Kuhlenbeck, H.-J. Freund, and P. S. Bagus, Phys. Rev. Lett. 93, 026 805 (2004).
R. A. Gibbs, N. Winograd, and V. Y. Young, J. Chem. Phys. 72, 4799 (1980).
P. H. Citrin and G. K. Wertheim, Phys. Rev. B: Condens. Matter 27, 3176 (1983).
G. K. Wertheim, Z. Phys. B: Condens. Matter 66, 53 (1987).
V. D. Borman, P. V. Borisyuk, V. V. Lebid’ko, M. A. Pushkin, V. N. Tronin, V. I. Troyan, D. A. Antonov, and D. O. Filatov, Zh. Éksp. Teor. Fiz. 129(2), 343 (2006) [JETP 102 (2), 303 (2006)].
P. W. Anderson, Phys. Rev. Lett. 18, 1049 (1967).
D. C. Langreth, Phys. Rev. B: Solid State 1, 471 (1970).
J. J. Hopfield, Comments Solid State Phys. 2, 2 (1969).
T. T. P. Cheung, Surf. Sci. 140, 151 (1984).
C. Binns, S. H. Baker, C. Demangeat, and J. C. Parlebas, Surf. Sci. Rep. 34, 107 (1999).
C. Binns, Surf. Sci. Rep. 44, 1 (2001).
A. Fritsch and P. Légaré, Surf. Sci. 145, L517 (1984).
A. Fritsch and P. Légaré, Surf. Sci. 162, 742 (1985).
P. H. Citrin and G. K. Wertheim, in Topics in Applied Physics: Photoemission in Solids, Vol. 26: General Principles, Ed. by M. Cardona and L. Ley, (Springer, Heidelberg, 1978), p. 197.
V. N. Nevolin, A. V. Zenkevich, X. Ch. Lai, M. A. Pushkin, V. N. Tronin, and V. I. Troyan, Laser Phys. 11, 824 (2001).
X. Ch. Lai, M. A. Pushkin, V. D. Borman, A. V. Zenkevich, Yu. Yu. Lebedinskiĭ, V. N. Nevolin, V. N. Tronin, and V. I. Troyan, Izv. Akad. Nauk, Ser. Fiz. 64, 702 (2000).
V. D. Borman, A. V. Zenkevich, V. N. Nevolin, M. A. Pushkin, V. N. Tronin, and V. I. Troyan, Zh. Éksp. Teor. Fiz. 130(6), 984 (2006) [JETP 103 (6), 850 (2006)].
M. P. Seah, I. S. Gilmore, and G. Beamson, Surf. Interface Anal. 26, 642 (1998).
NIST X-ray Photoelectron Spectroscopy Database, NIST Standard Reference Database: Version 3.5, Ed. by C. D. Wagner, A. V. Naumkin, and A. Kraut-Vass; http://srdata.nist.gov/xps.
G. K. Wertheim, Phys. Rev. B: Solid State 16, 4256 (1977).
S. Doniach and M. Sunjic, J. Phys.: Condens. Matter 3, 285 (1970).
S. Peredkov, G. Öhrvwall, J. Schulz, M. Lundwall, T. Rander, A. Lindblad, H. Bergersen, A. Rosso, W. Pokapanich, N. Mårtensson, S. Svensson, S. L. Sorensen, O. Björneholm, and M. Tchaplyguine, Phys. Rev. B: Condens. Matter 75, 235407 (2007).
S. B. DiCenzo, S. D. Berry, and E. H. Hartford, Jr., Phys. Rev. B: Condens. Matter 38, 8465 (1988).
W. Eberhardt, P. Fayet, D. M. Cox, Z. Fu, A. Kaldor, R. Sherwood, and D. Sondericker, Phys. Rev. Lett. 64, 780 (1990).
D.-Q. Yang, M. Meunier, and E. Sacher, Appl. Surf. Sci. 173, 134 (2001).
N. Mårtensson and B. Johansson, Phys. Rev. Lett. 45, 482 (1980).
I. Lopez-Salido, D. Ch. Lim, R. Dietsche, N. Bertram, and Y. D. Kim, J. Phys. Chem. B 110, 1128 (2006).
Handbook of Physical Quantities, Ed. by I. S. Grigoriev and E. Z. Meilikhov (Énergoatomizdat, Moscow, 1991; CRC Press, Boca Raton, Florida, United States, 1997); H. B. Michaelson, J. Appl. Phys. 48, 4729 (1977).
B. Gady and R. Reifenberger, J. Appl. Phys. 84, 319 (1998).
W. Song and M. Yoshitake, Appl. Surf. Sci. 251, 14 (2005).
L. D. Landau and E. M. Lifshitz, Course of Theoretical Physics, Vol. 8: Electrodynamics of Continuous Media (Nauka, Moscow, 1982; Butterworth-Heinemann, Oxford, 1984).
N. Ashcroft and N. Mermin, Solid State Physics (Holt, Rinehart and Winston, 1976; Mir, Moscow, 1979).
G. K. Wertheim, S. B. DiCenzo, and D. N. E. Buchanan, Phys. Rev. B: Condens. Matter 33, 5384 (1986).
A. Zangwill, Physics at Surfaces (Cambridge University Press, Cambridge, 1988; Mir, Moscow, 1990).
G. Apai, J. F. Hamilton, J. Stohr, and A. Thompson, Phys. Rev. Lett. 43, 165 (1979).
C. Xu, X. Lai, G. W. Zajac, and D. W. Goodman, Phys. Rev. B: Condens. Matter 56, 13 464 (1997).
P. N. First, J. A. Stroscio, R. A. Dragoset, D. T. Pierce, and R. J. Celotta, Phys. Rev. Lett. 63, 1416 (1989).
H. Hövel, B. Grimm, M. Bödecker, K. Fieger, and B. Reihl, Surf. Sci. 463, L603 (2000).
A. Bettac, L. Köller, V. Rank, and K. H. Meiwes-Broer, Surf. Sci. 402–404, 475 (1998).
H. Hövel, B. Grimm, M. Pollmann, and B. Reihl, Phys. Rev. Lett. 81, 4608 (1998).
D. Spanjaard, C. Guillot, M. C. Desjonqueres, G. Treglia, and J. Lecante, Surf. Sci. Rep. 5, 1 (1985).
M. Cini and P. Ascarelli, J. Phys. F: Met. Phys. 4, 1998 (1974).
P. Ascarelli, M. Cini, G. Missoni, and N. Nistico, J. Phys., Colloq. 38(C2), C2–125 (1977).
G. D. Mahan, Phys. Rev. 163, 612 (1967).
G. K. Wertheim and L. R. Walker, J. Phys. F: Met. Phys. 6, 2297 (1976).
P. Ascarelli, Solid State Commun. 21, 205 (1977).
J. F. Janak, Phys. Rev. B: Solid State 16, 255 (1977).
R. Ahuja, S. Auluck, O. Eriksson, and B. Johansson, J. Phys.: Condens. Matter 9, 9845 (1997).
I. Estermann, S. A. Friedberg, and J. E. Goldman, Phys. Rev. 87, 582 (1952).
D. G. Daunt and C. V. Heer, Phys. Rev. 76, 1324 (1949).
F. Batallan, I. Rosenman, and S. B. Sommers, Phys. Rev. B: Solid State 11, 545 (1975).
C. S. Wang and J. Callaway, Phys. Rev. B: Solid State 9, 4897 (1974).
D. D. Koelling, F. M. Mueller, A. J. Arko, J. B. Ketterson, Phys. Rev. B: Solid State 10, 4889 (1974).
T. S. Smith and J. G. Daunt, Phys. Rev. 88, 1172 (1952).
A. Wexler and W. S. Corak, Phys. Rev. 85, 85 (1952).
R. D. Worley, M. W. Zemansky, and H. A. Boorse, Phys. Rev. 99, 447 (1955).
M. F. Manning and M. I. Chodorow, Phys. Rev. 56, 787 (1939).
N. V. Smith, G. K. Wertheim, S. Hüfner, and M. M. Traum, Phys. Rev. B: Solid State 10, 3197 (1974).
L. Hodges, H. Ehrenreich, and N. D. Lang, Phys. Rev. 152, 505 (1966).
P. H. Citrin, G. K. Wertheim, and Y. Baer, Phys. Rev. B: Solid State 16, 4256 (1977).
P. H. Citrin, G. K. Wertheim, and Y. Baer, Phys. Rev. Lett. 35, 885 (1975).
F. Sette, G. K. Wertheim, Y. Ma, G. Meigs, S. Modesti, and C. T. Chen, Phys. Rev. B: Condens. Matter 41, 9766 (1990).
G. K. Wertheim and D. M. Riffe, Phys. Rev. B: Condens. Matter 52, 14 906 (1995).
G. K. Wertheim, D. M. Riffe, and P. H. Citrin, Phys. Rev. B: Condens. Matter 45, 8703 (1992).
S. Hüfner and G. K. Wertheim, Phys. Rev. B: Solid State 11, 678 (1975).
G. K. Wertheim and D. N. E. Buhanan, Phys. Rev. B: Solid State 16, 2613 (1977).
G. K. Wertheim and S. Hüfner, Phys. Rev. Lett. 35, 53 (1975).
D. M. Riffe, W. Hale, B. Kim, and J. L. Erskine, Phys. Rev. B: Condens. Matter 51, 11 012 (1995).
G. K. Wertheim, P. H. Citrin, and J. F. van der Veen, Phys. Rev. B: Condens. Matter 30, 4343 (1984).
S. Hüfner, G. K. Wertheim, and J. H. Wernick, Solid State Commun. 17, 417 (1975).
P. Blaha and J. Callaway, Phys. Rev. B: Condens. Matter 33, 1706 (1986).
G. Y. Guo and H. H. Wang, Phys. Rev. B: Condens. Matter 62, 5136 (2000).
K. Lee, J. Callaway, K. Kwong, R. Tang, and A. Ziegler, Phys. Rev. B: Condens. Matter 31, 1796 (1985).
K. Lee and J. Callaway, Phys. Rev. B: Condens. Matter 48, 15 358 (1993).
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Original Russian Text © V.D. Borman, M.A. Pushkin, V.N. Tronin, V.I. Troyan, 2010, published in Zhurnal Éksperimental’noĭ i Teoreticheskoĭ Fiziki, 2010, Vol. 137, No. 6, pp. 1151–1174.
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Borman, V.D., Pushkin, M.A., Tronin, V.N. et al. Evolution of the electronic properties of transition metal nanoclusters on graphite surface. J. Exp. Theor. Phys. 110, 1005–1025 (2010). https://doi.org/10.1134/S1063776110060117
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DOI: https://doi.org/10.1134/S1063776110060117