Evolution of the electronic properties of transition metal nanoclusters on graphite surface |
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Authors: | V D Borman M A Pushkin V N Tronin and V I Troyan |
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Institution: | 1.National Research Nuclear University (MEPhI),Moscow,Russia |
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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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