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New interpretations of XPS spectra of nickel metal and oxides

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Title: New interpretations of XPS spectra of nickel metal and oxides
Authors: Grosvenor, Andrew P.1, Biesinger, Mark C.1, Smart, Roger St.C.1,2 Roger.Smart@unisa.edu.au, McIntyre, N. Stewart1
Source: Surface Science. May2006, Vol. 600 Issue 9, p1771-1779. 9p.
Subjects: X-ray photoelectron spectroscopy, Nickel, Charge transfer, Spectrum analysis
Abstract: Abstract: A current interpretation of XPS spectra of Ni metal assumes that the main 6eV satellite is due to a two hole c3d94s2 (c is a core hole) final state effect. We report REELS observation in AES at low voltages of losses (plasmons and inter-band transitions) corresponding to the satellite structures in Ni metal 2p spectra. The satellite near 6eV is attributed to a predominant surface plasmon loss. A current interpretation of Ni 2p spectra of oxides and other compounds is based on charge transfer assignments of the main peak at 854.6eV and the broad satellite centred at around 861eV to the cd9L and the unscreened cd8 final-state configurations, respectively (L is a ligand hole). Multiplet splittings have been shown to be necessary for assignment of Fe 2p and Cr 2p spectral profiles and chemical states. The assignments of Ni 2p states are re-examined with intra-atomic multiplet envelopes applied to Ni(OH)2, NiOOH and NiO spectra. It is shown that the free ion multiplet envelopes for Ni2+ and Ni3+ simulate the main line and satellite structures for Ni(OH)2 and NiOOH. Fitting the NiO Ni 2p spectral profile is not as straightforward as the hydroxide and oxyhydroxide. It may involve contributions from inter-atomic, non-local electronic coupling and screening effects with multiplet structures significantly different from the free ions as found for MnO. A scheme for fitting these spectra using multiplet envelopes is proposed. [Copyright &y& Elsevier]
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Abstract:Abstract: A current interpretation of XPS spectra of Ni metal assumes that the main 6eV satellite is due to a two hole c3d94s2 (c is a core hole) final state effect. We report REELS observation in AES at low voltages of losses (plasmons and inter-band transitions) corresponding to the satellite structures in Ni metal 2p spectra. The satellite near 6eV is attributed to a predominant surface plasmon loss. A current interpretation of Ni 2p spectra of oxides and other compounds is based on charge transfer assignments of the main peak at 854.6eV and the broad satellite centred at around 861eV to the cd9L and the unscreened cd8 final-state configurations, respectively (L is a ligand hole). Multiplet splittings have been shown to be necessary for assignment of Fe 2p and Cr 2p spectral profiles and chemical states. The assignments of Ni 2p states are re-examined with intra-atomic multiplet envelopes applied to Ni(OH)2, NiOOH and NiO spectra. It is shown that the free ion multiplet envelopes for Ni2+ and Ni3+ simulate the main line and satellite structures for Ni(OH)2 and NiOOH. Fitting the NiO Ni 2p spectral profile is not as straightforward as the hydroxide and oxyhydroxide. It may involve contributions from inter-atomic, non-local electronic coupling and screening effects with multiplet structures significantly different from the free ions as found for MnO. A scheme for fitting these spectra using multiplet envelopes is proposed. [Copyright &y& Elsevier]
ISSN:00396028
DOI:10.1016/j.susc.2006.01.041