SP2/SP3 hybridization ratio in amorphous carbon from C 1s core-level shifts: X-ray photoelectron spectroscopy and first-principles calculation

Rainer Haerle, Rainer Haerle, Elisa Riedo, Alfredo Pasquarello, Alfredo Pasquarello, Alfonso Baldereschi, Alfonso Baldereschi

Research output: Contribution to journalArticle

Abstract

Using a combined experimental and theoretical approach, we address C 1s core-level shifts in amorphous carbon. Experimental results are obtained by x-ray photoelectron spectroscopy (XPS) and electron-energy-loss spectroscopy (EELS) on thin-film samples of different atomic density, obtained by a pulsed-laser deposition growth process. The XPS spectra are deconvoluted into two contributions, which are attributed to sp2- and sp3-hybridized atoms, respectively, separated by 0.9 eV, independent of atomic density. The sp3 hybridization content extracted from XPS is consistent with the atomic density derived from the plasmon energy in the EELS spectrum. In our theoretical study, we generate several periodic model structures of amorphous carbon of different densities applying two schemes of increasing accuracy in sequence. We first use a molecular-dynamics approach, based on an environmental-dependent tight-binding Hamiltonian to quench the systems from the liquid phase. The final model structures are then obtained by further atomic relaxation using a first-principles pseudopotential plane-wave approach within density-functional theory. Within the latter framework, we also calculate carbon 1s core-level shifts for our disordered model structures. We find that the shifts associated to threefold- and fourfold- coordinated carbon atoms give rise to two distinct peaks separated by about 1.0 eV, independent of density, in close agreement with experimental observations. This provides strong support for decomposing the XPS spectra into two peaks resulting from sp2- and sp3-hybridized atoms. Core-hole relaxations effects account for about 30% of the calculated shifts.

Original languageEnglish (US)
Article number045101
Pages (from-to)451011-451019
Number of pages9
JournalPhysical Review B - Condensed Matter and Materials Physics
Volume65
Issue number4
StatePublished - Jan 15 2002

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Core levels
Amorphous carbon
Photoelectron spectroscopy
X ray photoelectron spectroscopy
Model structures
x ray spectroscopy
photoelectron spectroscopy
X rays
Electron energy loss spectroscopy
carbon
shift
Atoms
x rays
Carbon
Hamiltonians
energy dissipation
electron energy
atoms
Pulsed laser deposition
Density functional theory

ASJC Scopus subject areas

  • Electronic, Optical and Magnetic Materials
  • Condensed Matter Physics

Cite this

SP2/SP3 hybridization ratio in amorphous carbon from C 1s core-level shifts : X-ray photoelectron spectroscopy and first-principles calculation. / Haerle, Rainer; Haerle, Rainer; Riedo, Elisa; Pasquarello, Alfredo; Pasquarello, Alfredo; Baldereschi, Alfonso; Baldereschi, Alfonso.

In: Physical Review B - Condensed Matter and Materials Physics, Vol. 65, No. 4, 045101, 15.01.2002, p. 451011-451019.

Research output: Contribution to journalArticle

Haerle, R, Haerle, R, Riedo, E, Pasquarello, A, Pasquarello, A, Baldereschi, A & Baldereschi, A 2002, 'SP2/SP3 hybridization ratio in amorphous carbon from C 1s core-level shifts: X-ray photoelectron spectroscopy and first-principles calculation', Physical Review B - Condensed Matter and Materials Physics, vol. 65, no. 4, 045101, pp. 451011-451019.
Haerle, Rainer ; Haerle, Rainer ; Riedo, Elisa ; Pasquarello, Alfredo ; Pasquarello, Alfredo ; Baldereschi, Alfonso ; Baldereschi, Alfonso. / SP2/SP3 hybridization ratio in amorphous carbon from C 1s core-level shifts : X-ray photoelectron spectroscopy and first-principles calculation. In: Physical Review B - Condensed Matter and Materials Physics. 2002 ; Vol. 65, No. 4. pp. 451011-451019.
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