Electronic structure and electron energy-loss spectroscopy of ZrO2 zirconia - Archive ouverte HAL
Article Dans Une Revue Physical Review B: Condensed Matter and Materials Physics (1998-2015) Année : 2004

Electronic structure and electron energy-loss spectroscopy of ZrO2 zirconia

Résumé

The atomic and electronic structures of zirconia are calculated within density functional theory, and their evolution is analyzed as the crystal-field symmetry changes from tetrahedral [cubic (c-ZrO2) and tetragonal (t-ZrO2) phases] to octahedral (hypothetical rutile ZrO2), to a mixing of these symmetries (monoclinic phase, m-ZrO2). We find that the theoretical bulk modulus in c-ZrO2 is 30% larger than the experimental value, showing that the introduction of yttria in zirconia has a significant effect. Electronic structure fingerprints which characterize each phase from their electronic spectra are identified. We have carried out electron energy-loss spectroscopy experiments at low momentum transfer and compared these results to the theoretical spectra calculated within the random phase approximation. We show a dependence of the valence and 4p (N2,3 edge) plasmons on the crystal structure, the dependence of the latter being brought into the spectra by local-field effects. Last, we attribute low energy excitations observed in EELS of m-ZrO2 to defect states 2 eV above the top of the intrinsic valence band, and the EELS fundamental band gap value is reconciled with the 5.2 or 5.8 eV gaps determined by vacuum ultraviolet spectroscopy
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Dates et versions

hal-00077926 , version 1 (01-06-2006)

Identifiants

  • HAL Id : hal-00077926 , version 1

Citer

L. K. Dash, N. Vast, P. Baranek, M. C. Cheynet, L. Reining. Electronic structure and electron energy-loss spectroscopy of ZrO2 zirconia. Physical Review B: Condensed Matter and Materials Physics (1998-2015), 2004, 70, pp.245116. ⟨hal-00077926⟩
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