Probing Surface Oxidation of Reduced Uranium Dioxide Thin Film Using Synchrotron Radiation

S. D. Senanayake, G. I. N. Waterhouse, A. S. Y. Chan, T. E. Madey, D. R. Mullins, Hicham Idriss

Research output: Contribution to journalArticle

21 Citations (Scopus)

Abstract

The work presents a study of the formation of defects created by argon ion sputtering of UO2 thin film surfaces using high-resolution X-ray photoelectron spectroscopy with photon energy of 625 eV. Stable-defected surfaces of UO2-x were monitored by the uranium core level lines found at the low-binding energy side of the U+4 features. The lower end of these states gave binding energies at 377.1 and 387.7 eV attributed to U4f(7/2) and U4f(5/2) core levels peaks, respectively, for metallic uranium (U-0). In between both states (U-0 and U+4), the clear presence of other electronic states is observed. These lines are attributed to intermediate, metastable states of uranium ions between U-0 and U+4. Temperature-programmed X-ray photoelectron spectroscopy is performed to observe the oxidation process of these reduced states with increasing temperature. The increase in the U+4 intensity is not correlated with the decrease of U ions signal with lower oxidation states indicating that the limitation is the photoelectron escape depth. In other words, sputtering has created reduced clusters or ridges on the surface of average dimensions larger than the escape depth of the 4f photoelectron with kinetic energy of 225 eV. The activation energy for surface oxidation to U+4 is approximate to 20 kJ mol(-1). This value is close to other values reported for vacancy-type diffusion mechanism in the fluorite structure.

Original languageEnglish
Pages (from-to)7963-7970
Number of pages8
JournalThe Journal of Physical Chemistry C
Volume111
Issue number22
DOIs
Publication statusPublished - 7 Jun 2007

Keywords

  • UO2(111) single-crystal
  • oxygen diffusion
  • photoelectron-spectroscopy
  • polycrystalline UO2
  • TIO2(001) surfaces
  • carbon-monoxide
  • CO oxidation
  • water-vapor
  • gas sensor
  • acetaldehyde

Cite this

Senanayake, S. D., Waterhouse, G. I. N., Chan, A. S. Y., Madey, T. E., Mullins, D. R., & Idriss, H. (2007). Probing Surface Oxidation of Reduced Uranium Dioxide Thin Film Using Synchrotron Radiation. The Journal of Physical Chemistry C, 111(22), 7963-7970. https://doi.org/10.1021/jp068828g

Probing Surface Oxidation of Reduced Uranium Dioxide Thin Film Using Synchrotron Radiation. / Senanayake, S. D.; Waterhouse, G. I. N.; Chan, A. S. Y.; Madey, T. E.; Mullins, D. R.; Idriss, Hicham.

In: The Journal of Physical Chemistry C, Vol. 111, No. 22, 07.06.2007, p. 7963-7970.

Research output: Contribution to journalArticle

Senanayake, SD, Waterhouse, GIN, Chan, ASY, Madey, TE, Mullins, DR & Idriss, H 2007, 'Probing Surface Oxidation of Reduced Uranium Dioxide Thin Film Using Synchrotron Radiation', The Journal of Physical Chemistry C, vol. 111, no. 22, pp. 7963-7970. https://doi.org/10.1021/jp068828g
Senanayake SD, Waterhouse GIN, Chan ASY, Madey TE, Mullins DR, Idriss H. Probing Surface Oxidation of Reduced Uranium Dioxide Thin Film Using Synchrotron Radiation. The Journal of Physical Chemistry C. 2007 Jun 7;111(22):7963-7970. https://doi.org/10.1021/jp068828g
Senanayake, S. D. ; Waterhouse, G. I. N. ; Chan, A. S. Y. ; Madey, T. E. ; Mullins, D. R. ; Idriss, Hicham. / Probing Surface Oxidation of Reduced Uranium Dioxide Thin Film Using Synchrotron Radiation. In: The Journal of Physical Chemistry C. 2007 ; Vol. 111, No. 22. pp. 7963-7970.
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abstract = "The work presents a study of the formation of defects created by argon ion sputtering of UO2 thin film surfaces using high-resolution X-ray photoelectron spectroscopy with photon energy of 625 eV. Stable-defected surfaces of UO2-x were monitored by the uranium core level lines found at the low-binding energy side of the U+4 features. The lower end of these states gave binding energies at 377.1 and 387.7 eV attributed to U4f(7/2) and U4f(5/2) core levels peaks, respectively, for metallic uranium (U-0). In between both states (U-0 and U+4), the clear presence of other electronic states is observed. These lines are attributed to intermediate, metastable states of uranium ions between U-0 and U+4. Temperature-programmed X-ray photoelectron spectroscopy is performed to observe the oxidation process of these reduced states with increasing temperature. The increase in the U+4 intensity is not correlated with the decrease of U ions signal with lower oxidation states indicating that the limitation is the photoelectron escape depth. In other words, sputtering has created reduced clusters or ridges on the surface of average dimensions larger than the escape depth of the 4f photoelectron with kinetic energy of 225 eV. The activation energy for surface oxidation to U+4 is approximate to 20 kJ mol(-1). This value is close to other values reported for vacancy-type diffusion mechanism in the fluorite structure.",
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AB - The work presents a study of the formation of defects created by argon ion sputtering of UO2 thin film surfaces using high-resolution X-ray photoelectron spectroscopy with photon energy of 625 eV. Stable-defected surfaces of UO2-x were monitored by the uranium core level lines found at the low-binding energy side of the U+4 features. The lower end of these states gave binding energies at 377.1 and 387.7 eV attributed to U4f(7/2) and U4f(5/2) core levels peaks, respectively, for metallic uranium (U-0). In between both states (U-0 and U+4), the clear presence of other electronic states is observed. These lines are attributed to intermediate, metastable states of uranium ions between U-0 and U+4. Temperature-programmed X-ray photoelectron spectroscopy is performed to observe the oxidation process of these reduced states with increasing temperature. The increase in the U+4 intensity is not correlated with the decrease of U ions signal with lower oxidation states indicating that the limitation is the photoelectron escape depth. In other words, sputtering has created reduced clusters or ridges on the surface of average dimensions larger than the escape depth of the 4f photoelectron with kinetic energy of 225 eV. The activation energy for surface oxidation to U+4 is approximate to 20 kJ mol(-1). This value is close to other values reported for vacancy-type diffusion mechanism in the fluorite structure.

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