Abstract
X-ray photoelectron spectroscopy (XPS) has applications in many fields ranging from development of thin films for semi-conductors to post failure analysis of organic coatings and structural adhesives. The current work expands on that versatility by applying XPS to the growing field of nuclear forensics. This was achieved by the synthesis and characterisation of several uranium compounds, predominantly in the hexavalent state associated with the nuclear fuel cycle, and by X-ray diffraction and Raman spectroscopy analysis prior to XPS. Spectral characteristics for each compound are discussed, and interpretations made through observations in the binding energy of the U4f region as well as secondary energy loss features such as shake up satellites. The interpretation of such features is related to the stoichiometry, oxidation state and bonding structure of a range of uranium compounds. As XPS is typically insensitive to structural (crystallographic) variations, a rationale is provided for the relationship between structural variations, as measured by Raman and X-ray diffraction and compared to the open literature, and the XPS satellite to parent peak intensity of uranium compounds, providing a novel and useful approach for uranium compound characterisation. In addition to the novel approach described, Wagner chemical state plots have also been generated to provide another comparison tool.
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Notes
The satellite features are nominally found at 4 and 10 eV from the parent peak and denoted as such, in this discussion 4 eV will be denoted as Sat 1 and 10 eV as Sat 2. This is to avoid confusion when comparing the shift of the satellites in greater detail.
References
Neimeyer S, Koch L (2014) The historical evolution of nuclear forensics: a technical viewpoint. IAEA Plenary Sess 1A 218(117):1–6
Schwantes J, Marsden O, Reilly D (2018) Fourth collaborative materials exercise of the nuclear forensics international technical working group. J Radioanal Nucl Chem 315(2):347–352
Ravindran T, Arora A (2011) Study of Raman spectrum of uranium using a surface-enhanced Raman scattering technique. J Raman Spectrosc 42(5):885–887
Watts JF, Wolstenholme J (2020) An introduction to surface analysis by electron spectroscopy, 2nd edn. Wiley, Chichester
Ilton E, Bagus P (2011) XPS determination of uranium oxidation states. Surf Interface Anal 43(13):1549–1560
Allen G, Crofts J, Curtis M, Tucker P, Chadwick D, Hampson P (1974) X-Ray photoelectron spectroscopy of some uranium oxide phases. J Chem Soc Dalton Trans 12:1296
Brisk M, Baker A (1975) Shake-up satellites in X-ray photoelectron spectroscopy. J Electron Spectrosc Relat Phenom 7(3):197–213
Wilson, P., 2001. The nuclear fuel cycle. Oxford [etc.]: Oxford University Press.
Baer Y, Schoenes J (1980) Electronic structure and Coulomb correlation energy in UO2 single crystal. Solid State Commun 33(8):885–888
Jensen M (1967) Investigations on methods of producing crystalline ammonium uranyl carbonate and its applicability for production of uranium-dioxide powder and pellets. Riso Natl Lab 15(1):1
Yi-Ming P, Che-Bao M, Nien-Nan H (1981) The conversion of UO2 via ammonium uranyl carbonate: study of precipitation, chemical variation and powder properties. J Nucl Mater 99(2–3):135–147
Katz J, Katz J, Rabinowitch E (1961) The chemistry of uranium. McGraw-Hill, New York
Larsen R (1959) Dissolution of uranium metal and its alloys. Anal Chem 31(4):545–549
Sato T, Shiota S, Ikoma S, Ozawa F (1977) Thermal decomposition of uranyl chloride hydrate. J Biochem Toxicol 27(1):275–280
Sweet L, Henager C, Hu S, Johnson T, Meier D, Peper S, Schwantes J (2011) Investigation of uranium polymorphs. US Dep Energy 1(1):1–28
Kraiem M, Mayer K, Gouder T, Seibert A, Wiss T, Hiernaut J (2010) Filament chemistry of uranium in thermal ionisation mass spectrometry. J Anal At Spectrom 25(7):1138
Filippov T, Kovalevskiy N, Solovyeva M, Chetyrin I, Prosvirin I, Lyulyukin M, Selishchev D, Kozlov D (2018) In situ XPS data for the uranyl-modified oxides under visible light. Data Brief 19:2053–2060
Bonato M, Allen G, Scott T (2008) Reduction of U(VI) to U(IV) on the surface of TiO2 anatase nanotubes. Micro Nano Lett 3(2):57
Allen G, Holmes N (1987) Surface characterisation of a-, p-, y-, and S-UO, using X-Ray photoelectron spectroscopy. J Chem Soc Dalton Trans 12:3009–3015
Chadwick D (1973) Uranium 4f binding energies studied by X-ray photoelectron spectroscopy. Chem Phys Lett 21:293
Fierro JLG, Salazar E, Legarreta JA (1985) Characterization of silica‐supported uranium–molybdenum oxide catalysts. Surf Interface Anal 7:97
Kawai J, Satoko C, Gohshi Y (1987) Chemical effects of satellites on X-ray emission spectra—II. A general theory of the origin of chemical effects and its application to Cl Kα spectra. Spectrochimica Acta Part B At Spectrosc 42(6):745–754
Kawai J, Tsuboyama S, Ishizu K, Miyamura K, Saburi M (1991) Covalency of copper complexes determined by Cu 2p X-ray photoelectron spectroscopy. Anal Sci 7(Suppl):337–340
Bagus P, Illas F, Pacchioni G, Parmigiani F (1999) Mechanisms responsible for chemical shifts of core-level binding energies and their relationship to chemical bonding. J Electron Spectrosc Relat Phenom 100(1–3):215–236
Podkovyrina Y, Pidchenko I, Prüßmann T, Bahl S, Göttlicher J, Soldatov A, Vitova T (2016) Probing covalency in the UO3 polymorphs by U M4edge HR-XANES. J Phys Conf Ser 712:012092
Di Pietro P, Kerridge A (2017) Ligand size dependence of U-N and U–O bond character in a series of uranyl hexaphyrin complexes: quantum chemical simulation and density based analysis. Phys Chem Chem Phys 19(11):7546–7559
Loopstra BO, Cordfunke HP (1966) On the structure of α-UO3. Recl Trav Chim Pays-Bas 95(2):135–142
Vochten R, Blaton N (1999) Synthesis of rutherfordine and its stability in water and alkaline solutions. Neues Jahrb. Mineral., Monatsh., 372–384
Debets PC (1966) The structure of β-UO3. Acta Cryst 21:598–593
Holliday K, Siekhaus W, Nelson A (2013) Measurement of the Auger parameter and Wagner plot for uranium compounds. J Vac Sci Technol A Vac Surf Films 31(3):031401
Biesinger M, Lau L, Gerson A, Smart R (2012) The role of the Auger parameter in XPS studies of nickel metal, halides and oxides. Phys Chem Chem Phys 14(7):2434
Moretti G (1998) Auger parameter and Wagner plot in the characterization of chemical states by X-ray photoelectron spectroscopy: a review. J Electron Spectrosc Relat Phenom 95(2–3):95–144
Snijders PC, Jeurgens LHP, Sloof WG (2005) Structural ordering of ultra-thin, amorphous aluminium-oxide films. Surf Sci 589(1–3):98–105
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Dunn, S., Roussel, P., Poile, C. et al. Identification of uranium hexavalent compounds using X-ray photoelectron spectroscopy. J Radioanal Nucl Chem 331, 79–88 (2022). https://doi.org/10.1007/s10967-021-08085-0
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DOI: https://doi.org/10.1007/s10967-021-08085-0