Quantitative XPS of plutonium: Evaluation of the Pu4f peak shape, relative sensitivity factors and estimated detection limits

Roussel, Paul; Nelson, Art J.

doi:10.1002/sia.7083

Title: Quantitative XPS of plutonium: Evaluation of the Pu4f peak shape, relative sensitivity factors and estimated detection limits

Journal Article · 25 February 2022 · Surface and Interface Analysis

DOI: https://doi.org/10.1002/sia.7083 · OSTI ID:1860699

^[1]; Nelson, Art J. ^[2]

AWE plc, Berkshire (United Kingdom)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

We report that high-resolution X-ray photoelectron spectra have been acquired from sputter cleaned and in situ oxidized samples of α-plutonium and a face-centred cubic δ-plutonium–gallium alloy. The differences in the Pu4f peak shape in these two materials have been investigated, and the poorly screened satellite peaks have been quantified. Curve fitting parameters for the Pu4p_3/2, Pu4d_5/2, Pu4f and Pu6p_3/2 photoelectron peaks are reported, and relative sensitivity factors have been determined. The Pu4f curve fit model has been applied to data acquired using different spectrometers and alloys. Examples of quantification of the plutonium spectra are provided and minimum detection limits are calculated for common impurities in plutonium metal.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE; USDOE National Nuclear Security Administration (NNSA)

Grant/Contract Number:: AC52-07NA27344

OSTI ID:: 1860699

Report Number(s):: LLNL-JRNL-827762; 1040560

Journal Information:: Surface and Interface Analysis, Journal Name: Surface and Interface Analysis Journal Issue: 7 Vol. 54; ISSN 0142-2421

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Effect of phosphorus concentration on the electronic structure of nanocrystalline electrodeposited Ni–P alloys: an XPS and XAES investigation Elsener, B.; Atzei, D.; Krolikowski, A. Surface and Interface Analysis, Vol. 40, Issue 5 https://doi.org/10.1002/sia.2802	journal	January 2008
Detection limits in XPS for more than 6000 binary systems using Al and Mg Kα X-rays: XPS detection limits Shard, Alexander G. Surface and Interface Analysis, Vol. 46, Issue 3 https://doi.org/10.1002/sia.5406	journal	February 2014
Oxidation of a depleted uranium‐5 wt% molybdenum (U‐5Mo) alloy in UHV by AES and XPS Bacon, Simon R.; Brierley, Martin; Baker, Mark A. Surface and Interface Analysis, Vol. 51, Issue 8 https://doi.org/10.1002/sia.6659	journal	April 2019
A discussion of approaches for fitting asymmetric signals in X‐ray photoelectron spectroscopy (XPS), noting the importance of Voigt‐like peak shapes Major, George H.; Avval, Tahereh G.; Patel, Dhananjay I. Surface and Interface Analysis, Vol. 53, Issue 8 https://doi.org/10.1002/sia.6958	journal	May 2021
Empirical atomic sensitivity factors for quantitative analysis by electron spectroscopy for chemical analysis Wagner, C. D.; Davis, L. E.; Zeller, M. V. Surface and Interface Analysis, Vol. 3, Issue 5 https://doi.org/10.1002/sia.740030506	journal	October 1981
Improved dynamic range and automated lineshape differentiation in AES/XPS composition versus depth profiles Watson, D. G. Surface and Interface Analysis, Vol. 15, Issue 9 https://doi.org/10.1002/sia.740150904	journal	September 1990
Widths of the Atomic k–n7 Levels Campbell, J. L.; Papp, Tibor Atomic Data and Nuclear Data Tables, Vol. 77, Issue 1 https://doi.org/10.1006/adnd.2000.0848	journal	January 2001
Examples of Quantification in XPS on 5f Materials Gouder, Thomas; Havela, Ladislav Microchimica Acta, Vol. 138, Issue 3-4 https://doi.org/10.1007/s006040200024	journal	May 2002
The plutonium-oxygen phase diagram Gardner, E. R.; Markin, T. L.; Street, R. S. Journal of Inorganic and Nuclear Chemistry, Vol. 27, Issue 3 https://doi.org/10.1016/0022‐1902(65)80259‐7	journal	March 1965
Surface analysis of actinide materials Naegele, J. R. Journal of Nuclear Materials, Vol. 166, Issue 1-2 https://doi.org/10.1016/0022‐3115(89)90176‐1	journal	July 1989
XPS study of plutonium oxides Courteix, D.; Chayrouse, J.; Heintz, L. Solid State Communications, Vol. 39, Issue 2 https://doi.org/10.1016/0038‐1098(81)90658‐X	journal	July 1981
Core-level binding-energy shifts at surfaces and in solids Egelhoff, W. F. Surface Science Reports, Vol. 6, Issue 6-8 https://doi.org/10.1016/0167‐5729(87)90007‐0	journal	May 1987
Hartree-Slater subshell photoionization cross-sections at 1254 and 1487 eV Scofield, J. H. Journal of Electron Spectroscopy and Related Phenomena, Vol. 8, Issue 2 https://doi.org/10.1016/0368‐2048(76)80015‐1	journal	January 1976
Relative intensities in photoelectron spectroscopy of atoms and molecules Reilman, Robert F.; Msezane, Alfred; Manson, Steven T. Journal of Electron Spectroscopy and Related Phenomena, Vol. 8, Issue 5 https://doi.org/10.1016/0368‐2048(76)80025‐4	journal	January 1976
Photoemission study (XPS, UPS) of PuFe2 Ghijsen, J. Journal of Electron Spectroscopy and Related Phenomena, Vol. 35, Issue 1 https://doi.org/10.1016/0368‐2048(85)80039‐6	journal	January 1985
Detection of plutonium hydride using X-ray photoelectron spectroscopy Larson, D. T.; Motyl, K. M. Journal of Electron Spectroscopy and Related Phenomena, Vol. 50, Issue 1 https://doi.org/10.1016/0368‐2048(90)80008‐X	journal	January 1990
5f Resonant photoemission from plutonium Terry, J.; Schulze, R. K.; Farr, J. D. Surface Science, Vol. 499, Issue 1 https://doi.org/10.1016/S0039‐6028(01)01757‐5	journal	February 2002
Mechanisms responsible for chemical shifts of core-level binding energies and their relationship to chemical bonding Bagus, Paul S.; Illas, Francesc; Pacchioni, Gianfranco Journal of Electron Spectroscopy and Related Phenomena, Vol. 100, Issue 1-3 https://doi.org/10.1016/S0368‐2048(99)00048‐1	journal	October 1999
Systematic and collaborative approach to problem solving using X-ray photoelectron spectroscopy Fairley, Neal; Fernandez, Vincent; Richard‐Plouet, Mireille Applied Surface Science Advances, Vol. 5 https://doi.org/10.1016/j.apsadv.2021.100112	journal	September 2021
Resolving surface chemical states in XPS analysis of first row transition metals, oxides and hydroxides: Cr, Mn, Fe, Co and Ni Biesinger, Mark C.; Payne, Brad P.; Grosvenor, Andrew P. Applied Surface Science, Vol. 257, Issue 7, p. 2717-2730 https://doi.org/10.1016/j.apsusc.2010.10.051	journal	January 2011
Electronic and optical properties of plutonium metal and oxides from Reflection Electron Energy Loss Spectroscopy Roussel, P.; Graham, K. S.; Hernandez, S. C. Applied Surface Science, Vol. 553 https://doi.org/10.1016/j.apsusc.2021.149559	journal	July 2021
New insight into δ-Pu alloy oxidation kinetics highlighted by using in-situ X-ray diffraction coupled with an original Rietveld refinement method Ravat, B.; Jolly, L.; Oudot, B. Corrosion Science, Vol. 138 https://doi.org/10.1016/j.corsci.2018.03.046	journal	July 2018
Parabolic oxidation kinetics of a plutonium alloy at room temperature Donald, Scott B.; Stanford, Jeff A.; Haschke, John M. Corrosion Science, Vol. 187 https://doi.org/10.1016/j.corsci.2021.109527	journal	July 2021
Evidence of an oxidation induced phase transformation for a delta phase plutonium-gallium alloy Donald, Scott B.; Stanford, Jeff A.; Talbot, William A. Corrosion Science, Vol. 194 https://doi.org/10.1016/j.corsci.2021.109923	journal	January 2022
Inverse photoemission measurements of plutonium metal and oxides Roussel, Paul Journal of Electron Spectroscopy and Related Phenomena, Vol. 246 https://doi.org/10.1016/j.elspec.2020.147030	journal	January 2021
Determination of the clean 4f peak shape in XPS for plutonium metal Morrall, P.; Roussel, P.; Jolly, L. Journal of Nuclear Materials, Vol. 385, Issue 1 https://doi.org/10.1016/j.jnucmat.2008.10.009	journal	March 2009
Bulk properties and photoelectron spectroscopy of the ζ-U–Pu phase Havela, Ladislav; Adamska, Anna; Eloirdi, Rachel Journal of Nuclear Materials, Vol. 414, Issue 3 https://doi.org/10.1016/j.jnucmat.2011.05.033	journal	July 2011
Electronic structure information of metals and alloys from auger and photoemission Kleiman, George G. Journal of Molecular Catalysis A: Chemical, Vol. 228, Issue 1-2 https://doi.org/10.1016/j.molcata.2004.09.057	journal	March 2005
Characterization and stability of thin oxide films on plutonium surfaces Flores, H. G. García; Roussel, P.; Moore, D. P. Surface Science, Vol. 605, Issue 3-4 https://doi.org/10.1016/j.susc.2010.10.034	journal	February 2011
Multiplet splitting for the XPS of heavy elements: Dependence on oxidation state Bagus, Paul S.; Nelin, Connie J.; Al-Salik, Yahya Surface Science, Vol. 643 https://doi.org/10.1016/j.susc.2015.06.002	journal	January 2016
Inverse photoemission of the light actinide metals and dioxides Roussel, Paul; Bishop, Alexander J.; Carley, Albert F. Surface Science, Vol. 714 https://doi.org/10.1016/j.susc.2021.121914	journal	December 2021
XPS-AES characterization of plutonium oxides and oxide carbide. The existence of plutonium monoxide Larson, D. T.; Haschke, John M. Inorganic Chemistry, Vol. 20, Issue 7 https://doi.org/10.1021/ic50221a001	journal	July 1981
Ellipsometer studies of plutonium oxidation Larson, Donelly T.; Cash, D. L. The Journal of Physical Chemistry, Vol. 73, Issue 9 https://doi.org/10.1021/j100843a004	journal	September 1969
Synchrotron-based ambient pressure X-ray photoelectron spectroscopy of hydrogen and helium Zhong, Jian-Qiang; Wang, Mengen; Hoffmann, William H. Applied Physics Letters, Vol. 112, Issue 9 https://doi.org/10.1063/1.5022479	journal	February 2018
Initial Studies of Plutonium Corrosion Roussel, Paul; Shaw, Daniel S.; Geeson, David A. Journal of Nuclear Science and Technology, Vol. 39, Issue sup3 https://doi.org/10.1080/00223131.2002.10875412	journal	November 2002
X-ray photoemission study of plutonium metal Baptist, R.; Courteix, D.; Chayrouse, J. Journal of Physics F: Metal Physics, Vol. 12, Issue 9 https://doi.org/10.1088/0305‐4608/12/9/028	journal	September 1982
Variability of 5f states in plutonium carbides Gouder, T.; Havela, L.; Shick, A. B. Journal of Physics: Condensed Matter, Vol. 19, Issue 47 https://doi.org/10.1088/0953-8984/19/47/476201	journal	October 2007
Photoelectron spectroscopy of NpPd ₃ and PuPd ₃ Le, M. D.; Walker, H. C.; McEwen, K. A. Journal of Physics: Condensed Matter, Vol. 20, Issue 27 https://doi.org/10.1088/0953-8984/20/27/275220	journal	June 2008
The growth and evolution of thin oxide films on δ-plutonium surfaces Flores, Harry G. García; Pugmire, David L. IOP Conference Series: Materials Science and Engineering, Vol. 9 https://doi.org/10.1088/1757-899X/9/1/012038	journal	March 2010
Core-level lifetimes as determined by x-ray photoelectron spectroscopy measurements Fuggle, John C.; Alvarado, Santos F. Physical Review A, Vol. 22, Issue 4 https://doi.org/10.1103/PhysRevA.22.1615	journal	October 1980
X-ray photoelectron-spectroscopy study of oxides of the transuranium elements Np, Pu, Am, Cm, Bk, and Cf Veal, B. W.; Lam, D. J.; Diamond, H. Physical Review B, Vol. 15, Issue 6 https://doi.org/10.1103/PhysRevB.15.2929	journal	March 1977
X-ray photoemission study of δ − Pu stabilized by 1 wt.% Ga: Electronic structure and sputter-induced surface phase transformation Cox, L. E. Physical Review B, Vol. 37, Issue 14 https://doi.org/10.1103/PhysRevB.37.8480	journal	May 1988
Variable-takeoff-angle x-ray-photoelectron-spectroscopy evidence for an electronically modified surface in α-Pu Cox, L. E.; Eriksson, O.; Cooper, B. R. Physical Review B, Vol. 46, Issue 20 https://doi.org/10.1103/PhysRevB.46.13571	journal	November 1992
Electronic structure of α- and δ-Pu from photoelectron spectroscopy Arko, A. J.; Joyce, J. J.; Morales, L. Physical Review B, Vol. 62, Issue 3 https://doi.org/10.1103/PhysRevB.62.1773	journal	July 2000
Photoelectron spectroscopy study of PuN Havela, L.; Wastin, F.; Rebizant, J. Physical Review B, Vol. 68, Issue 8 https://doi.org/10.1103/PhysRevB.68.085101	journal	August 2003
Oxidation and aging in U and Pu probed by spin-orbit sum rule analysis: Indications for covalent metal-oxide bonds Moore, K. T.; van der Laan, G.; Haire, R. G. Physical Review B, Vol. 73, Issue 3 https://doi.org/10.1103/PhysRevB.73.033109	journal	January 2006
Electronic structure and nonmagnetic character of δ − Pu − Am alloys Shick, Alexander; Havela, Ladislav; Kolorenč, Jindřich Physical Review B, Vol. 73, Issue 10 https://doi.org/10.1103/PhysRevB.73.104415	journal	March 2006
Valence-band UPS, 6 p core-level XPS, and LEED of a uranium (001) single crystal Opeil, C. P.; Schulze, R. K.; Manley, M. E. Physical Review B, Vol. 73, Issue 16 https://doi.org/10.1103/PhysRevB.73.165109	journal	April 2006
Valence fluctuations in thin films and the α and δ phases of Pu metal determined by 4 f core-level photoemission calculations van der Laan, G.; Taguchi, M. Physical Review B, Vol. 82, Issue 4 https://doi.org/10.1103/PhysRevB.82.045114	journal	July 2010
Electronic Structure and 4 f -Hole Lifetime in Rare-Earth Borides Chazalviel, J. N.; Campagna, M.; Wertheim, G. K. Physical Review Letters, Vol. 37, Issue 14 https://doi.org/10.1103/PhysRevLett.37.919	journal	October 1976
Observation of a Relationship between Core-Level Line Shapes in Photoelectron Spectroscopy and the Localization of Screening Orbitals Fuggle, J. C.; Campagna, M.; Zolnierek, Z. Physical Review Letters, Vol. 45, Issue 19 https://doi.org/10.1103/PhysRevLett.45.1597	journal	November 1980
Localization of 5 f Electrons in Americium: A Photoemission Study Naegele, J. R.; Manes, L.; Spirlet, J. C. Physical Review Letters, Vol. 52, Issue 20 https://doi.org/10.1103/PhysRevLett.52.1834	journal	May 1984
5 f -Electron Localization in PuSe and PuSb Gouder, T.; Wastin, F.; Rebizant, J. Physical Review Letters, Vol. 84, Issue 15 https://doi.org/10.1103/PhysRevLett.84.3378	journal	April 2000
Applicability of the Spin-Orbit Sum Rule for the Actinide 5 f States van der Laan, G.; Moore, K. T.; Tobin, J. G. Physical Review Letters, Vol. 93, Issue 9 https://doi.org/10.1103/PhysRevLett.93.097401	journal	August 2004
Low temperature oxidation of plutonium Nelson, Art J.; Roussel, Paul Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 31, Issue 3 https://doi.org/10.1116/1.4802596	journal	May 2013
X-ray excited Auger transitions of Pu compounds Nelson, Art J.; Grant, William K.; Stanford, Jeff A. Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 33, Issue 3 https://doi.org/10.1116/1.4913886	journal	May 2015
Practical guide for inelastic mean free paths, effective attenuation lengths, mean escape depths, and information depths in x-ray photoelectron spectroscopy Powell, Cedric J. Journal of Vacuum Science & Technology A, Vol. 38, Issue 2 https://doi.org/10.1116/1.5141079	journal	March 2020
Practical guides for x-ray photoelectron spectroscopy: Quantitative XPS Shard, Alexander G. Journal of Vacuum Science & Technology A, Vol. 38, Issue 4 https://doi.org/10.1116/1.5141395	journal	July 2020
X-ray photoelectron spectroscopy: A perspective on quantitation accuracy for composition analysis of homogeneous materials Brundle, Christopher Richard; Crist, Bruce Vincent Journal of Vacuum Science & Technology A, Vol. 38, Issue 4 https://doi.org/10.1116/1.5143897	journal	July 2020
AES and XPS study of plutonium oxidation Larson, D. T. Journal of Vacuum Science and Technology, Vol. 17, Issue 1 https://doi.org/10.1116/1.570503	journal	January 1980
Introductory guide to backgrounds in XPS spectra and their impact on determining peak intensities Engelhard, Mark H.; Baer, Donald R.; Herrera-Gomez, Alberto Journal of Vacuum Science & Technology A, Vol. 38, Issue 6 https://doi.org/10.1116/6.0000359	journal	December 2020
Practical guide for curve fitting in x-ray photoelectron spectroscopy Major, George H.; Fairley, Neal; Sherwood, Peter M. A. Journal of Vacuum Science & Technology A, Vol. 38, Issue 6 https://doi.org/10.1116/6.0000377	journal	December 2020

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36 MATERIALS SCIENCE
75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
plutonium
x-ray photoelectron spectroscopy
quantification
detection limits

Title: Quantitative XPS of plutonium: Evaluation of the Pu4f peak shape, relative sensitivity factors and estimated detection limits

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