Deriving Stable Peak Models to Fit Complex XPS Data From Cu Contaminated Pt Electrocatalysts

Saini, Sonakshi; Bargiela, Pascal; Fernandez, Vincent; Fairley, Neal; Parvin, Sahanaz; Lee, Seunghoon; Weber, Juliane; McDowell, Matthew T.; Baltrusaitis, Jonas

doi:10.1002/sia.7401

Deriving Stable Peak Models to Fit Complex XPS Data From Cu Contaminated Pt Electrocatalysts

Journal Article · Thu Apr 10 00:00:00 EDT 2025 · Surface and Interface Analysis

DOI:https://doi.org/10.1002/sia.7401· OSTI ID:3002514

Saini, Sonakshi ^[1]; Bargiela, Pascal ^[2]; Fernandez, Vincent ^[3]; Fairley, Neal ^[4]; Parvin, Sahanaz ^[5]; Lee, Seunghoon ^[6]; ^[6]; McDowell, Matthew T. ^[1]; ^[5]

Georgia Institute of Technology, Atlanta, GA (United States)
The Institute for Research on Catalysis and the Environment of Lyon (IRCELYON), Villeurbanne (France)
Nantes Université (France); Centre National de la Recherche Scientifique (CNRS) (France)
Casa Software Ltd, Devon (United Kingdom)
Lehigh Univ., Bethlehem, PA (United States)
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division

X-ray Photoelectron Spectroscopy spectra peak models, designed to partition photoemission signals emanating from different elements or chemical states within an atom, are fitted to data limited to an energy interval over which inelastically scattered photoemission signal can be estimated. While the choice of background approximation and line shapes of components to the peak model requires careful consideration, the energy interval used to define the data to which the peak model is optimized has a significant impact on the final peak model. The relationship between the background intensity and data intensity at the start and end of the energy interval dictates the line shapes used in the peak model. In this work, we devise a method to peak fit a complex overlapping Cu 3p and Pt 4f XPS peak structure to perform the elemental quantification. We first use an Al 2s peak to illustrate how background curves approach data at the limits of the energy interval over which the background is defined, influencing the analysis of XPS spectra. Next, we demonstrate the nature of interactions between specific line shapes (Voigt and pseudo-Voigt profiles) suitable for photoemission peaks and a specific background curve (Shirley) and a peak model is presented that includes components to the peak model that accommodates background intensity during fitting of the peak model to data. The peak model allowed for quantification of the contributions of Pt 4f peaks emanating from the substrate that exhibits strong asymmetry in the presence of the inhomogeneously distributed Cu species, mostly of Lorentzian character.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC05-00OR22725; SC0012577

OSTI ID:: 3002514

Journal Information:: Surface and Interface Analysis, Journal Name: Surface and Interface Analysis Journal Issue: 6 Vol. 57; ISSN 1096-9918; ISSN 0142-2421

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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