When Photoelectrons Meet Gas Molecules: Determining the Role of Inelastic Scattering in Ambient Pressure X-ray Photoelectron Spectroscopy.

Abstract

Inelastic photoelectron scattering (IPES) by gas molecules, a critical phenomenon observed in ambient pressure X-ray photoelectron spectroscopy (APXPS), complicates spectral interpretation due to kinetic energy loss in the primary spectrum and the appearance of additional features at higher binding energies. In this study, we systematically investigate IPES in various gas environments using APXPS, providing detailed insights into interactions between photoelectrons emitted from solid surfaces and surrounding gas molecules. Core-level XPS spectra of Au, Ag, Zn, and Cu metals were recorded over a wide kinetic energy range in the presence of CO₂, N₂, Ar, and H₂ gases, demonstrating the universal nature of IPES across different systems. Additionally, we analyzed spectra of scattering effects induced by gas-phase interactions without metal solids. In two reported CO₂-reduction systems (p-GaN/Au/Cu and p-Si/TaO _x /Cu), we elucidated that IPES is independent of the composition, structure, or size of the solid materials. Using metal foil platforms, we further developed an analytical model to extract electron excitation cross sections of gas molecules. These findings enhance our understanding of IPES mechanisms and enable the predictions of IPES structures in other solid-gas systems, providing a valuable reference for future APXPS studies and improving the accuracy of spectral analysis in gas-rich catalytic interfaces.