Bridging classical and quantum interpretation of chemical state analysis by XPS/HAXPES to resolve short-range order in amorphous alumina films
Abstract
Probing the local structure and chemistry of wide-bandgap amorphous oxide thin films remains challenging due to the limitations of lab-based spectroscopy. This work integrates X-ray photoelectron spectroscopy (XPS), hard X-ray photoemission spectroscopy (HAXPES), molecular dynamics simulations using machine-learning interatomic potentials, density-functional theory (DFT) calculations, and classical electrostatic modeling of final-state core-ionization effects in Al atoms to uncover the structure and chemistry of amorphous alumina polymorphs made with atomic layer deposition (ALD). DFT calculations using the ΔKohn-Sham method supported the interpretation of final-state effects and validated electrostatic model assumptions. Shifts in the measured Auger parameters were interpreted as extra-atomic relaxation energies, revealing sensitivity to the local coordination environment. Structural disorder and thermal fluctuations were found to govern the distribution of extra-atomic relaxation energies, suggesting that cryo-XPS can isolate and reveal intrinsic structural building blocks of amorphous oxides. Simulated heating and annealing demonstrated that Auger parameter shifts can serve as indicators of phase decomposition in H-supersaturated ALD amorphous alumina. These findings provide a pathway for comprehensive interpretation and predictive modeling of XPS spectra in amorphous wide-bandgap oxides.
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BibTeX
@article{gramatte2026bridging,
title = {{Bridging classical and quantum interpretation of chemical state analysis by XPS/HAXPES to resolve short-range order in amorphous alumina films}},
author = {Simon Gramatte and Xing Wang and Michael Alejandro Hernández Bertrán and Claudia Cancellieri and Giovanni Pizzi and Deborah Prezzi and Iurii Timrov and Olivier Politano and Ivo Utke and Lars Jeurgens and Vladyslav Turlo},
journal = {Journal of Materials Chemistry A},
year = {2026},
month = oct,
doi = {10.1039/d5ta08586a},
url = {https://hal.science/hal-05795654v1},
note = {CC BY},
}
RIS
TY - JOUR
TI - Bridging classical and quantum interpretation of chemical state analysis by XPS/HAXPES to resolve short-range order in amorphous alumina films
AU - Simon Gramatte
AU - Xing Wang
AU - Michael Alejandro Hernández Bertrán
AU - Claudia Cancellieri
AU - Giovanni Pizzi
AU - Deborah Prezzi
AU - Iurii Timrov
AU - Olivier Politano
AU - Ivo Utke
AU - Lars Jeurgens
AU - Vladyslav Turlo
PY - 2026
DA - 2026/10/12
JO - Journal of Materials Chemistry A
DO - 10.1039/d5ta08586a
UR - https://hal.science/hal-05795654v1
AB - Probing the local structure and chemistry of wide-bandgap amorphous oxide thin films remains challenging due to the limitations of lab-based spectroscopy. This work integrates X-ray photoelectron spectroscopy (XPS), hard X-ray photoemission spectroscopy (HAXPES), molecular dynamics simulations using machine-learning interatomic potentials, density-functional theory (DFT) calculations, and classical electrostatic modeling of final-state core-ionization effects in Al atoms to uncover the structure and chemistry of amorphous alumina polymorphs made with atomic layer deposition (ALD). DFT calculations using the ΔKohn-Sham method supported the interpretation of final-state effects and validated electrostatic model assumptions. Shifts in the measured Auger parameters were interpreted as extra-atomic relaxation energies, revealing sensitivity to the local coordination environment. Structural disorder and thermal fluctuations were found to govern the distribution of extra-atomic relaxation energies, suggesting that cryo-XPS can isolate and reveal intrinsic structural building blocks of amorphous oxides. Simulated heating and annealing demonstrated that Auger parameter shifts can serve as indicators of phase decomposition in H-supersaturated ALD amorphous alumina. These findings provide a pathway for comprehensive interpretation and predictive modeling of XPS spectra in amorphous wide-bandgap oxides.
SN - 2050-7488
SN - 2050-7496
ER -