Structural and chemical properties of NiO x thin films: the role of oxygen vacancies in NiOOH formation in a H 2 O atmosphere

• Published in: Physical chemistry chemical physics : PCCP 2023-09, Vol.25 (37), p.25552-25565
• Main Authors: Blume, A. Raoul, Calvet, Wolfram, Ghafari, Aliakbar, Mayer, Thomas, Knop-Gericke, Axel, Schlögl, Robert
• Format: Article
• Language: English
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/D3CP02047A

NiO x films grown from 50 nm thick Ni on Si(111) were put in contact with oxygen and subsequently water vapor at elevated temperatures. Near ambient pressure (NAP)-XPS and -XAS reveal the formation of oxygen vacancies at elevated temperatures, followed by H 2 O dissociation and saturation of the oxygen vacancies with chemisorbing OH. Through repeated heating and cooling, OH-saturated oxygen vacancies act as precursors for the formation of thermally stable NiOOH on the sample surface. This is accompanied by a significant restructuring of the surface which increases the probability of NiOOH formation. Exposure of a thin NiO x film to H 2 O can lead to a partial reduction of NiO x to metallic Ni accompanied by a distinct shift of the NiO x spectra with respect to the Fermi edge. DFT calculations show that the formation of oxygen vacancies and subsequently Ni 0 leads to a state within the band gap of NiO which pins the Fermi edge.