SCHEDULED MAINTENANCE
Structural and chemical properties of NiOx thin films: the role of oxygen vacancies in NiOOH formation in a H2O atmosphere†
*a
Thomas
Mayer,
c
Abstract
NiOx 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 H2O 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 NiOx film to H2O can lead to a partial reduction of NiOx to metallic Ni accompanied by a distinct shift of the NiOx spectra with respect to the Fermi edge. DFT calculations show that the formation of oxygen vacancies and subsequently Ni0 leads to a state within the band gap of NiO which pins the Fermi edge.
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