Journal
APPLIED PHYSICS LETTERS
Volume 106, Issue 10, Pages -Publisher
AMER INST PHYSICS
DOI: 10.1063/1.4914180
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Funding
- Laboratory Directed Research and Development program (LDRD) from Idaho National Laboratory [12026]
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-AC02-98CH10886]
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The chemical state of Zr during the initial, self-limiting stage of oxidation on single crystal zirconium (0001), with oxide thickness on the order of 1 nm, was probed by synchrotron x-ray photoelectron spectroscopy. Quantitative analysis of the Zr 3d spectrum by the spectrum reconstruction method demonstrated the formation of Zr1+, Zr2+, and Zr3+ as non-equilibrium oxidation states, in addition to Zr4+ in the stoichiometric ZrO2. This finding resolves the long-debated question of whether it is possible to form any valence states between Zr-0 and Zr4+ at the metal-oxide interface. The presence of local strong electric fields and the minimization of interfacial energy are assessed and demonstrated as mechanisms that can drive the formation of these non-equilibrium valence states of Zr. (C) 2015 AIP Publishing LLC.
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