Non-equilibrium oxidation states of zirconium during early stages of metal oxidation
Abstract
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 Zr0 and Zr4+ at the metal-oxide interface. As a result, 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.
- Authors:
-
- Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
- Brookhaven National Lab. (BNL), Upton, NY (United States)
- Publication Date:
- Research Org.:
- Brookhaven National Laboratory (BNL), Upton, NY (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1234379
- Alternate Identifier(s):
- OSTI ID: 1420494
- Report Number(s):
- BNL-111675-2015-JA
Journal ID: ISSN 0003-6951; APPLAB; R&D Project: CO009; KC0302010
- Grant/Contract Number:
- SC00112704; 12-026
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Applied Physics Letters
- Additional Journal Information:
- Journal Volume: 106; Journal Issue: 10; Journal ID: ISSN 0003-6951
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; oxidation; electric fields; surface oxidation; photoelectron spectra; X-ray photoelectron spectroscopy
Citation Formats
Ma, Wen, Senanayake, Sanjaya D., Herbert, F. William, and Yildiz, Bilge. Non-equilibrium oxidation states of zirconium during early stages of metal oxidation. United States: N. p., 2015.
Web. doi:10.1063/1.4914180.
Ma, Wen, Senanayake, Sanjaya D., Herbert, F. William, & Yildiz, Bilge. Non-equilibrium oxidation states of zirconium during early stages of metal oxidation. United States. https://doi.org/10.1063/1.4914180
Ma, Wen, Senanayake, Sanjaya D., Herbert, F. William, and Yildiz, Bilge. Wed .
"Non-equilibrium oxidation states of zirconium during early stages of metal oxidation". United States. https://doi.org/10.1063/1.4914180. https://www.osti.gov/servlets/purl/1234379.
@article{osti_1234379,
title = {Non-equilibrium oxidation states of zirconium during early stages of metal oxidation},
author = {Ma, Wen and Senanayake, Sanjaya D. and Herbert, F. William and Yildiz, Bilge},
abstractNote = {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 Zr0 and Zr4+ at the metal-oxide interface. As a result, 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.},
doi = {10.1063/1.4914180},
journal = {Applied Physics Letters},
number = 10,
volume = 106,
place = {United States},
year = {Wed Mar 11 00:00:00 EDT 2015},
month = {Wed Mar 11 00:00:00 EDT 2015}
}
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