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Title: 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 Zr 1+, Zr 2+, and Zr 3+ as non-equilibrium oxidation states, in addition to Zr 4+ in the stoichiometric ZrO 2. This finding resolves the long-debated question of whether it is possible to form any valence states between Zr 0 and Zr 4+ 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:
 [1];  [2];  [1];  [1]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
Publication Date:
Research Org.:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
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. doi: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. doi: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 = {2015},
month = {3}
}

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Cited by: 4 works
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