Non-equilibrium oxidation states of zirconium during early stages of metal oxidation
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 d...
| Main Authors: | , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Institute of Physics (AIP)
2016
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| Online Access: | http://hdl.handle.net/1721.1/104888 https://orcid.org/0000-0003-0060-9417 https://orcid.org/0000-0002-2688-5666 |
| Summary: | 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[superscript 1+], Zr[superscript 2+], and Zr[superscript 3+] as non-equilibrium oxidation states, in addition to Zr[superscript 4+] in the stoichiometric ZrO2. This finding resolves the long-debated question of whether it is possible to form any valence states between Zr[superscript 0] and Zr[superscript 4+] 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. |
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