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Self-Doping and Electrical Conductivity in Spinel Oxides: Experimental Validation of Doping Rules

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SLAC National Accelerator Laboratory, Menlo Park, California 94025, United States
National Renewable Energy Laboratory, Golden, Colorado 80401, United States
§ Northwestern University, Evanston, Illinois 60208, United States
NCSR Demokritos, Institute of Nuclear Physics,GR-15310, Athens, Greece
Nuclear Science and Instrumentation Laboratory, IAEA Laboratories, Austria A-2444, Seibersdorf, Austria
# University of Colorado at Boulder, Boulder, Colorado 80309, United States
Cite this: Chem. Mater. 2014, 26, 5, 1867–1873
Publication Date (Web):February 12, 2014
Copyright © 2014 American Chemical Society

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    Self-doping of cations on the tetrahedral and octahedral sites in spinel oxides creates “anti-site” defects, which results in functional optical, electronic, magnetic, and other materials properties. Previously, we divded the III–II spinel family into four doping types (DTs) based on first-principle calculations in order to understand their electrical behavior. Here, we present experimental evidence on two prototype spinels for each major doping type (DT1 and DT4) that test the first principles calculations. For the DT-1 Ga2ZnO4 spinel, we show that the anti-site defects in a stoichiometric film are equal in concentration and compenstate each other, whereas, for nonstoichiometric Cr2MnO4, a representative DT-4 spinel, excess Mn on the tetrahedral sites becomes electrically inactive as the Mn species switch from (III) to (II). The agreement between experiment and theory validates the Doping Rules distilled from the theoretical framework and significantly enhances our understanding of the defect chemistry of spinel oxides.

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    Review of the doping type theory, the target fabrication method, lab-source X-ray characterization of the biaxially textured films, and the detailed quantitative methods used for XAS, XRF, XES, as well as REXD analysis. This material is available free of charge via the Internet at

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