Abstract
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.
| Original language | English |
|---|---|
| Pages (from-to) | 1867-1873 |
| Number of pages | 7 |
| Journal | Chemistry of Materials |
| Volume | 26 |
| Issue number | 5 |
| DOIs | |
| Publication status | Published - Mar 11 2014 |
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ASJC Scopus subject areas
- Materials Chemistry
- Chemical Engineering(all)
- Chemistry(all)
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Self-doping and electrical conductivity in spinel oxides : Experimental validation of doping rules. / Shi, Yezhou; Ndione, Paul F.; Lim, Linda Y.; Sokaras, Dimosthenis; Weng, Tsu Chien; Nagaraja, Arpun R.; Karydas, Andreas G.; Perkins, John D.; Mason, Thomas O; Ginley, David S.; Zunger, Alex; Toney, Michael F.
In: Chemistry of Materials, Vol. 26, No. 5, 11.03.2014, p. 1867-1873.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Self-doping and electrical conductivity in spinel oxides
T2 - Experimental validation of doping rules
AU - Shi, Yezhou
AU - Ndione, Paul F.
AU - Lim, Linda Y.
AU - Sokaras, Dimosthenis
AU - Weng, Tsu Chien
AU - Nagaraja, Arpun R.
AU - Karydas, Andreas G.
AU - Perkins, John D.
AU - Mason, Thomas O
AU - Ginley, David S.
AU - Zunger, Alex
AU - Toney, Michael F.
PY - 2014/3/11
Y1 - 2014/3/11
N2 - 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.
AB - 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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U2 - 10.1021/cm404031k
DO - 10.1021/cm404031k
M3 - Article
VL - 26
SP - 1867
EP - 1873
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 5
ER -