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• W2061375357 abstract "For perovskites with the general formula $A$CoO${}_{3ensuremath{-}ensuremath{delta}}$ ($A$ $=$ La, Pr, Nd, Sm, and Gd) the influence of the $A$-site cation on the electrical conductivity, electronic structure, thermodynamic stability, and oxygen stoichiometry was studied. The perovskite oxide powders were produced by a combined citric acid and ethylenediaminetetraacetic acid complexing method. Ceramic specimens sintered at 1100 ifmmode^circelsetextdegreefi{}C in air were single-phase perovskites. With increasing temperature, the electrical conductivity shows three discrete regimes. All compositions show semiconductivity up to a transition temperature of ensuremath{sim}300 ifmmode^circelsetextdegreefi{}C--450 ifmmode^circelsetextdegreefi{}C and then behave like metallic conductors. The activation energies for the semiconductivity, as well as the transition temperatures to the metallic-like conduction, decrease monotonically with increasing pseudocubic lattice parameters, i.e., with increasing ionic radii of the $A$ cation. This behavior correlates with decreasing oxygen nonstoichiometry and increased thermodynamic stability. The highest conductivity and the lowest activation energy of 0.66 eV were found for LaCoO${}_{3ensuremath{-}ensuremath{delta}}$, which also had the lowest semiconductor--metal transition temperature at 269 ifmmode^circelsetextdegreefi{}C, the lowest oxygen nonstoichiometry of ensuremath{delta} $=$ 0.008, and the highest Gibbs free energy change for the decomposition reaction of 42.37 kJ/mol at 850 ifmmode^circelsetextdegreefi{}C. GdCoO${}_{3ensuremath{-}ensuremath{delta}}$ had the highest oxygen nonstoichiometry with ensuremath{delta} $=$ 0.032, a high activation energy of 1.19 eV for the semiconductivity with a high transition temperature at 452 ifmmode^circelsetextdegreefi{}C, and the lowest Gibbs free energy change of 26.54 kJ/mol at 850 ifmmode^circelsetextdegreefi{}C. X-ray absorption spectroscopy data imply an increasing Co low-spin character with decreasing cation radius from La to Gd, while an increase in temperature increases the number of holes or Co 3$d$ bandwidth. This correlates well with the electrical conductivity data." @default.
• W2061375357 created "2016-06-24" @default.
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• W2061375357 date "2011-08-22" @default.
• W2061375357 modified "2023-10-17" @default.
• W2061375357 title "Correlation between electrical properties and thermodynamic stability of<mml:math xmlns:mml=http://www.w3.org/1998/Math/MathML display=inline><mml:mi>A</mml:mi></mml:math>CoO<mml:math xmlns:mml=http://www.w3.org/1998/Math/MathML display=inline><mml:msub><mml:mrow /><mml:mrow><mml:mn>3</mml:mn><mml:mo>−</mml:mo><mml:mi>δ</mml:mi></mml:mrow></mml:msub></mml:math>perovskites (<mml:math xmlns:mml=http://www.w3.org/1998/Math/MathML display=inline><mml:mrow><mml:mi>A</mml:mi><mml:mo>=</…" @default.
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• W2061375357 doi "https://doi.org/10.1103/physrevb.84.085113" @default.
• W2061375357 hasPublicationYear "2011" @default.
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