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Non-stoichiometry in Oxide Thin Films: A Chemical Capacitance Study of the Praseodymium-Cerium Oxide System

Authors

  • Di Chen,

    1. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA
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  • Sean R. Bishop,

    1. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA
    2. International Institute for Carbon Neutral, Energy Research (WPI-I2CNER), Kyushu University, Nishi-ku Fukuoka 819-0395, Japan
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  • Harry L. Tuller

    Corresponding author
    1. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA
    • Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
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Abstract

While the properties of functional oxide thin films often depend strongly on their oxygen stoichiometry, there have been few ways to extract this information reliably and in situ. In this work, the derivation of the oxygen non-stoichiometry of dense Pr0.1Ce0.9O2−δ thin films from an analysis of chemical capacitance obtained by impedance spectroscopy is described. Measurements are performed on electrochemical cells of the form Pr0.1Ce0.9O2−δ/Y0.16Zr0.84O1.92/Pr0.1Ce0.9O2−δ over the temperature range of 450 to 800 °C and oxygen partial pressure range of 10−5 to 1 atm O2. With the aid of a defect equilibria model, approximations relate chemical capacitance directly to non-stoichiometry, without need for fitting parameters. The calculated non-stoichiometry allows extraction of the thermodynamic constants defining defect generation. General agreement of these constants with bulk values derived by thermogravimetric analysis is found, thereby confirming the suitability of this technique for measuring oxygen non-stoichiometry of thin oxide films. Potential sources of error observed in earlier chemical capacitance studies on perovskite structured oxide films are also discussed.

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