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Crystal structure and high-temperature electrical conductivity of novel perovskite-related gallium and indium oxides

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Abstract

Novel complex oxides Sr2Ga1+x In1−x O5, x = 0.0–0.2 with brownmillerite-type structure were prepared in air at T = 1,273 K, 24 h. Study of the crystal structure of Sr2Ga1.1In0.9O5 refined using X-ray powder diffraction data (S.G. Icmm, a = 5.9694(1) Å, b = 15.2091(3) Å, c = 5.7122(1) Å, χ 2 = 2.48, R F 2  = 0.0504, R p = 0.0458) revealed ordering of Ga3+ and In3+ cations over tetrahedral and octahedral positions, respectively. A partial replacement of Sr2+ by La3+ according to formula Sr1−y La y Ga0.5In0.5O2.5+y/2, leads to the formation of a cubic perovskite (a = 4.0291(5) Å) for y = 0.3. No ordering of oxygen vacancies or cations was observed in Sr0.7La0.3Ga0.5In0.5O2.65 as revealed by electron diffraction study. The trace diffusion coefficient (D T) of oxygen for cubic perovskite Sr0.7La0.3Ga0.5In0.5O2.65 is in the range 2.0 × 10−9–6.3 × 10−8 cm2/s with activation energy 1.4(1) eV as determined by isotopic exchange depth profile technique using secondary ion mass spectrometry at 973–1,223 K. These values are close to those reported for Ca-doped ZrO2. High-temperature electrical conductivity of Sr0.7La0.3Ga0.5In0.5O2.65 studied by AC impedance was found to be nearly independent on oxygen partial pressure. Calculated values of activation energy at T < 1,073 K for hole and oxide-ion conductivities are 0.96 and 1.10 eV, respectively.

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Acknowledgments

This work was partially supported by Ministry of Science and Education of Russian Federation (state contract 14.740.12.1358), Russian Foundation for Basic Research (grant no. 11-08-01159a and 11-03-01225), and MSU-development Program up to 2020. This work is financially supported by the Swedish Research Council (VR) and the Baltic Sea/Visby program from the Swedish Institute. The electron microscopy facility was supported by Knut and Alice Wallenberg Foundation.

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Authors and Affiliations

  1. Department of Chemistry, Moscow State University, Leninskie Gory, Moscow, 119991, Russia

    S. Ya. Istomin & E. V. Antipov

  2. Institute of Solid State Physics RAS, Chernogolovka, 142432, Russia

    Yu. S. Fedotov & S. I. Bredikhin

  3. Institute of Problems of Chemical Physics RAS, Chernogolovka, 142432, Russia

    N. V. Lyskov

  4. Department of Materials and Environmental Chemistry, Stockholm University, Stockholm, 10691, Sweden

    S. Shafeie, G. Svensson, Y. Liu & Z. Shen

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  1. S. Ya. Istomin
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  2. E. V. Antipov
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  8. Y. Liu
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  9. Z. Shen
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Correspondence to S. Ya. Istomin.

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Istomin, S.Y., Antipov, E.V., Fedotov, Y.S. et al. Crystal structure and high-temperature electrical conductivity of novel perovskite-related gallium and indium oxides. J Solid State Electrochem 18, 1415–1423 (2014). https://doi.org/10.1007/s10008-013-2190-4

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  • DOI: https://doi.org/10.1007/s10008-013-2190-4

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