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Divacancy superstructures in thermoelectric calcium-doped sodium cobaltate

Abstract : We have grown single crystals of NaxCayCoO2 and determined their superstructures as a function of composition using neutron and x-ray diffraction. Inclusion of Ca 2+ stabilises a single superstructure across a wide range of temperatures and concentrations. The superstructure in the Na + layers is based on arrays of divacancy clusters with Ca 2+ ions occupying the central site, and it has an ideal concentration Na 4/7 Ca 1/7 CoO2. Previous measurements of the thermoelectric properties on this system are discussed in light of this superstructure. Na 4/7 Ca 1/7 CoO2 corresponds to the maximum in thermoelectric performance of this system.
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D. Porter, M. Roger, M. J. Gutmann, S. Uthayakumar, D. Prabhakaran, et al.. Divacancy superstructures in thermoelectric calcium-doped sodium cobaltate. Physical Review B: Condensed Matter and Materials Physics, American Physical Society, 2014, 90, pp.054101. ⟨10.1103/PhysRevB.90.054101⟩. ⟨cea-01376304⟩

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