Bi-substitution effects on crystal structure and thermoelectric properties of Ca3Co4O9 single crystals

Masashi Mikam, Kanji Chong, Yuzuru Miyazaki, Tsuyoshi Kajitani, Takahiro Inoue, Satoshi Sodeoka, Ryoji Funahashi

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40 Citations (Scopus)


We grew single crystals of partially Bi-substituted Ca3Co 4O9 phase in a solution consisting of K2CO 3-KCl solvent. All the X-ray diffraction patterns of the single crystals with different Bi contents were attributable to the Ca 3Co4O9 structure, although weak diffraction peaks from a secondary phase of Bi2Ca2Co2O x were observed in the crystals grown from a starting composition molar ratio of Ca : Bi : Co = 2.5 : 0.5 : 4.0 (BC-0.5 crystal). Thermoelectric properties of the crystals in the ab-plane were measured at various temperatures. Seebeck coefficient (S) was increased by the partial Bi-substitution at room temperature, whereas electrical resistivity (ρ) was decreased at room temperature except for BC-0.5 crystals. The simultaneous increase in S and decrease in ρ suggest an increase in carrier mobility. Although Bi atoms are heavier than the replaced Ca or Co atoms, the phonon part of thermal conductivity is increased by the Bi-substitution. We suggest that these effects of the Bi-substitution on thermoelectric properties are largely governed by changes in the peculiar crystal structure, such as the misfit relationship between the CoO2 and Ca2CoO3 layers, which constitute the layered structure of the Co3O 4O9 phase.

Original languageEnglish
Pages (from-to)4131-4136
Number of pages6
JournalJapanese Journal of Applied Physics, Part 1: Regular Papers and Short Notes and Review Papers
Issue number5 A
Publication statusPublished - 2006 May 9


  • Layered structure
  • Misfit structure
  • Oxides
  • Single-crystal
  • Thermoelectric properties

ASJC Scopus subject areas

  • Engineering(all)
  • Physics and Astronomy(all)


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