Systematic study on synthesis and structural, electrical transport and magnetic properties of Pb-substituted Bi-Ca-Co-O misfit-layer cobaltites

Single-phases of Pb-substituted Bi-Ca-Co-O misfit-layer cobaltites with various Pb concentrations have been synthesized and the Pb-substitution effects on the structural, electrical and magnetic properties have been systematically investigated. Powder X-ray diffraction analysis showed that the single-phases of Bi_1.8−x/2Pb_xCa₂Co₂O_z were obtained up to x=0.6-0.7 under the optimized synthesis conditions. The lattice parameters of Bi_1.8−x/2Pb_xCa₂Co₂O_z continuously changed with increasing Pb concentration. The electron diffraction analysis suggested that the structure consisted of two different sublattices with a rock salt structure (RS) and a hexagonal CdI₂ structure (H), respectively, without modulation. In combined with the chemical composition analysis, the chemical formulas of the x=0 and x=0.6 samples were determined approximately as [Bi_1.74Co_0.31Ca_2.01O₄]^RS[CoO₂]_1.69 and [Bi_1.47Pb_0.38Co_0.29Ca_1.98O₄]^RS[CoO₂]_1.71, respectively. The electrical resistivity became more metallic with increasing the Pb concentration up to x=0.6. Moreover, the Pb-substitution simultaneously increased the antiferromagnetic Weiss temperatures and decreased the effective magnetic moments of the Co ions.