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Materials design, synthesis, and transport properties of disordered rare-earth Zintl bismuthides with the anti-Th3P4 structure type.

The synthesis, structural elucidation, and transport properties of the extended series Ca4-xRExBi3 (RE = Y, La-Nd, Sm, Gd-Tm, and Lu; x ≈ 1) and Ca4-xRExBi3-δSbδ (RE = La, Ho, Er, and Lu; x ≈ 1, δ ≈ 1.5) are presented. Structural elucidation is based on single-crystal X-ray diffraction data and confirms the chemical drive of Ca4Bi3 with the cubic anti-Th3P4 structure type (space group I4̄3d, no. 220, Z = 4) into a Zintl phase by the introduction of trivalent rare-earth atoms. The structure features complex bonding, heavy elements, and electron count akin to that of valence-precise semiconductors, making it an ideal target for thermoelectrics development. Introducing crystallographic site disorders at the cation site for the Ca4-xRExBi3 phase and both the cation and anion sites for the Ca4-xRExBi3-δSbδ phase brings about additional desirable characteristics for thermoelectric materials in the context of tuning knobs for lowering thermal conductivity. Electronic structure calculations of idealized Ca3YBi3 and Ca3LaBi3 compounds indicate the opening of indirect bandgaps at the Fermi level with magnitudes Eg = 0.38 eV and 0.57 eV, respectively. The electrical resistivity ρ(T) of some of the investigated phases measured on single crystals evolve in a metallic manner with magnitudes of order 1.4 mΩ cm near 500 K, thus supporting the notion of a degenerate semiconducting state, with the temperature dependence of the Seebeck coefficient α(T) suggesting the p-type behavior. The low electrical resistivity and the realization of a degenerate semiconducting state in the title phases present a window of opportunity for optimizing their carrier concentrations for enhanced thermoelectric performance.