Phosphide–Tetrahedrite Ag6Ge10P12: Thermoelectric Performance of a Long-Forgotten Silver-Cluster Compound

Abstract

The air-stable phosphide, Ag6Ge10P12, was synthesized from its elements in gram amounts. As its structure is closely related to high-performance thermoelectric tetrahedrites (Ag6□Ge4Ge6P12 ≡ Cu6SSb4Cu6S12), we studied temperature dependent single-crystal X-ray diffraction experiments, quantum chemical calculations, and thermoelectric transport properties of spark plasma sintered and pristine, single crystalline samples, in order to give a comprehensive picture of its thermoelectric performance and its origin. The semiconducting character of this material is reflected in band structure calculations. Measurements of the thermal diffusivity exhibit a very low thermal conductivity, κ < 1 W m–1 K–1, which is close to a phonon glass-like behavior, and has its origin in a strong local bonding asymmetry, induced by strong bonding of the phosphorus–germanium (Ge4+) covalent framework and weak bonding of lone-pair electrons (Ge2+). This chemical bond hierarchy creates a pronounced anisotropic behavior of the silver...