Thermoelectric Material SnPb₂Bi₂S₆: The ^4,4L Member of Lillianite Homologous Series with Low Lattice Thermal Conductivity

Abstract

Although the binary sulfides Bi2S3, PbS, and SnS have attracted extensive interest as thermoelectric materials, no quaternary sulfides containing Sn/Pb/Bi/S elements have been reported. Herein, we report the synthesis of a new quaternary sulfide, SnPb2Bi2S6, which crystallizes in the orthorhombic space group Pnma with unit cell parameters of a = 20.5458(12) Å, b = 4.0925(4) Å, c = 13.3219(10) Å. SnPb2Bi2S6 has a lillianite-type crystal structure consisting of two alternately aligned NaCl-type structural motifs separated by a mirror plane of PbS7 monocapped trigonal prisms. In the lillianite homologous series, SnPb2Bi2S6 can be classified as 4,4L, where the superscripted numbers indicate the maximum numbers of edge-sharing octahedra in the two adjacent NaCl-shaped slabs along the diagonal direction. The obtained SnPb2Bi2S6 phase exhibited good thermal stability up to 1000 K and n-type degenerate semiconducting behavior, with a power factor of 3.7 μW cm–1 K–2 at 773 K. Notably, this compound exhibited a very low lattice thermal conductivity of 0.69–0.92 W m–1 K–1 at 300–1000 K. Theoretical calculations revealed that the low thermal conductivity is caused by the complex crystal structure and the related elastic properties of a low Debye temperature, low phonon velocity, and large Grüneisen parameters. A reasonable figure of merit (ZT) of ∼0.3 was obtained at 770 K.