Germanium Antimony Bonding in Ba₄Ge₂Sb₂Te₁₀ with Low Thermal Conductivity

Abstract

A new quaternary telluride, Ba₄Ge₂Sb₂Te₁₀, was synthesized at high temperature via the reaction of elements. A single-crystal X-ray diffraction study shows that the title compound crystallizes in its own structure type in the monoclinic <i>P</i>2₁/<i>c</i> space group having cell dimensions of <i>a</i> = 13.984(3) Å, <i>b</i> = 13.472(3) Å, <i>c</i> = 13.569(3) Å, and β = 90.16(3)° with four formula units per unit cell (<i>Z</i> = 4). The pseudo-one-dimensional crystal structure of Ba₄Ge₂Sb₂Te₁₀ consists of infinite ₁^∞[Ge₂Sb₂Te₁₀]^8- stripes, which are separated by Ba²⁺ cations. Each of the Ge(1) atoms is covalently bonded to four Te atoms, whereas the Ge(2) atom is covalently bonded with one Sb(2) and three Te atoms in a distorted tetrahedral geometry. The title compound is the first example of a chalcogenide that shows Ge-Sb bonding. The Sb(1) atom is present at the center of the seesaw geometry of four Te atoms. In contrast, the Sb(2) atom forms a seesaw geometry by coordinating with one Ge(2) and three Te atoms. Condensation of these Ge and Sb centered polyhedral units lead to the formation of ₁^∞[Ge₂Sb₂Te₁₀]^8- stripes. The temperature-dependent resistivity study suggests the semimetallic/degenerate semiconducting nature of polycrystalline Ba₄Ge₂Sb₂Te₁₀. The positive sign of Seebeck coefficient values indicates that the predominant charge carriers are holes in Ba₄Ge₂Sb₂Te₁₀. An extremely low lattice thermal conductivity of ∼0.34 W/mK at 773 K was observed for polycrystalline Ba₄Ge₂Sb₂Te₁₀, which is presumably due to the lattice anharmonicity induced by the stereochemically active 5s² lone pair of Sb. The electronic structure of Ba₄Ge₂Sb₂Te₁₀ and the bonding of atom pairs in the structure have been analyzed by means of ELF analysis and crystal orbital Hamilton population (COHP) analysis.