Layered Manganese Bismuth Tellurides with GeBi4Te7– and GeBi6Te10–type Structures: Towards Multifunctional Materials

The crystal structures of new layered manganese bismuth tellurides with the compositions Mn0.85(3)Bi4.10(2)Te7 and Mn0.73(4)Bi6.18(2)Te10 were determined by single-crystal X-ray diffraction, including the use of microfocused synchrotron radiation. These analyses reveal that the layered structures deviate from the idealized stoichiometry of the 12 P -GeBi4Te7 (space group P 3 m 1) and 51 R -GeBi6Te10 (space group R 3 m ) structure types they adopt. Modified compositions Mn1– x Bi4+2 x /3Te7 ( x = 0.15 – 0.2) and Mn1– x Bi6+2 x /3Te10 ( x = 0.19 – 0.26) assume cation vacancies and lead to homogenous bulk samples as confirmed by Rietveld refinements. Electron diffraction patterns exhibit no diffuse streaks that would indicate stacking disorder. The alternating quintuple-layer [M2Te3] and septuple-layer [M3Te4] slabs (M = mixed occupied by Bi and Mn) with 1:1 sequence (12 P stacking) in Mn0.85Bi4.10Te7 and 2:1 sequence (51 R stacking) in Mn0.81Bi6.13Te10 were also observed in HRTEM images. Temperature-dependent powder diffraction and differential scanning calorimetry show that the compounds are high temperature phases, which are metastable at ambient temperature. Magnetization measurements are in accordance with a MnII oxidation state and point at predominantly ferromagnetic coupling in both compounds. The thermoelectric figures of merit of n-type conducting Mn0.85Bi4.10Te7 and Mn0.81Bi6.13Te10 reach zT = 0.25 at 375 °C and zT = 0.28 at 325 °C, respectively. Although the compounds are metastable, compact ingots exhibit still up to 80% of the main phases after thermoelectric measurements up to 400 °C.