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 12P-GeBi4Te7 (space group P3m1) and 51R-GeBi6Te10 (space group R3m) structure types they adopt. Modified compositions Mn1−xBi4+2x/3Te7 (x = 0.15–0.2) and Mn1−xBi6+2x/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 (12P stacking) in Mn0.85Bi4.10Te7 and 2 : 1 sequence (51R 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.