Synthesis, structure, magnetism, and high temperature thermoelectric properties of Ge doped Yb₁₄MnSb₁₁

The Zintl phase Yb₁₄MnSb₁₁ was successfully doped with Ge utilizing a tin flux technique. The stoichiometry was determined by microprobe analysis to be Yb_13.99(14)Mn_1.05(5)Sb _10.89(16)Ge_0.06(3). This was the maximum amount of Ge that could be incorporated into the structure via flux synthesis regardless of the amount included in the reaction. Single crystal X-ray diffraction could not unambiguously determine the site occupancy for Ge. Bond lengths varied by about 1% or less, compared with the undoped structure, suggesting that the small amount of Ge dopant does not significantly perturb the structure. Differential scanning calorimetry/thermogravimetry (DSC/TG) show that the doped compound's melting point is greater than 1200 K. The electrical resistivity and magnetism are virtually unchanged from the parent material, suggesting that Yb is present as Yb²⁺ and that the Ge dopant has little effect on the magnetic structure. At 900 K the resistivity and Seebeck coefficient decrease resulting in a zT of 0.45 at 1100 K, significantly lower than the undoped compound.