Hg_0.04Zn_3.96Sb₃: Synthesis, Crystal Structure, Phase Transition, and Thermoelectric Properties

The thermoelectric material Zn 4 Sb 3 was mercury doped by introduction of 1 at. % Hg into the synthesis mixture, resulting in Hg 0.04 Zn 3.96 Sb 3 . The doped compound and an undoped reference were characterized by multitemperature short wavelength synchrotron X-ray powder diffraction, SEM/EDX, differential scanning calorimetry (DSC), and physical property measurements. Rietveld refinements suggest that mercury substitution takes place solely on the Zn1 framework site of the disordered room temperature β-phase crystal structure, while the interstitial positions are mercury-free. The refined composition suggests a doping level of 0.6%. The remaining mercury is present as elemental Hg as evidenced by SEM/EDX analysis, the presence of peaks corresponding to crystalline Hg below the Hg freezing temperature, and the presence of a drop in the resistivity at the superconducting transition temperature of Hg. Rietveld refinements of multitemperature synchrotron X-ray powder diffraction data (180 K < T < 290 K, Δ T = 10 K) reveal a significant change in the α–α′–β phase transition temperatures between undoped and 1% Hg-doped samples. This is corroborated by DSC data that show that the transition enthalpies are very small, about 0.1–0.4 J/g. The largest enthalpy change is observed in the α–α′ transition for the undoped sample, whereas the largest transition enthalpy is found in the α′–β transition for the Hg-doped compound. Complete thermoelectric properties have been measured in the temperature range 2–400 K on dense samples prepared by spark plasma sintering. The Hg doping has a very large effect on the transport properties in the ordered α-phase crystal structure but only a minor influence on the properties in the disordered β-phase. The thermoelectric figure of merit, ZT, is found to be ∼0.3 for both the undoped and the Hg-doped sample at 300 K.