The effect of Mg doping on the thermoelectric performance of Zn4Sb3

Cation doping studies of high performance thermoelectric Zn4Sb3 have so far focused on elements with larger electronegativity than Zn. Mg has a lower electronegativity than Zn, and, in the present paper, the effect of Mg doping of Zn4Sb3 on phase transition temperatures and thermal and thermoelectric properties have been studied on five samples with a doping degree ranging from 0.1 to 2 at. % Mg. The results are compared with data obtained for a pure, undoped sample. Laboratory x-ray powder diffraction shows that all samples are single phase materials as further evidenced with higher confidence by Rietveld refinement of high resolution synchrotron powder diffraction of as synthesized 1 and 2 at. % Mg doped samples. Multitemperature synchrotron powder diffraction and differential scanning calorimetry reveal a significant effect of Mg-doping on the low temperature phase transitions in one sample (0.5 at. % Mg), whereas the other samples showed only small or no effect. Physical properties have been evaluated from 2–400 K for all samples. Some physical property parameters are affected by doping but no immediate improvement of ZT was achieved. The reason for this is discussed in relation to differences in sample compaction.