Thermoelectric stability of Eu- and Na-substituted PbTe

As one family of the most investigated thermoelectrics (TE), PbTe-based materials have been developed into state-of-the-art p-type and n-type TE materials. However, there are quite a few studies focusing on the reproducibility of TE properties and microstructure evolution during different heat treatments. In this work, Pb_0.98-xNa_0.02Eu_xTe (x = 0-0.030) samples were systematically examined after three different kinds of heat treatments: spark plasma sintering (SPS), laser flash measurement (LFA), and long-term annealing. The maximal solubility of Eu (ca. 1.0 atom%) in Pb_0.98-xNa_0.02Eu_xTe was established at 873 K. The most inhomogeneous samples (samples after SPS) show highest values of figure-of-merit, ZT_max, of up to 2.1 at 760 K, due to a large number of micrometer-scale sodium- and europium-rich aggregations in them. After additional heat treatment (LFA measurement or long-term annealing), the ZT_max value reduces to 1.6. The distribution of Eu and Na in the samples becomes much more homogeneous, accompanied by increased lattice parameters and decreased carrier concentrations. The long-term annealed samples have the best stable TE properties and good mechanical stability in the cyclic measurements. Surface protection needs to be considered for the temperatures above 773 K in order to avoid material decomposition.