In situ nanostructuring in bulk thermoelectric materials through thermo-dynamic phase segregation has established itself as an effective paradigm for optimizing the performance of thermoelectric materials. In bulk PbTe small compositional variations create coherent and semicoherent nanometer sized precipitates embedded in a PbTe matrix, where they can impede phonon propagation at little or no expense to the electronic properties. In this paper the nanostructuring paradigm is for the first time extended to a bulk PbS based system, which despite obvious advantages of price and abundancy, so far has been largely disregarded in thermoelectric research due to inferior room temperature thermoelectric properties relative to the pristine fellow chalcogenides, PbSe and PbTe. Herein we report on the synthesis, microstructural morphology and thermoelectric properties of two phase (PbS)(1-x)(PbTe)(x)x = 0-0.16 samples. We have found that the addition of only a few percent PbTe to PbS results in a highly nanostructured material, where PbTe precipitates are coherently and semicoherently embedded in a PbS matrix. The present (PbS)(1-x)(PbTe)(x) nanostructured samples show substantial decreases in lattice thermal conductivity relative to pristine PbS, while the electronic properties are left largely unaltered. This in turn leads to a marked increase in the thermoelectric figure of merit. This study underlines the efficiency of the nanostructuring approach and strongly supports its generality and applicability to other material systems. We demonstrate that these PbS-based materials, which are made primarily from abundant Pb and S, outperform optimally n-type doped pristine PbTe above 770 K.

The effect of K and K-Na substitution for Pb atoms in the rock salt lattice of PbTe was investigated to test a hypothesis for development of resonant states in the valence band that may enhance the thermoelectric power. We combined high temperature Hall-effect, electrical conductivity and thermal conductivity measurements to show that K-Na co-doping do not form resonance states but2 can control the energy difference of the maxima of the two primary valence sub-bands in PbTe. This leads to an enhanced interband interaction with rising temperature and a significant rise in the thermoelectric figure of merit of p-type PbTe. The experimental data can be explained by a combination of a single and two-band model for the valence band of PbTe depending on hole density that varies in the range of 1 − 15 × 10 19 cm −3 .

We report promising thermoelectric properties of the rock salt PbSe-PbS system which consists of chemical elements with high natural abundance. Doping with PbCl(2), excess Pb, and Bi gives n-type behavior without significantly perturbing the cation sublattice. Thus, despite the great extent of dissolution of PbS in PbSe, the transport properties in this system, such as carrier mobilities and power factors, are remarkably similar to those of pristine n-type PbSe in fractions as high as 16%. The unexpected finding is the presence of precipitates ~2-5 nm in size, revealed by transmission electron microscopy, that increase in density with increasing PbS concentration, in contrast to previous reports of the occurrence of a complete solid solution in this system. We report a marked impact of the observed nanostructuring on the lattice thermal conductivity, as highlighted by contrasting the experimental values (~1.3 W/mK) to those predicted by Klemens-Drabble theory at room temperature (~1.6 W/mK). Our thermal conductivity results show that, unlike in PbTe, optical phonon excitations in PbSe-PbS systems contribute to heat transport at all temperatures. We show that figures of merit reaching as high as ~1.2-1.3 at 900 K can be obtained, suggesting that large-scale applications with good conversion efficiencies are possible from systems based on abundant, inexpensive chemical elements.