Sn-Sb alloys are important high-temperature solders. However, inconsistencies are found in the available phase diagrams, and some phase boundaries in the Sn-Sb system have not been determined. Sn-Sb alloys were prepared, equilibrated at 160°C to 300°C, and the equilibrium phases and their compositions were determined. The b-SnSb phase has a very wide compositional homogeneity range, and its composition varies from Sn-47.0at.%Sb to Sn-62.8at.%Sb. There is no order-disorder transformation of the b-SnSb phase. There are three peritectic reactions in the Sn-Sb system, L + Sb = b-SnSb, L + b-SnSb = Sn 3 Sb 2 , and L + Sn 3 Sb 2 = Sn, and their temperatures are 424°C, 323°C, and 243°C, respectively. Thermodynamic models of the Sn-Sb binary system were developed using the CALPHAD approach based on the experimental results of this study and the data in the literature. The calculated phase diagram and thermodynamic properties are in good agreement with the experimental determinations.

Thermoelectric (TE) research is not only a course of materials by discovery but also a seedbed of novel concepts and methodologies. Herein, the focus is on recent advances in three emerging paradigms: entropy engineering, phase‐boundary mapping, and liquid‐like TE materials in the context of thermodynamic routes. Specifically, entropy engineering is underpinned by the core effects of high‐entropy alloys; the extended solubility limit, the tendency to form a high‐symmetry crystal structure, severe lattice distortions, and sluggish diffusion processes afford large phase space for performance optimization, high electronic‐band degeneracy, rich multiscale microstructures, and low lattice thermal conductivity toward higher‐performance TE materials. Entropy engineering is successfully implemented in half‐Huesler and IV–VI compounds. In Zintl phases and skutterudites, the efficacy of phase‐boundary mapping is demonstrated through unraveling the profound relations among chemical compositions, mutual solubilities of constituent elements, phase instability, microstructures, and resulting TE properties at the operation temperatures. Attention is also given to liquid‐like TE materials that exhibit lattice thermal conductivity at lower than the amorphous limit due to intensive mobile ion disorder and reduced vibrational entropy. To conclude, an outlook on the development of next‐generation TE materials in line with these thermodynamic routes is given.

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The stability of intrinsic point defects in PbTe, one of the most widely studied and efficient thermoelectric material, is explored by means of Density Functional Theory (DFT). The origin of nand p-type conductivity in PbTe is attributed to particular intrinsic charged defects by calculating their formation energies. These DFT calculated defect formation energies are then used in the Gibbs free energy description of this phase as part of the Pb-Te thermodynamic model built using the CALPHAD method, and in the resulting phase diagram it is found that its solubility lines and non-stoichiometric range agree very well with experimental data. Such an approach of using DFT in conjunction with CALPHAD for compound semiconductor phases that exhibit very small ranges of non-stoichiometry does not only make the process of calculating phase diagrams for such systems more physical, but is necessary and critical for the assessment of unknown phase diagrams.

Single-crystalline SnSe has attracted much attention because of its record high figure-of-merit ZT ≈ 2.6; however, this high ZT has been associated with the low mass density of samples which leaves the intrinsic ZT of fully dense pristine SnSe in question. To this end, we prepared high-quality fully dense SnSe single crystals and performed detailed structural, electrical, and thermal transport measurements over a wide temperature range along the major crystallographic directions. Our single crystals were fully dense and of high purity as confirmed via high statistics 119 Sn Mössbauer spectroscopy that revealed <0.35 at. % Sn(IV) in pristine SnSe. The temperature-dependent heat capacity ( C p ) provided evidence for the displacive second-order phase transition from Pnma to Cmcm phase at T c ≈ 800 K and a small but finite Sommerfeld coefficient γ 0 which implied the presence of a finite Fermi surface. Interestingly, despite its strongly temperature-dependent band gap inferred from density functional theory calculations, SnSe behaves like a low-carrier-concentration multiband metal below 600 K, above which it exhibits a semiconducting behavior. Notably, our high-quality single-crystalline SnSe exhibits a thermoelectric figure-of-merit ZT ∼1.0, ∼0.8, and ∼0.25 at 850 K along the b , c , and a directions, respectively.