We report the evaluation of the thermoelectric performance of polycrystalline p-type SnSe, a material in which unprecedented values of the thermoelectric figure of merit ZT have been recently discovered in single crystals Besides anisotropic transport properties, our results confirm that this compound exhibits intrinsically very low thermal conductivity values The electrical properties show trends typical of lightly doped, intrinsic semiconductors with thermopower values reaching 500 μV K−1 in a broad temperature range An orthorhombic-to-orthorhombic transition sets in at 823 K, a temperature at which the power factor reaches its maximum value A maximum ZT of 05 was obtained at 823 K, suggesting that proper optimization of the transport properties of SnSe might lead to higher ZT values These findings indicate that this system represents an interesting experimental platform for the search of highly efficient thermoelectric materials

Assessment of the thermoelectric performance of polycrystalline p-type SnSe

SnSe has attracted some attention due to the recent report of record high thermoelectric figure-of-merit (ZT) of ∼2.6 at about 923 K in single crystals. Even though the ZT is high in single crystal SnSe, it was very low in its polycrystalline form due to the very low electrical conductivity (<103 S m−1) from 300 K to 700 K. In this work, we report studies on enhancement of electrical conductivity by Na doping to optimize the carrier concentration in polycrystalline SnSe prepared by melting and hot pressing. A room temperature carrier concentration of ∼2.7 × 1019 cm−3 was obtained in 2 atm% Na-doped SnSe samples with the highest power factor obtained in 1.5 atm% Na-doping. A peak ZT of ∼0.8 was achieved at 773 K along the hot pressing direction and the average ZT was improved.

Studies on thermoelectric figure of merit of Na-doped p-type polycrystalline SnSe

Due to the urgency of our energy and environmental issues, a variety of cost-effective and pollution-free technologies have attracted considerable attention, among which thermoelectric technology has made enormous progress. Substantial numbers of new thermoelectric materials are created with high figure of merit (ZT) by using advanced nanoscience and nanotechnology. This is especially true in the case of metal-chalcogenide-based materials, which possess both relatively high ZT and low cost among all the different kinds of thermoelectric materials. Here, comprehensive coverage of recent advances in metal chalcogenides and their correlated thermoelectric enhancement mechanisms are provided. Several new strategies are summarized with the hope that they can inspire further enhancement of performance, both in metal chalcogenides and in other materials.

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Thermoelectric Enhancement of Different Kinds of Metal Chalcogenides

The ability of some materials with a perfectly ordered crystal structure to mimic the heat conduction of amorphous solids is a remarkable physical property that finds applications in numerous areas of materials science, for example, in the search for more efficient thermoelectric materials that enable to directly convert heat into electricity. Here, we unveil the mechanism in which glass-like thermal conductivity emerges in tetrahedrites, a family of natural minerals extensively studied in geology and, more recently, in thermoelectricity. By investigating the lattice dynamics of two tetrahedrites of very close compositions (Cu12Sb2Te2S13 and Cu10Te4S13) but with opposite glasslike and crystal thermal transport by means of powder and single-crystal inelastic neutron scattering, we demonstrate that the former originates from the peculiar chemical environment of the copper atoms giving rise to a strongly anharmonic excess of vibrational states.

From crystal to glass-like thermal conductivity in crystalline minerals

Ultralow thermal conductivity is of great interest in a variety of fields, including thermoelectric energy conversion. We report, for the first time, experimental evidence that Ga-doping in SnTe may lower the lattice thermal conduction slightly below the theoretical amorphous minimum at high temperature. Such an effect is justified by the spontaneous formation of nanoprecipitates we characterized as GaTe. Remarkably, the introduction of Ga (2–10%) in SnTe also improves the electronic transport properties by activating several hole pockets in the multivalley valence band. Experimental results are supported by density functional theory calculations. The thermoelectric figure of merit, ZT, reaches ∼1 at 873 K in Sn0.96Ga0.07Te, which corresponds to an ∼80% improvement with respect to pure SnTe.

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Ultralow Lattice Thermal Conductivity and Enhanced Thermoelectric Performance in SnTe:Ga Materials

Polycrystalline samples and single crystals of the new compound Ag3In2Mo15Se19 were synthesized by solid-state reaction in a sealed molybdenum crucible at 1300 °C. Its crystal structure (space group R3c, a = 9.9755(1) A, c = 57.2943(9) A, and Z = 6) was determined from single-crystal X-ray diffraction data and constitutes an Ag-filled variant of the In2Mo15Se19 structure-type containing octahedral Mo6 and bioctahedral Mo9 clusters in a 1:1 ratio. The increase of the cationic charge transfer due to the Ag insertion induces a modification of the Mo–Mo distances within the Mo clusters that is discussed with regard to the electronic structure. Transport properties were measured in a broad temperature range (2–1000 K) to assess the thermoelectric potential of this compound. The transport data indicate an electrical conduction dominated by electrons below 25 K and by holes above this temperature. The metallic character of the transport properties in this material is consistent with electronic band structure ca...

Synthesis, Crystal and Electronic Structures, and Thermoelectric Properties of the Novel Cluster Compound Ag3In2Mo15Se19

We report on a detailed investigation of the crystal and electronic band structures and of the transport and thermodynamic properties of the Mo-based cluster compound Ag2Tl2Mo9Se11. This novel structure type crystallizes in the trigonal space group R3c and is built of a three-dimensional network of interconnected Mo9Se11 units. Single-crystal X-ray diffraction indicates that the Ag and Tl atoms are distributed in the voids of the cluster framework, both of which show unusually large anisotropic thermal ellipsoids indicative of strong local disorder. First-principles calculations show a weakly dispersive band structure around the Fermi level as well as a semiconducting ground state. The former feature naturally explains the presence of both hole-like and electron-like signals observed in Hall effect. Of particular interest is the very low thermal conductivity that remains quasi-constant between 150 and 800 K at a value of approximately 0.6 W·m(-1)·K(-1). The lattice thermal conductivity is close to its minimum possible value, that is, in a regime where the phonon mean free path nears the mean interatomic distance. Such extremely low values likely originate from the disorder induced by the Ag and Tl atoms giving rise to strong anharmonicity of the lattice vibrations. The strongly limited ability of this compound to transport heat is the key feature that leads to a dimensionless thermoelectric figure of merit ZT of 0.6 at 800 K.

X-ray characterization, electronic band structure, and thermoelectric properties of the cluster compound Ag2Tl2Mo9Se11.

We present a detailed study of the evolution of the electrical, galvanomagnetic, and thermodynamic properties of polycrystalline AgxMo9Se11 compounds for 3.4 ≤ x ≤ 3.8 at low temperatures (2–350 K). In agreement with density functional theory calculations, the collected data show an overall gradual variation in the transport properties from metallic to semiconducting behavior on going from x = 3.4 to 3.8. The results evidence subtle variations in the electronic properties with the Ag content, typified by both positive and negative phonon-drag effects together with thermopower and Hall coefficient of opposite signs. Analysis of the data suggests that these features may be due to peculiarities of the dispersion of the valence bands in the vicinity of the chemical potential. A drastic influence of the Ag content on the thermal transport was evidenced by a pronounced change in the temperature dependence of the specific heat below 10 K. Nonlinearities in the Cp(T3) data are correlated to the concentration of A...

Malika Colin

Papers

Synthesis, Crystal and Electronic Structures, and Thermoelectric Properties of the Novel Cluster Compound Ag3In2Mo15Se19

X-ray characterization, electronic band structure, and thermoelectric properties of the cluster compound Ag2Tl2Mo9Se11.

Comprehensive Study of the Low-Temperature Transport and Thermodynamic Properties of the Cluster Compounds AgxMo9Se11 (3.41 ≤ x ≤ 3.78)