Jean-Baptiste Vaney

Assessment of the thermoelectric performance of polycrystalline p-type SnSe

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 0.5 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.

Reinvestigation of the thermal properties of single-crystalline SnSe

The simple binary SnSe has been recently proposed as a prospective candidate for thermoelectric applications due to its exceptionally low lattice thermal conductivity. However, the thermal transport in single crystals was found to be significantly lower than in polycrystalline samples despite the presence of grain boundary scattering in the latter. In order to better understand the origin of this issue, we report here on a detailed characterization of the thermoelectric properties of a vertical-Bridgman-grown single-crystal of SnSe along the a, b, and c crystallographic axes in a wide range of temperatures (5–700 K). We find that the thermal conductivity features a pronounced Umklapp peak near 12 K whose magnitude depends on the crystal orientation. Unlike prior reports, our results evidence a significant anisotropy between the a, b, and c directions with lattice thermal conductivity values reaching 1.2, 2.3, and 1.7 W m−1 K−1 at 300 K, respectively. While the fundamental reasons behind these differences ...

High thermoelectric performance in Sn-substituted α-As2Te3

Lead chalcogenides PbX (X = Te, Se, S) have been the materials of choice for thermoelectric power generation at mid-range temperatures (500–700 K). Here, we report on a new family of chalcogenides α-As2Te3 that exhibit similar thermoelectric performances near 500 K. Sn doping in p-type polycrystalline α-As2−xSnxTe3 (x ≤ 0.075) provides an efficient control parameter to tune the carrier concentration leading to thermopower values that exceed 300 μV K−1 at 500 K. Combined with the structural complexity of the monoclinic lattice that results in extremely low thermal conductivity (0.55 W m−1 K−1 at 523 K), a peak ZT value of 0.8 is achieved at 523 K for x = 0.05. A single-parabolic band model is found to capture well the variations in the transport properties with the Sn concentration and suggests that higher ZT values could be achieved through band structure engineering. These results surpass those obtained in the sister compounds β-As2−xSnxTe3 and further show that α-As2Te3 based materials are competitive with other chalcogenides for thermoelectric applications at intermediate temperatures.

Electronic structure, low-temperature transport and thermodynamic properties of polymorphic β-As2Te3

β-As2Te3 belongs to the prominent family of Bi2Te3-based materials, which show excellent thermoelectric properties near room temperature. In this study, we report a joint theoretical and experimental investigation of its electronic and thermal properties at low temperatures (5–300 K). These results are complemented by specific heat measurements (1.8–300 K) that provide further experimental evidence of the first order lattice distortion undergone by β-As2Te3 near 190 K. Data taken on cooling and heating across this transition show that the lattice distortion has little influence on the electronic properties and further evidence a weak hysteretic behavior. Although first-principles calculations predict a semiconducting ground state, these measurements show that β-As2Te3 behaves as a degenerate p-type semiconductor with a high carrier concentration of 1020 cm−3 at 300 K likely due to intrinsic defects. Calculations of the vibrational properties indicate that the extremely low lattice thermal conductivity values (0.8 W m−1 K−1 at 300 K) mainly originate from low-energy Te optical modes that limit the energy window of the acoustic branches. This limited ability to transport heat combined with a relatively large band gap suggest that high thermoelectric efficiency could be achieved in this compound when appropriately doped.

High-temperature thermoelectric properties of the β-As2−xBixTe3 solid solution

Bi2Te3-based compounds are a well-known class of outstanding thermoelectric materials. β-As2Te3, another member of this family, exhibits promising thermoelectric properties around 400 K when appropriately doped. Herein, we investigate the high-temperature thermoelectric properties of the β-As2−xBixTe3 solid solution. Powder X-ray diffraction and scanning electron microscopy experiments showed that a solid solution only exists up to x = 0.035. We found that substituting Bi for As has a beneficial influence on the thermopower, which, combined with extremely low thermal conductivity values, results in a maximum ZT value of 0.7 at 423 K for x = 0.017 perpendicular to the pressing direction.

Electrical, Thermal, and Magnetic Characterization of Natural Tetrahedrites–Tennantites of Different Origin

Naturally occurring sulfosalt minerals of the tetrahedrite–tennantite series ((Cu,Fe,Zn,Ag,Hg)12(Sb,As)4S13) are studied because of their potential use as basic components in the manufacture of thermoelectric devices for moderate-temperature applications. In the work reported herein, the chemical, crystallographic, thermoelectric, and magnetic properties of four specimens from different ores from Europe and America were exhaustively characterized. Our study revealed that these natural tetrahedrites usually behave as low-to-moderately doped p-type semiconductors with low mobility. Their carrier charge transport is thus located at the edge between hopping and itinerant mechanisms. The magnetic study, probing the behavior of the constituent iron species, revealed that an insignificant part of the iron occurs as ferromagnetic impurities. The dominant iron species is Fe2+ ions with antiferromagnetic interactions. The maximum value of ZT observed was 0.13 at 700 K; this value is impaired, primarily, by high electrical resistivity.