SnSe has been prepared by arc-melting, as mechanically robust pellets, consisting of highly oriented polycrystals. This material has been characterized by neutron powder diffraction (NPD), scanning electron microscopy, and transport measurements. A microscopic analysis from NPD data demonstrates a quite perfect stoichiometry SnSe0.98(2) and a fair amount of anharmonicity of the chemical bonds. The Seebeck coefficient reaches a record maximum value of 668 μV K−1 at 380 K; simultaneously, this highly oriented sample exhibits an extremely low thermal conductivity lower than 0.1 W m−1 K−1 around room temperature, which are two of the main ingredients of good thermoelectric materials. These excellent features exceed the reported values for this semiconducting compound in single crystalline form in the moderate-temperatures region and highlight its possibilities as a potential thermoelectric material.
Thermoelectric materials may contribute in the near future as new alternative sources of sustainable energy. Unprecedented thermoelectric properties in p-type SnSe single crystals have been recently reported, accompanied by extremely low thermal conductivity in polycrystalline samples. In order to enhance thermoelectric efficiency through proper tuning of this material we report a full structural characterization and evaluation of the thermoelectric properties of novel Ge-doped SnSe prepared by a straightforward arc-melting method, which yields nanostructured polycrystalline samples. Ge does not dope the system in the sense of donating carriers, yet the electrical properties show a semiconductor behavior with resistivity values higher than that of the parent compound, as a consequence of nanostructuration, whereas the Seebeck coefficient is higher and thermal conductivity lower, favorable to a better ZT figure of merit.
Thermoelectric materials constitute an alternative source of sustainable energy, harvested from waste heat. Bi2Te3 is the most utilized thermoelectric alloy. We show that it can be readily prepared in nanostructured form by arc-melting synthesis, yielding mechanically robust pellets of highly oriented polycrystals. This material has been characterized by neutron powder diffraction (NPD), scanning electron microscopy (SEM), and electronic and thermal transport measurements. A microscopic analysis from NPD data demonstrates a near-perfect stoichiometry of Bi2Te3 and a fair amount of anharmonicity of the chemical bonds. The as-grown material presents a metallic behavior, showing a record-low resistivity at 320 K of 2 μΩ m, which is advantageous for its performance as a thermoelectric material. SEM analysis shows a stacking of nanosized sheets, each of them presumably single-crystalline, with large surfaces perpendicular to the c crystallographic axis. This nanostructuration notably affects the thermoelectric properties, involving many surface boundaries that are responsible for large phonon scattering factors, yielding a thermal conductivity as low as 1.2 W m−1 K−1 around room temperature.
Sb-doped Bi2Te3 is known since the 1950s as the best thermoelectric material for near-room temperature operation. Improvements in material performance are expected from nanostructuring procedures. We present a straightforward and fast method to synthesize already nanostructured pellets that show an enhanced ZT due to a remarkably low thermal conductivity and unusually high Seebeck coefficient for a nominal composition optimized for arc-melting: Bi0.35Sb1.65Te3. We provide a detailed structural analysis of the Bi2−xSbxTe3 series (0 ≤ x ≤ 2) based on neutron powder diffraction as a function of composition and temperature that reveals the important role played by atomic vibrations. Arc-melting produces layered platelets with less than 50 nm-thick sheets. The low thermal conductivity is attributed to the phonon scattering at the grain boundaries of the nanosheets. This is a fast and cost-effective production method of highly efficient thermoelectric materials.
SnSe has been recently reported as an attractive thermoelectric material, with an extraordinarily high, positive, Seebeck coefficient. Here, we describe the synthesis, structural, microscopic, and thermoelectric characterization of Sn1–xSbxSe intermetallic alloys prepared by a straightforward arc-melting technique. Sb-doped tin selenide was synthesized as strongly nanostructured polycrystalline pellets. Neutron diffraction studies reveal that Sb is placed at the Sn sublattice in the crystal structure, showing concentrations as high as 30%, and generates a significant number of Sn vacancies, while the increase of the interlayer distances favors the nanostructuration. The material is nanostructured both out-of-plane in nanometer-scale layers and in-plane by ∼5 nm undulations of these layers. This nanostructuring, along with an increased amount of Sn vacancies, accounts for a reduction of the thermal conductivity, which is highly desirable for thermoelectric materials. The phonon mean free path is estimated to be on the order of 2 nm from low temperature, thermal conductivity, and specific heat, in accordance with the nanostructuration observed by high-resolution transmission electron microscopy. The thermal conductivity of SnSe is characterized by three independent techniques to assure a room temperature value of Sn0.8Sb0.2Se of κ ∼ 0.6 W/m K. The freshly prepared Sb-doped compounds exhibit an abrupt change in the type of charge carriers, leading to large, negative Seebeck coefficients, although the arc-melt synthesized pellets remain too resistive for thermoelectric applications. Cold-pressed pellets evolve to be p-type at room temperature, but reproducibly turn n-type around 500 K, with increased electrical conductivity and maximum observed figure of merit, ZT ∼ 0.3 at 908 K.
In competitive thermoelectric devices for energy conversion and generation, high-efficiency materials of both n-type and p-type are required. For this, Bi2Te3-based alloys have the best thermoelectric properties in room temperature applications. Partial replacement of tellurium by selenium is expected to introduce new donor states in the band gap, which would alter electrical conductivity and thermopower. We report on the preparation of n-type Bi2(Te1-xSex)3 solid solutions by a straightforward arc-melting technique, yielding nanostructured polycrystalline pellets. X-ray and neutron powder diffraction was used to assess Se inclusion, also indicating that the interactions between quintuple layers constituting this material are weakened upon Se doping, while the covalency of intralayer bonds is augmented. Moreover, scanning electron microscopy shows large surfaces perpendicular to the c crystallographic axis assembled as stacked sheets. Grain boundaries related to this 2D nanostructuration affect the thermal conductivity reducing it below 0.8 Wm−1K−1 at room temperature. Furthermore, Se doping increases the absolute Seebeck coefficient up to −140 μV K−1 at 400 K, which is also beneficial for improved thermoelectric efficiency.
Thermoelectric materials constitute an alternative to harvest sustainable energy from waste heat. Among the most commonly utilized thermoelectric materials, we can mention Bi 2 Te 3 (hole and electron conductivity type), PbTe and recently reported SnSe intermetallic alloys. We review recent results showing that all of them can be readily prepared in nanostructured form by arc-melting synthesis, yielding mechanically robust pellets of highly oriented polycrystals. These materials have been characterized by neutron powder diffraction (NPD), scanning electron microscopy (SEM) and electronic and thermal transport measurements. Analysis of NPD patterns demonstrates near-perfect stoichiometry of above-mentioned alloys and fair amount of anharmonicity of chemical bonds. SEM analysis shows stacking of nanosized sheets, each of them presumably single-crystalline, with large surfaces parallel to layered slabs. This nanostructuration affects notably thermoelectric properties, involving many surface boundaries (interfaces), which are responsible for large phonon scattering factors, yielding low thermal conductivity. Additionally, we describe homemade apparatus developed for the simultaneous measurement of Seebeck coefficient and electric conductivity at elevated temperatures.
Thermoelectric materials are outstanding to transform temperature differences directly and reversibly into electrical voltage. Exploiting waste heat recovery as a source of power generation could help towards energy sustainability. Recently, the SnSe semiconductor was identified, in single-crystal form, as a mid-temperature thermoelectric material with record high figure of merit, high power factor and surprisingly low thermal conductivity. We describe the preparation of polycrystals of alloys of SnSe obtained by arc-melting; a rapid synthesis that results in strongly nanostructured samples with low thermal conductivity, advantageous for thermoelectricity, approaching the amorphous limit, around 0.3-0.5 W/mK. An initial screening of novel samples Sn 1−x M x Se, by alloying with 3d and 4d transition metals such as M = Mn, Y, Ag, Mo, Cd or Au, provides for a means to optimize the power factor. M=Mo, Ag, with excellent values, are described in detail with characterization by x-ray powder diffraction (XRD), scanning electron microscopy (SEM), and electronic and thermal transport measurements. Rietveld analysis of XRD data demonstrates near-perfect stoichiometries of the above-mentioned alloys. SEM analysis shows stacking of nanosized sheets, with large surfaces parallel to layered slabs. An apparatus was developed for the simultaneous measurement of the Seebeck coefficient and electric conductivity at elevated temperatures.
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