An oxide semiconductor (perovskite-type Mn2 O3 ) is reported which has a narrow and direct bandgap of 0.45 eV and a high Vickers hardness of 15 GPa. All the known materials with similar electronic band structures (e.g., InSb, PbTe, PbSe, PbS, and InAs) play crucial roles in the semiconductor industry. The perovskite-type Mn2 O3 described is much stronger than the above semiconductors and may find useful applications in different semiconductor devices, e.g., in IR detectors.
We experimentally investigate the thermoelectric power (Seebeck effect) of quasi-two-dimensional single crystals of titanium and zirconium trichalcogenides (TiS 3 , ZrS 3 , ZrSe 3 , and ZrTe 3 ) under applied high pressure up to 10 GPa. Both sulfides were characterized by n-type semiconducting conduction in the whole pressure range investigated and, generally, showed moderate pressure responses of their electronic properties. Metallic ZrTe 3 conserved its p-type conduction under pressure, and its Seebeck coefficient curve displayed a distinct crossover near 2 GPa. Semiconducting ZrSe 3 demonstrated more remarkable responses to applied pressure, which included a multiorder gradual drop in its electrical resistance value up to 9 GPa and an n−p inversion of the dominant conduction type around 6 GPa. Furthermore, we found that a thermoelectric power factor of ZrSe 3 may be greatly improved under high applied pressure, achieving a value of an order of 3.5 mW/(K 2 m) at 9.5 GPa. Thus, an appropriately strained p-type ZrSe 3 with a dramatically reduced band gap value turns to be a promising thermoelectrics. One can anticipate that ZrSe 3 −ZrTe 3 solid solutions, in which the addition of ZrTe 3 should decrease the band gap value of ZrSe 3 in a controlled manner, could also demonstrate high thermoelectric performance parameters. Reversibility and reproducibility of the pressure-driven changes in the electronic properties of ZrSe 3 suggest that it has a potential for other industrial applications linked to cyclic stress loads, for example, in n−p switches or control of p−n−p transistor elements.
We investigated the effects of applied high pressure on thermoelectric, electric, structural, and optical properties of single-crystalline thermoelectrics, Bi2Te3, BixSb2−xTe3 (x = 0.4, 0.5, 0.6), and Bi2Te2.73Se0.27 with the high thermoelectric performance. We established that moderate pressure of about 2–4 GPa can greatly enhance the thermoelectric power factor of all of them. X-ray diffraction and Raman studies on Bi2Te3 and Bi0.5Sb1.5Te3 found anomalies at similar pressures, indicating a link between crystal structure deformation and physical properties. We speculate about possible mechanisms of the power factor enhancement and suppose that pressure/stress tuning can be an effective tool for the optimization of the thermoelectric performance.
We report results of investigations of electronic transport properties and lattice dynamics of Al-doped magnesium silicide (Mg2Si) thermoelectrics at ambient and high pressures to and beyond 15 GPa. High-quality samples of Mg2Si doped with 1 at. % of Al were prepared by spark plasma sintering technique. The samples were extensively examined at ambient pressure conditions by X-ray diffraction studies, Raman spectroscopy, electrical resistivity, magnetoresistance, Hall effect, thermoelectric power (Seebeck effect), and thermal conductivity. A Kondo-like feature in the electrical resistivity curves at low temperatures indicates a possible magnetism in the samples. The absolute values of the thermopower and electrical resistivity, and Raman spectra intensity of Mg2Si:Al dramatically diminished upon room-temperature compression. The calculated thermoelectric power factor of Mg2Si:Al raised with pressure to 2–3 GPa peaking in the maximum the values as high as about 8 × 10−3 W/(K2m) and then gradually decreased with further compression. Raman spectroscopy studies indicated the crossovers near ∼5–7 and ∼11–12 GPa that are likely related to phase transitions. The data gathered suggest that Mg2Si:Al is metallized under moderate pressures between ∼5 and 12 GPa.
We describe the current state of experimental studies of the effects of applied high pressure or stress on the thermoelectric properties and performance parameters of thermoelectric materials, as well as the challenges faced in this area and possible directions for future work. We summarize and analyze literature data on the effects of high pressure on the Seebeck coefficient (thermoelectric power) of different materials that are related to common families of thermoelectrics, such as Bi
Controlled tuning the electrical, optical, magnetic, mechanical and other characteristics of the leading semiconducting materials is one of the primary technological challenges. Here, we demonstrate that the electronic transport properties of conventional single-crystalline wafers of germanium may be dramatically tuned by application of moderate pressures. We investigated the thermoelectric power (Seebeck coefficient) of p– and n–type germanium under high pressure to 20 GPa. We established that an applied pressure of several GPa drastically shifts the electrical conduction to p–type. The p–type conduction is conserved across the semiconductor-metal phase transition at near 10 GPa. Upon pressure releasing, germanium transformed to a metastable st12 phase (Ge-III) with n–type semiconducting conductivity. We proposed that the unusual electronic properties of germanium in the original cubic-diamond-structured phase could result from a splitting of the “heavy” and “light” holes bands, and a related charge transfer between them. We suggested new innovative applications of germanium, e.g., in technologies of printing of n–p and n–p–n junctions by applied stress. Thus, our work has uncovered a new face of germanium as a ‘smart’ material.
We propose a model of a thermoelectric module in which the performance parameters can be controlled by applied tuneable stress. This model includes a miniature high-pressure anvil-type cell and a specially designed thermoelectric module that is compressed between two opposite anvils. High thermally conductive high-pressure anvils that can be made, for instance, of sintered technical diamonds with enhanced thermal conductivity, would enable efficient heat absorption or rejection from a thermoelectric module. Using a high-pressure cell as a prototype of a stress-controlled thermoelectric converter, we investigated the effect of applied high pressure on the power factors of several single-crystalline thermoelectrics, including binary p-type Bi2Te3, and multi-component (Bi,Sb)2Te3 and Bi2(Te,Se,S)3 solid solutions. We found that a moderate applied pressure of a few GPa significantly enhances the power factors of some of these thermoelectrics. Thus, they might be more efficiently utilized in stress-controlled thermoelectric modules. In the example of one of these thermoelectrics crystallizing in the same rhombohedral structure, we examined the crystal lattice stability under moderate high pressures. We uncovered an abnormal compression of the rhombohedral lattice of (Bi0.25,Sb0.75)2Te3 along the c-axis in a hexagonal unit cell, and detected two phase transitions to the C2/m and C2/c monoclinic structures above 9.5 and 18 GPa, respectively.
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