Effect of Chemical Composition on the Thermoelectric Properties of n-Type Bi2Te3 Alloys Fabricated by Gas Atomization and Hot Extrusion

In this research, n-type (Bi₂Te₃)_1?x (Bi₂Se₃) _x -based thermoelectric (TE) materials were produced through a gas atomization process, and subsequently hot extruded with an extrusion ratio of 10:1 at 400 °C. The effect of chemical composition on TE properties was investigated. The microstructure of all extruded bars showed a homogeneous and fine distribution of grains due to the dynamic recrystallization during the hot extrusion process. With increasing Bi₂Te₃ content, from 0.85 to 0.90, both electrical resistivity and Seebeck coefficient values were increased. The maximum figure of merit (ZT) 0.673 was obtained at room temperature for (Bi₂Te₃)₀.₉₀(Bi₂Se₃)_0.10 alloys due to them exhibiting higher seebeck coefficient and lower thermal conductivity than other compositions.     

Thermoelectric Properties of n-Type Bi2Te3/PbSe0.5Te0.5 Segmented Thermoelectric Material

To investigate the effects of segmentation of thermoelectric materials on performance levels, n-type segmented Bi₂Te₃/PbSe_0.5Te_0.5 thermoelectric material was fabricated, and its output power was measured and compared with those of Bi₂Te₃ and PbSe_0.5Te_0.5. The two materials were bonded by diffusion bonding with a diffusion layer that was ～18 μm thick. The electrical conductivity, Seebeck coefficient, and power factor of the segmented Bi₂Te₃/PbSe_0.5Te_0.5 sample were close to the average of the values for Bi₂Te₃ and PbSe_0.5Te_0.5. The output power of Bi₂Te₃ was higher than those of PbSe_0.5Te_0.5 and the segmented sample for small ΔT (300 K to 400 K and 300 K to 500 K), but that of the segmented sample was higher than those of Bi₂Te₃ and PbSe_0.5Te_0.5 when ΔT exceeded 300 K (300 K to 600 K and 300 K to 700 K). The output power of the segmented sample was about 15% and 73% higher than those of the Bi₂Te₃ and PbSe_0.5Te_0.5 samples, respectively, when ΔT was 400 K (300 K to 700 K). The efficiency of thermoelectric materials for large temperature differences can be enhanced by segmenting materials with high performance in different temperature ranges.     

Thermoelectric Properties of Nano/microstructured p-Type Bi0.4Sb1.6Te3 Powders Fabricated by Mechanical Alloying and Vacuum Hot Pressing

Two kinds of Bi_0.4Sb_1.6Te₃ powder with different particle and grain sizes were fabricated by high-energy ball milling. Powder mixtures with varied weight ratios were consolidated by vacuum hot pressing (HP) to produce nano/ microstructured composites of identical chemical composition. From measurements of the Seebeck coefficient, electrical resistivity, and thermal conductivity of these composites, a figure of merit (ZT) value of up to 1.19 was achieved at 373 K for the sample containing 40% nanograin powder. This ZT value is higher than that of monolithic nanostructured Bi_0.4Sb_1.6Te₃. It is further noted that the ZT value of this sample in the temperature range of 450 K to 575 K is in the range of 0.7 to 1.1. Such ZT characteristics are suitable for power generation applications as no other material with a similar high ZT value in this temperature range has been observed until now. The achieved high ZT value can probably be attributed to the unique nano/microstructure, in which the dispersed nanograin powder increases the number of phonon scattering sites, which in turn results in a decrease of the thermal conductivity while simultaneously increasing the electrical conductivity, owing to the existence of the microsized powder that can provide a fast carrier transportation network. These results indicate that the nano/microstructured Bi_0.4Sb_1.6Te₃ alloy can serve as a high-performance material for application in thermoelectric devices.     

Thermoelectric Properties of Higher Manganese Silicides Prepared by Mechanical Alloying and Hot Pressing

Higher manganese silicides (HMS), MnSi_1.75–δ , were synthesized by mechanical alloying and consolidated by hot pressing. The optimum condition of mechanical alloying was ball milling at 400 rpm for 6 h, and sound sintered compacts could be obtained by hot pressing at temperature higher than 1073 K. The phase fraction of HMS showed no significant difference with compositional (δ) variation, but the MnSi_1.75 specimen had the lowest fraction of MnSi of approximately 3%. The lattice constants of HMS with compositional variation were similar to values reported in the literature. All specimens showed Nowotny phase with tetragonal structure, and exhibited i-type conduction at measuring temperatures between 323 K and 823 K. HMS behaved as degenerate semiconductors in that the absolute values of the Seebeck coefficient increased and the electrical conductivity slightly decreased with increasing temperature. MnSi_1.73 showed the highest figure of merit of 0.28 at 823 K.     

Effect of Sintering on the Thermoelectric Transport Properties of Bulk Nanostructured Bi0.5Sb1.5Te3 Pellets Prepared by Chemical Synthesis

Considerable research effort has gone into improving the performance of traditional thermoelectric materials such as Bi_2?x Sb _x Te₃ through a variety of nanostructuring approaches. Bottom-up, chemical approaches have the potential to produce very small nanoparticles (?100?nm) with narrow size distribution and controlled shape. For this study, nanocrystalline powder of Bi_0.5Sb_1.5Te₃ was synthesized using a ligand-assisted chemical method, and consolidated into pellets with cold pressing followed by sintering in Ar atmosphere. The thermoelectric transport properties were measured from 7?K to 300?K as a function of sintering temperature. Sintering is found to increase ZT and to move the maximum in ZT to lower temperatures due to a reduction in the free charge concentration. Hall mobility studies indicate that sintering increases the electron mean free path more than it increases the phonon mean free path up to sintering temperature of 598?K. A maximum ZT of 0.42 was measured at temperature of 275?K.     

Thermoelectric Properties of Bi0.5Sb1.5Te3 Prepared by Liquid-Phase Growth Using a Sliding Boat

A liquid-phase growth process using a graphite sliding boat was applied for synthesis of p-type Bi_0.5Sb_1.5Te₃. The process lasted only 60 min, including rapid heating for melting, boat-sliding, and cooling. Thick sheets and bars of 1 mm and 2 mm in thickness having preferable crystal orientation for thermoelectric conversion were successfully prepared by the process. Control of carrier concentration was attempted through addition of excess tellurium (1 mass% to 10 mass%) to optimize the thermoelectric properties of the material. The Hall carrier concentration was found to be decreased by addition of excess tellurium. The electrical resistivity and Seebeck coefficient varied depending on the carrier concentration. As a result, the maximum observed power factor near 300 K was 4.4 × 10^?3 W/K²m, with corresponding Hall carrier concentration of 4.6 × 10²⁵ m^?3. Thus, thermoelectric properties were controllable by addition of excess tellurium, and a large power factor was thus obtained through a simple and short process.     

Effect of NiTe Nanoinclusions on Thermoelectric Properties of Bi2Te3

Metal nanoinclusions in bulk thermoelectric matrix create metal?Csemiconductor interfaces, which can result in improvement in the thermoelectric power factor due to low-energy electron filtering and a simultaneous reduction in lattice thermal conductivity due to increased phonon scattering at grain boundaries. The combined effect results in enhancement of the thermoelectric figure of merit. We report the effect of NiTe nanoinclusions in a Bi₂Te₃ matrix. The Bi₂Te₃/NiTe nanocomposite was synthesized by planetary ball milling. Different volume fractions of NiTe nanoinclusions were incorporated into the bulk (Bi₂Te₃) matrix and uniaxially hot pressed at 100?MPa and 500°C. The presence of nanoinclusions was confirmed by x-ray diffraction and transmission electron microscopy. The Seebeck coefficient, electrical conductivity, and thermal diffusivity were measured from room temperature to 150°C. The carrier concentration of the matrix (Bi₂Te₃) and the nanocomposites (NiTe/Bi₂Te₃) at room temperature were deduced from Hall-effect measurements. Addition of NiTe decreased the carrier concentration, and the power factor increased in the 1?vol.% NiTe/Bi₂Te₃ compared with inclusion-free Bi₂Te₃ matrix due to an increase in mobility.     

Effects of Different Morphologies of Bi2Te3 Nanopowders on Thermoelectric Properties

Thermoelectric Bi₂Te₃ alloy nanopowders with different morphologies were synthesized by hydrothermal processes with different surfactants. The nanopowders were hot-pressed into pellets, and their thermoelectric properties were investigated. The results show that the morphologies of the nanopowders have remarkable effects on the thermoelectric properties of the hot-pressed bulk pellets. A suitable microstructure of the bulk pellet prepared from flower-like nanosheets was found, having a lower electrical resistivity, larger Seebeck coefficient, and lower thermal conductivity, resulting in a high figure of merit ZT ≈ 1.16. The effects of the nanopowders with different morphologies on the microstructure and thermoelectric properties of hot-pressed bulk pellets are discussed.     

Influence of the Sintering Temperature on the Thermoelectric Properties of the Bi1.9Gd0.1Te3 Compound

Semiconductors - The regularities of the influence of the sintering temperature (750, 780, 810, and 840 K) on the elemental composition, crystal-lattice parameters, electrical resistivity, Seebeck...     

Preparation and Thermoelectric Properties of Doped Bi2Te3-Bi2Se3 Solid Solutions

Since Bi₂Te₃ and Bi₂Se₃ have the same crystal structure, they form a homogeneous solid solution. Therefore, the thermal conductivity of the solid solution can be reduced by phonon scattering. The thermoelectric figure of merit can be improved by controlling the carrier concentration through doping. In this study, Bi₂Te_2.85Se_0.15:D _m (D: dopants such as I, Cu, Ag, Ni, Zn) solid solutions were prepared by encapsulated melting and hot pressing. All specimens exhibited n-type conduction in the measured temperature range (323 K to 523 K), and their electrical conductivities decreased slightly with increasing temperature. The undoped solid solution showed a carrier concentration of 7.37 × 10¹⁹ cm^?3, power factor of 2.1 mW m^?1 K^?1, and figure of merit of 0.56 at 323 K. The figure of merit (ZT) was improved due to the increased power factor by I, Cu, and Ag dopings, and maximum ZT values were obtained as 0.76 at 323 K for Bi₂Te_2.85Se_0.15:Cu_0.01 and 0.90 at 423 K for Bi₂Te_2.85Se_0.15:I_0.005. However, the thermoelectric properties of Ni- and Zn-doped solid solutions were not enhanced.     

Effects of Bi2Se3 Nanoparticle Inclusions on the Microstructure and Thermoelectric Properties of Bi2Te3-Based Nanocomposites

A series of thermoelectric nanocomposite samples were prepared by integrating Bi₂Se₃ nanoparticles into a bulk Bi₂Te₃ matrix. Primarily, spherical Bi₂Se₃ nanoparticles with diameter of ～30 nm were synthesized by combining bismuth acetate with elemental Te in oleic acid solution. Bi₂Te₃-based nanocomposite samples were prepared by consolidating the appropriate quantity of Bi₂Se₃ nanoparticles with the starting elements (Bi and Te) using typical solid-state synthetic reactions. The microstructure and composition of the Bi₂Te₃-based nanocomposites, as well as the effects of the Bi₂Se₃ nanoparticles on their thermoelectric properties, are investigated. Transmission electron microscopy observation of the Bi₂Te₃-based nanocomposites reveals two types of interface between the constituent materials, i.e., coherent and incoherent, depending on the Bi₂Se₃ concentration. The Bi₂Se₃ nanoparticles in the Bi₂Te₃ matrix act as scattering centers for a wider range of phonon frequencies, thereby reducing the thermal conductivity. As a result, the maximum ZT value of 0.75 is obtained for the Bi₂Te₃ nanocomposite with 10 wt.% Bi₂Se₃ nanoparticles at room temperature. It is clear that the reduction in the thermal conductivity plays a central role in the enhancement of the ZT value.     

Nanostructure, Excitations, and Thermoelectric Properties of Bi2Te3-Based Nanomaterials

The effect of dimensionality and nanostructure on thermoelectric properties in Bi₂Te₃-based nanomaterials is summarized. Stoichiometric, single-crystalline Bi₂Te₃ nanowires were prepared by potential-pulsed electrochemical deposition in a nanostructured Al₂O₃ matrix, yielding transport in the basal plane. Polycrystalline, textured Sb₂Te₃ and Bi₂Te₃ thin films were grown at room temperature using molecular beam epitaxy and subsequently annealed at 250°C. Sb₂Te₃ films revealed low charge carrier density of 2.6?×?10¹⁹?cm^?3, large thermopower of 130???V?K^?1, and large charge carrier mobility of 402?cm²?V^?1?s^?1. Bi₂(Te_0.91Se_0.09)₃ and (Bi_0.26Sb_0.74)₂Te₃ nanostructured bulk samples were prepared from as-cast materials by ball milling and subsequent spark plasma sintering, yielding grain sizes of 50?nm and thermal diffusivities reduced by 60%. Structure, chemical composition, as well as electronic and phononic excitations were investigated by x-ray and electron diffraction, nuclear resonance scattering, and analytical energy-filtered transmission electron microscopy. Ab?initio calculations yielded point defect energies, excitation spectra, and band structure. Mechanisms limiting the thermoelectric figure of merit ZT for Bi₂Te₃ nanomaterials are discussed.     

Synthesis and Thermoelectric Characterization of Bi2Te3 Nanoparticles

Here, a novel synthesis for near monodisperse, sub‐10 nm Bi₂Te₃ nanoparticles is reported. A new reduction route to bismuth nanoparticles is described, which are then applied as starting materials in the formation of rhombohedral Bi₂Te₃ nanoparticles. After ligand removal by a novel hydrazine hydrate etching procedure, the nanoparticle powder is spark plasma sintered to a pellet with preserved crystal grain sizes. Unlike previous works on the properties of Bi₂Te₃ nanoparticles, the full thermoelectric characterization of such sintered pellets shows a highly reduced thermal conductivity and the same electric conductivity as bulk n‐type Bi₂Te₃.     

Thermoelectric Properties of TlCu3Te2 and TlCu2Te2

We performed thermoelectric characterizations on TlCu₃Te₂: (Tl¹⁺)(Cu¹⁺)₃ (Te²⁻)₂ and TlCu₂Te₂: (Tl¹⁺)(Tl³⁺)(Cu¹⁺)₄(Te²⁻)₄, in order to understand the relationship between the thermoelectric properties (especially the lattice thermal conductivity κ _lat) and the valence states of Tl. The thermal conductivity of TlCu₂Te₂ is high (about 8 W m⁻¹ K⁻¹), while that of TlCu₃Te₂ is extremely low (around 0.5 W m⁻¹ K⁻¹) like other thallium tellurides. This high κ of TlCu₂Te₂ was caused not only by its large electronic contribution but also by its intrinsically high κ _lat. The present study implies that the valence states of Tl would play some important roles in determining the magnitude of κ _lat.     

Thermoelectric Figure of Merit Enhancement in Bi2Te3-Coated Bi Composites

This study examines the thermoelectric behavior of composites containing hydrothermally processed tellurium-coated bismuth particles of various sizes. Since only a very thin layer of Bi₂Te₃ forms on the particle surface, the high-pressure compacted composite is still dominated by bismuth as the main ingredient (??96% Bi). Thermoelectric figure of merit ZT values are derived from measurements of thermal conductivity, electrical resistivity, and Seebeck coefficient. As expected, a ZT value almost three times higher than that of bismuth is found. This enhancement appears to be caused mainly by lowered thermal conductivity due to the significant number of grain boundaries, short phonon mean free path in the coating layers, and lattice mismatch.     

Thermoelectric Properties of Bi2Te2Se Compensated by Native Defects and Sn Doping

In Bi₂Te₂Se the defect chemistry involves native defects that compete such that they can either exchange dominance or else significantly compensate each other. Here we show how the net carrier concentration, n ? p, which depends on the relative amounts of these defects and is readily obtained from Hall data, can be used as a fundamental materials parameter to describe the varied behavior of the thermoelectric properties as a function of compensation. We report the effects of tuning this parameter over multiple orders of magnitude by hole-doping the n-type material Bi₂Te₂Se_0.995, which is already significantly compensated because of its Se deficiency. Crystals with different levels of hole doping were achieved by two separate approaches, namely by selecting pieces from different locations in an undoped crystal in which a systematic carrier concentration gradient had been induced by its growth conditions, and alternatively by doping with Sn for Bi. The thermoelectric power factors for Bi_2?x Sn _x Te₂Se_0.995 for x = 0, 0.002, 0.005, 0.010, and 0.040 are reported, and the dependence of the transport properties on the extent of compensation is discussed.     

Effect of Spark Plasma Sintering Temperature on Thermoelectric Properties of Grained Bi1.9Gd0.1Te3 Compound

Semiconductors - Patterns in changes of the microstructure (grain structure) and the thermoelectric properties of the n-type grained Bi1.9Gd0.1Te3 compound, spark-plasma-sintered at different...