Synthesis of Bi0.5Sb1.5Te3 Thermoelectric Powder Using an Oxide-Reduction Process

The present study focused on synthesis of Bi_0.5Sb_1.5Te₃ thermoelectric powder using an oxide-reduction process. The phase structure and particle size of the synthesized powders were analyzed using x-ray diffractometry and scanning electron microscopy. The synthesized powder was sintered using the spark plasma sintering method. The thermoelectric properties of the sintered body were evaluated by measuring the Seebeck coefficient, electrical resistivity, and thermal conductivity. Bi_0.5Sb_1.5Te₃ powder was synthesized using a combination of mechanical milling, calcination, and reduction processes, using a mixture of Bi₂O₃, Sb₂O₃, and TeO₂ powders. The sintered body of the oxide-reduction-synthesized Bi_0.5Sb_1.5Te₃ powder showed p-type thermoelectric characteristics. The thermoelectric properties of the sintered bodies depended on the reduction time. After being reduced for 2 h at 663 K, the sintered body of the Bi_0.5Sb_1.5Te₃ powder showed a figure of merit of approximately 1.0 at room temperature.     

Thermoelectric Power Generation Characteristics of a Thin-Film Device Consisting of Electrodeposited n-Bi2Te3 and p-Sb2Te3 Thin-Film Legs

A thermoelectric thin-film device of the cross-plane configuration was fabricated by flip-chip bonding of the top electrodes to 242 pairs of electrodeposited n-type Bi₂Te₃ and p-type Sb₂Te₃ thin-film legs on the bottom substrate. The electrodeposited Bi₂Te₃ and Sb₂Te₃ films of 20-μm thickness exhibited Seebeck coefficients of ?59 μV/K and 485 μV/K, respectively. The internal resistance of the thin-film device was measured as 3.7 kΩ, most of which was attributed to the interfacial resistance of the flip-chip joints. The actual temperature difference ΔT _G working across the thin-film legs was estimated to be 10.4 times smaller than the apparent temperature difference ΔT applied across the thin-film device. The thin-film device exhibited an open-circuit voltage of 0.294 V and a maximum output power of 5.9 μW at an apparent temperature difference ΔT of 22.3 K applied across the thin-film device.     

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.     

Low Thermal Conductivity in High-Z Thermoelectric Materials with Controlled Nanodispersions

We report wet chemical synthesis of a hierarchical nanocomposite thermoelectric material, (Bi,Sb)₂Te₃ + 2 vol.% Sb₂O₃, which exhibits a very high ZT value of 1.5 at 333 K. The key to such a high ZT value is to design the interfacial density (ID) of the nanodispersion and the mean diameter of the matrix (d) in the nanocomposite. To this end, (Bi,Sb)₂Te₃ with Sb₂O₃ nanodispersion was developed using in situ precipitation during solvothermal treatment. Nanocomposite structure was observed in sintered specimens. By evaluation of thermoelectric properties, it was confirmed that phonon scattering on the surface of Sb₂O₃ dispersion and κ _ph correspondingly decreased with ID. The formation of a well-controlled Sb₂O₃ dispersion (mean diameter of dispersion: D = 1.5 nm, ID = 0.06 nm^?1) and fine grains (d = 38 nm) led to an extremely low lattice thermal conductivity of 0.28 W m^?1 K^?1, while reducing the electrical conductivity moderately according to the conventional mixture rule.     

Fabrication of a Flexible Bismuth Telluride Power Generation Module Using Microporous Polyimide Films as Substrates

In this study, we investigated the effect of the structure of microporous p-type (Bi_0.4Te₃Sb_1.6) and n-type (Bi_2.0Te_2.7Se_0.3) BiTe-based thin films on their thermoelectric performance. High-aspect-ratio porous thin films with pore depth greater than 1 μm and pore diameter ranging from 300 nm to 500 nm were prepared by oxygen plasma etching of polyimide (PI) layers capped with a heat-resistant block copolymer, which acted as the template. The cross-plane thermal conductivities of the porous p- and n-type thin films were 0.4 W m^?1 K^?1 and 0.42 W m^?1 K^?1, respectively, and the dimensionless figures of merit, ZT, of the p- and n-type BiTe films were estimated as 1.0 and 1.0, respectively, at room temperature. A prototype thermoelectric module consisting of 20 pairs of p- and n-type strips over an area of 3 cm × 5 cm was fabricated on the porous PI substrate. This module produced an output power of 0.1 mW and an output voltage of 0.6 V for a temperature difference of 130°C. The output power of the submicrostructured module was 1.5 times greater than that of a module based on smooth BiTe-based thin films. Thus, the thermoelectric performance of the thin films was improved owing to their submicroscale structure.     

BiSbTe‐Based Nanocomposites with High ZT: The Effect of SiC Nanodispersion on Thermoelectric Properties

Thermoelectric materials have potential applications in energy harvesting and electronic cooling devices, and bismuth antimony telluride (BiSbTe) alloys are the state‐of‐the‐art thermoelectric materials that have been widely used for several decades. It is demonstrated that mixing SiC nanoparticles into the BiSbTe matrix effectively enhances its thermoelectric properties; a high dimensionless figure of merit (ZT) value of up to 1.33 at 373 K is obtained in Bi_0.3Sb_1.7Te₃ incorporated with only 0.4 vol% SiC nanoparticles. SiC nanoinclusions possessing coherent interfaces with the Bi_0.3Sb_1.7Te₃ matrix can increase the Seebeck coefficient while increasing the electrical conductivity, in addition to its effect of reducing lattice thermal conductivity by enhancing phonon scattering. Nano‐SiC dispersion further endows the BiSbTe alloys with better mechanical properties, which are favorable for practical applications and device fabrication.     

Preparation and Characterization of Bi0.4Sb1.6Te3 Bulk Thermoelectric Materials

This work focused on the preparation of p-type Bi_0.4Sb_1.6Te₃ bulk materials by combining mechanical alloying (MA) and hot extrusion, with emphasis on grain refinement and preferred grain orientation. Pure Bi, Sb, and Te powders were mechanically alloyed then hot extruded in the temperature range 360–450°C. Bi_0.4Sb_1.6Te₃ bulk materials were successfully prepared by MA and hot extrusion. All the samples had sound appearance, with single phases and high densities. The hot-extruded samples had small grain sizes, and the lower the extrusion temperature, the smaller the grain sizes. The results indicated that the extrudates had preferred orientation. The basal plane was predominantly oriented parallel to the direction of extrusion. Similar Seebeck coefficients were obtained when extrusion temperature was in the range 380–420°C. Electrical resistivity decreased with increasing extrusion temperature. Thermal conductivity was relatively low, even if the extrusion temperature was 450°C. As a result, a ZT value of 1.2 was obtained at room temperature for the sample extruded at 400°C. Therefore, combination of MA and hot extrusion results in significant improvement of both the thermoelectric and mechanical performance of Bi_0.4Sb_1.6Te₃ bulk materials.     

Thermal Conductivity of Exfoliated p-Type Bismuth Antimony Telluride

A bulk p-type thermoelectric compound with nominal composition Bi_0.5Sb_1.5 Te₃ has been exfoliated using dimethyl sulfoxide as a solvent. Samples have been prepared from the exfoliated platelets by pressing followed by sintering or hot pressing. The exfoliated nanoplatelets have been characterized for size distribution and composition using scanning electron microscopy and energy-dispersive spectrometry. The smallest size platelet was 40 nm, and the maximum in the size distribution was near 80 nm. The exfoliated platelets and sintered sample showed significant deficiency in Sb and Te. The nonstoichiometry in the composition of the exfoliated platelets indicates that the mechanism of exfoliation may not be between quintuplets only, with other layers also being active. The composition of the hot-pressed sample remained closer to that of the bulk. Results of x-ray diffraction indicated the presence of Bi₂Te₃ and Bi_0.5Sb_1.5Te₃ phases and pure Te and Sb. Residual porosity was observed in the hot-pressed and sintered samples. The thermal conductivity of the samples was measured by transient thermoreflectance. The results showed that the thermal conductivity of the hot-pressed sample was reduced by a factor of two compared with that of the bulk as a result of the presence of a high density of interfaces and residual porosity. The thermal conductivity of the sintered sample showed an increase above that of the bulk sample, which is explained by the change in composition due to loss of Sb and Te.     

Improvement of Thermoelectric Power Factor of Hydrothermally Prepared Bi<Subscript>0.5</Subscript>Sb<Subscript>1.5</Subscript>Te<Subscript>3</Subscript> Compared with its Solvothermally Prepared Counterpart

We report on the successful hydrothermal synthesis of Bi_0.5Sb_1.5Te₃, using water as the solvent. The products of the hydrothermally prepared Bi_0.5 Sb_1.5Te₃ were hexagonal platelets with edges of 200–1500 nm and thicknesses of 30–50 nm. Both the Seebeck coefficient and electrical conductivity of the hydrothermally prepared Bi_0.5Sb_1.5Te₃ were larger than those of the solvothermally prepared counterpart. Hall measurements of Bi_0.5Sb_1.5Te₃ at room temperature indicated that the charge carrier was p-type, with a carrier concentration of 9.47 × 10¹⁸ cm⁻³ and 1.42 × 10¹⁹ cm⁻³ for the hydrothermally prepared Bi_0.5Sb_1.5Te₃ and solvothermally prepared sample, respectively. The thermoelectric power factor at 290 K was 10.4 μW/cm K² and 2.9 μW/cm K² for the hydrothermally prepared Bi_0.5Sb_1.5Te₃ and solvothermally prepared sample, respectively.     

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.     

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.     

Layered Sb2Te3 Nanoflakes as Chalcogenide Dielectrics

Dielectric nanoflakes of Sb₂Te₃ represent an important advance in science and technology due to their extraordinary properties. Polycrystalline layered Sb₂Te₃ nanoflakes have been successfully synthesized via a high-throughput chemical route at 60°C. The frequency and temperature dependence of the dielectric constant and dielectric loss of the layered Sb₂Te₃ nanoflakes have been measured in the frequency range from 30 Hz to 758,000 Hz and temperature range from 313 K to 373 K. As-synthesized Sb₂Te₃ nanoflakes are shown to be promising alternative dielectrics because of their high dielectric constant (ε′ ≈ 7.3 to 6022) and low dielectric loss (tan δ ≈ 0.2 to 9.2). These higher values of ε′ and lower values of tan δ of Sb₂Te₃ nanoflakes confirm that capacitors with capacity (C) of ～5.2 pF to 4336 pF may be fabricated for storing renewable energy. Raman spectroscopy confirms that the peak located at ～142 cm^?1 corresponds to one in-plane vibrational mode (E _g ² ) of layered Te–Sb–Te–Sb–Te lattice vibration.     

Preparation of Bi0.5Sb1.5Te3 Thermoelectric Materials by Pulse-Current Sintering Under Cyclic Uniaxial Pressure

The effects of applying cyclic uniaxial pressure during the pulse-current sintering process on the crystal alignment and thermoelectric properties of p-type Bi_0.5Sb_1.5Te₃ were investigated. Sintering was performed at 673 K using pulse-current heating under 70 MPa or 100 MPa of cyclic uniaxial pressure. x-Ray diffraction patterns and electron backscattered diffraction analyses showed that application of the cyclic uniaxial pressure enhanced crystal grain orientation. The texture consisted of flattened crystal grains stacked in the thickness direction of the sintered materials. The hexagonal c-plane strongly tended to align in the direction perpendicular to the uniaxial pressure. Owing to the crystal alignment, the Hall mobility in the direction perpendicular to the uniaxial pressure became larger than that of equivalent samples prepared with a constant uniaxial pressure. As a result of the increase in Hall mobility, the resistivity of the material was decreased while the equivalent Seebeck coefficient was maintained and the power factor was improved.     

Enhanced Thermoelectric Properties of Antimony Telluride Thin Films with Preferred Orientation Prepared by Sputtering a Fan-Shaped Binary Composite Target

p-Type antimony telluride (Sb₂Te₃) thermoelectric thin films were deposited on BK7 glass substrates by ion beam sputter deposition using a fan-shaped binary composite target. The deposition temperature was varied from 100°C to 300°C in increments of 50°C. The influence of the deposition temperature on the microstructure, surface morphology, and thermoelectric properties of the thin films was systematically investigated. x-Ray diffraction results show that various alloy composition phases of the Sb₂Te₃ materials are grown when the deposition temperature is lower than 200°C. Preferred c-axis orientation of the Sb₂Te₃ thin film became obvious when the deposition temperature was above 200°C, and thin film with single-phase Sb₂Te₃ was obtained when the deposition temperature was 250°C. Scanning electron microscopy reveals that the average grain size of the films increases with increasing deposition temperature and that the thin film deposited at 250°C shows rhombohedral shape corresponding to the original Sb₂Te₃ structure. The room-temperature Seebeck coefficient and electrical conductivity range from 101 μV K^?1 to 161 μV K^?1 and 0.81 × 10³ S cm^?1 to 3.91 × 10³ S cm^?1, respectively, as the deposition temperature is increased from 100°C to 300°C. An optimal power factor of 6.12 × 10^?3 W m^?1 K^?2 is obtained for deposition temperature of 250°C. The thermoelectric properties of Sb₂Te₃ thin films have been found to be strongly enhanced when prepared using the fan-shaped binary composite target method with an appropriate substrate temperature.     

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 Sintered n-Type and p-Type Tellurides

Characterization of powder-metallurgically manufactured (Bi _x Sb_1?x )₂(Te _y Se_1?y )₃ thermoelectric materials is presented. The manufacturing methods were spark plasma sintering (SPS) and hot isostatic pressing (HIP). x-Ray diffraction (XRD) and density measurements as well as transport characterization and scanning electron microscopy were performed on the materials. It is shown that both sintering techniques yield reasonable thermoelectric characteristics for p-type (x = 0.2, y = 1) as well as n-type (x = 0.95, y = 0.95) materials. Insight into the underlying reasons such as the scattering processes limiting the characteristics is gained by fitting experimental transport data using a theoretical model. The limitations and further optimization issues of our approach in thermoelectric material preparation are discussed.     

Improvement of Thermoelectric Properties in (Bi0.5Sb0.5)2Te3 Films of Nanolayered Pillar Arrays

In this work, it is found that unique pillar arrays with nanolayered structure can favorably influence the carrier and phonon transport properties of films. p-(Bi_0.5Sb_0.5)₂Te₃ pillar array film with (0 1 5) orientation was successfully achieved by a simple ion-beam-assisted technique at deposition temperature of 400°C, owing to the enhanced mobility of deposited atoms for more sufficient growth along the in-plane direction. The pillar diameter was about 250 nm, and the layered nanostructure was clear, with each layer in the pillar array being <30 nm. The properties of the oriented (Bi_0.5Sb_0.5)₂Te₃ pillar array were greatly enhanced in comparison with those of ordinary polycrystalline films synthesized at deposition temperature of 350°C and 250°C. The (Bi_0.5Sb_0.5)₂Te₃ pillar array film with (0 1 5) preferred orientation exhibited a thermoelectric dimensionless figure of merit of ZT = 1.25 at room temperature. The unique pillar array with nanolayered structure is the main reason for the observed improvement in the properties of the (Bi_0.5Sb_0.5)₂Te₃ film.     

Electrodeposition of Bi<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Sb<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Thermoelectric Films from DMSO Solution

The electrochemical behavior of nonaqueous dimethyl sulfoxide solutions of Bi^III, Te^IV, and Sb^III was investigated using cyclic voltammetry. On this basis, Bi _x Sb_2−x Te _y thermoelectric films were prepared by the potentiodynamic electrodeposition technique in nonaqueous dimethyl sulfoxide solution, and the composition, structure, morphology, and thermoelectric properties of the films were analyzed. Bi _x Sb_2−x Te _y thermoelectric films prepared under different potential ranges all possessed a smooth morphology. After annealing treatment at 200°C under N₂ protection for 4 h, all deposited films showed p-type semiconductor properties, and their resistances all decreased to 0.04 Ω to 0.05 Ω. The Bi_0.49Sb_1.53Te_2.98 thermoelectric film, which most closely approaches the stoichiometry of Bi_0.5Sb_1.5Te₃, possessed the highest Seebeck coefficient (85 μV/K) and can be obtained under potentials of −200 mV to −400 mV.     

Thermoelectric properties of the (Bi,Sb)2Te3-based material obtained by spark plasma sintering

The dependence of the thermoelectric properties of the nanostructured bulk (Bi,Sb)₂Te₃ material on the composition and the spark plasma-sintering (SPS) temperature T _SPS has been studied. It has been revealed that the Bi_0.4Sb_1.6Te₃ solid solution sintered at a temperature of 450–500°C has a thermoelectric figure of merit ZT = 1.25–1.28. The dependence of thermoelectric properties on the sintering temperature T _SPS above 400°C is correlated to the transformation of the fine structure of the material due to the rearrangement of point vacancy-donor defects in the process of repeated recrystallization. It has been established that point structural defects make a considerable contribution to the formation of the thermoelectric properties of nanostructured material.