Lorenz Function of Bi2Te3/Sb2Te3 Superlattices

Combining first-principles density functional theory and semiclassical Boltzmann transport, the anisotropic Lorenz function was studied for thermoelectric Bi₂Te₃/Sb₂Te₃ superlattices and their bulk constituents. It was found that, already for the bulk materials Bi₂Te₃ and Sb₂Te₃, the Lorenz function is not a clear function of charge carrier concentration and temperature. For electron-doped Bi₂Te₃/Sb₂Te₃ superlattices, large oscillatory deviations of the Lorenz function from the metallic limit were found even at high charge carrier concentrations. The latter can be referred to quantum well effects, which occur at distinct superlattice periods.     

Thermoelectric Properties of Highly Deformed and Subsequently Annealed p-Type (Bi0.25Sb0.75)2Te3 Alloys

The effects of mechanical deformation and subsequent annealing on the thermoelectric properties and microstructure have been investigated for p-type (Bi_0.25Sb_0.75)₂Te₃ alloys prepared by melting followed by quenching. The mechanically deformed pellets were prepared by repetition of cold-pressing of quenched samples at room temperature. Cold-pressed pellets were then annealed at 300°C in vacuum, and the thermoelectric properties and microstructure were traced through the course of the heat treatment. For the heavily deformed samples, the Seebeck coefficient rapidly increased at the very early stage of annealing and did not change as the annealing time increased, due to recrystallization of a new δ-phase which equilibrated at the annealing temperature of 300°C (δ₃₀₀-phase). At the initial stage of annealing (recovery stage), the electrical resistivity sharply increased, probably due to the interaction of antistructural defects with vacancies produced during the cold-pressing treatment. However, for the lightly deformed samples, recrystallization occurred only at some portion of the grain boundaries, and the newly generated δ₃₀₀-phase slowly replaced the original, as-solidified δ_ingot-phase.     

Sb2Te3 and Bi2Te3 Thin Films Grown by Room-Temperature MBE

Sb₂Te₃ and Bi₂Te₃ thin films were grown on SiO₂ and BaF₂ substrates at room temperature using molecular beam epitaxy. Metallic layers with thicknesses of 0.2?nm were alternately deposited at room temperature, and the films were subsequently annealed at 250°C for 2?h. x-Ray diffraction and energy-filtered transmission electron microscopy (TEM) combined with high-accuracy energy-dispersive x-ray spectrometry revealed stoichiometric films, grain sizes of less than 500?nm, and a texture. High-quality in-plane thermoelectric properties were obtained for Sb₂Te₃ films at room temperature, i.e., low charge carrier density (2.6?×?10¹⁹?cm^?3), large thermopower (130???V?K^?1), large charge carrier mobility (402?cm²?V^?1?s^?1), and resulting large power factor (29???W?cm^?1?K^?2). Bi₂Te₃ films also showed low charge carrier density (2.7?×?10¹⁹?cm^?3), moderate thermopower (?153???V?K^?1), but very low charge carrier mobility (80?cm²?V^?1?s^?1), yielding low power factor (8???W?cm^?1?K^?2). The low mobilities were attributed to Bi-rich grain boundary phases identified by analytical energy-filtered TEM.     

Design and Fabrication of Segmented GeTe/(Bi,Sb)2Te3 Thermoelectric Module with Enhanced Conversion Efficiency

GeTe and (Bi,Sb)₂Te₃ are two representative thermoelectric (TE) materials showing maximum performance at middle and low temperature, respectively. In order to achieve higher performance over the whole temperature range, their segmented one-leg TE modules are designed and fabricated by one-step spark plasma sintering (SPS). To search for contact and connect layers, the diffusion behavior of Fe, Ni, Cu, and Ti metal layers in GeTe is studied systematically. The results show that Ti with a similar linear expansivity (10.80 × 10⁻⁶ K⁻¹) to GeTe, has low contact resistance (3 µΩ cm²) and thin diffusion layer (0.4 µm), and thus is an effective metallization layer for GeTe. The geometric structure of the GeTe/(Bi,Sb)₂Te₃ segmented one-leg TE module and the ratio of GeTe to (Bi,Sb)₂Te₃ are determined by finite element simulation method. When the GeTe height ratio is 0.66, its theoretical maximum conversion efficiency (η_max) can reach 15.9% without considering the thermal radiation and thermal/electrical contact resistance. The fabricated GeTe/(Bi,Sb)₂Te₃ segmented one-leg TE module showed a η_max up to 9.5% with a power density ≈ 7.45 mW mm⁻², which are relatively high but lower than theoretical predictions, indicating that developing segmented TE modules is an effective approach to enhance TE conversion efficiency.     

High-Temperature Mechanical and Thermoelectric Properties of p-Type Bi0.5Sb1.5Te3 Commercial Zone Melting Ingots

Bismuth telluride-based compounds have been extensively utilized for commercial application. However, thermoelectric materials must suffer numerous mechanical vibrations and thermal stresses while in service, making it equally important to discuss the mechanical properties, especially at high temperature. In this study, the compressive and bending strengths of Bi_0.5Sb_1.5Te₃ commercial zone melting (ZM) ingots were investigated at 25, 100, and 200 °C, respectively. Due to the obvious anisotropy of materials prepared by ZM method, the effect of anisotropy on the strengths was also explored. Two-parameter Weibull distribution was employed to fit a series of values acquired by a universal testing machine. And digital speckle photography was applied to record the strain field evolution, providing visual observation of surface strain. The compressive and bending strengths along ZM direction were approximately three times as large as those perpendicular to the ZM direction independent of the temperature, indicating a weak van der Waals bond along the c axis.     

Optical constants of Bi2Te3 and Sb2Te3 measured using spectroscopic ellipsometry

In this work, we present the optical constants of bismuth telluride (Bi₂Te₃), and antimony telluride (Sb₂Te₃) determined using spectroscopic ellipsometry (SE). The spectral range of the optical constants is from 404 nm to 740 nm. Bi₂Te₃ and Sb₂Te₃ films with different thicknesses were grown by metalorganic chemical vapor deposition (MOCVD). Multiple sample analysis (MSA) technique was employed in order to eliminate the parameter correlation in the SE data analysis caused by the presence of the overalyer on top of Bi₂Te₃ and Sb₂Te₃ films. Optical constants and thicknesses for both Bi₂Te₃ and Sb₂Te₃ overlayers were also determined. Independent Bi₂Te₃ and Sb₂Te₃ samples were used to check the results obtained. In addition, SE analysis was performed on two Sb₂Te₃ samples after being etched in diluted NH₄OH solution in order to characterize the overlayer and confirm the reliability of the results.     

In-situ monitoring of the growth of Bi2 Te2 and Sb2 Te3 films and Bi2 Te3-Sb2 Te3 superlattice using spectroscopic ellipsometry

In this work, we present in-situ monitoring of the growth of bismuth telluride (Bi₂Te₃) and antimony telluride (Sb₂Te₃) thin films as well as Bi₂ Te₃-Sb₂Te₃ superlattice using a spectroscopic ellipsometer (SE). Bi₂Te₃ and Sb₂ Te₃ films were grown by metalorganic chemical vapor deposition (MOCVD) at 350 C. A44-wavelength ellipsometer with spectral range from 404 nm to 740 nm was used in this work. The optical constants of Bi₂ Te₃ and Sb₂Te₃ at growth temperature were determined by fitting a model to the extracted in-situ SE data of optically thick Bi₂ Te₃ and Sb₂ Te₃ films. Compared to the optical constants of Bi₂ Te₃ and Sb₂ Te₃ at room temperature, significant temperature dependence was observed. Using their optical constants at growth temperature, the in-situ growth of Bi₂ Te₃ and Sb₂ Te₃ thin films were modeled and excellent fit between the experimental data and data generated from the best-fit model was obtained. In-situ growth of different Bi₂ Te₃-Sb₂ Te₃ superlattices was also monitored and modeled. The growth of Bi₂ Te₃ and Sb₂ Te₃ layers can be seen clearly in in-situ SE data. Modeling of in-situ superlattice growth shows perfect superlattice growth with an abrupt interface between the two constituent films.     

(Bi2Te3)0.90(Sb2Te3)0.05(Sb2Se3)0.05热压合金微观结构和电学性能相关性研究

通过熔炼,研磨制备N型(Bi2Te3)0．90(Sb2Te3)0．05(Sb2Se3)0．05热电材料的粉末,热压制备混合粉末热压合金。通过SEM和XRD研究热压合金的微观结构,在室温测量热压合金样品的电学性能。结果表明热压合金在微观结构和电学性能上存在各向异性,从而预示能够在增强材料机械强度的同时提高其热电性能。     

Texturing of (Bi0.2Sb0.8)2Te3 Nanopowders by Open Die Pressing

Open die pressing (ODP) at 370°C to 420°C has been employed as a straightforward forming process for sintering and texturing p-type (Bi_0.2Sb_0.8)₂Te₃ nanopowders. x-Ray diffraction pattern analysis showed that ODP samples were strongly textured, with the basal (00l) planes of the hexagonal crystal cell oriented parallel to the pressing plates. The degree of texturing, evaluated as the orientation factor, f, by the Lotgering method, increased with decreasing final thickness of the samples. It was about f = 45% for 10-mm-thick samples and reached 70% for 2-mm-thick samples. Thermoelectric properties of ODP specimens were measured by the Harman method in the range from 20°C to 170°C. The dimensionless figure of merit, ZT, for 10-mm-thick samples was around 1 from room temperature up to 100°C.     

Inorganic Colloidal Solution-Based Approach to Nanocrystal Synthesis of (Bi,Sb)2Te3

There is an interest in higher-ZT thermoelectric materials for high-watt-density cooling of electronics. Reducing thermal conductivity through increased phonon scattering in nanomaterials has been shown to be effective and is being investigated by many groups. Solution-based synthesis is a method for making thermoelectric nanomaterials that can provide particle sizes <20?nm and can be scaled to production quantities of materials. We are exploring an approach that proceeds through formation of an ??ink?? that contains inorganic colloidal nanocrystals of thermoelectric materials. This approach has the advantage that, by adjustments within the basic synthesis process, the size, shape, and composition of the nanocrystals can be tightly controlled to study changes in the transport properties. Currently we are making materials from inks that contain Bi₂Te₃ nanocrystals with Sb₂Te₃ ligands, suspended in a solvent. Powders formed by curing the inks are made into solid pellets by hot pressing, and the pellets are used for characterization and transport property measurements. The best result from our thermoelectric property measurements is ZT?=?0.9 with power factor of 27???W/cm?K², which to our knowledge is the best value for solution-based synthesis.     

The effect of Tl2Te3 on the properties of the solid solution (Sb2Te3)0.75.(Bi2Te3)0.25

The effect on transport properties of the addition of 0.5-5% Tl₂Te₃ to p-type solid solutions of antimony and bismuth tellurides was studied. It was found that the addition of Tl₂Te₃ caused a lessening of the increase of hole concentration as low temperatures were approached, resulting in a slower decrease of the Seebeck coefficient with a decrease in temperature. In partial fulfillment of M.Sc. degree, Hebrew University, Jerusalem. Permanent address, Dept. of Inorganic and Analytical Chemistry, Hebrew University, Jerusalem.     

Design and Optimization of Gradient Interface of p-Type Ba0.3In0.3FeCo3Sb12/Bi0.48Sb1.52Te3 Thermoelectric Materials

A series of p-type Ba_0.3In_0.3FeCo₃Sb₁₂/Bi_0.48Sb_1.52Te₃ (FS/BT) thermoelectric (TE) materials containing one gradient layer (1GL) with FS/BT volume ratio of 5:5, 3GLs-I with 7:3–5:5–3:7, 3GLs-II with 3:7–5:5–7:3, and 3GLs-III with 3:7–5:5–3:7 from FS to BT were fabricated by a two-step spark plasma sintering method. The interface structure and mechanical properties of the p-type FS/BT TE materials were investigated in this work. Designing the GLs at the interface of FS and BT bulk TE materials can effectively relax the thermal stress induced by the large difference in thermal expansion coefficient and eliminate the macroscopic cracks that occur in FS/BT TE materials with no GL, hence resulting in a remarkable enhancement in the interface mechanical properties of the FS/BT TE materials with the GLs. The optimized gradient interface of the FS/BT TE materials is 3GLs-II with FS/BT volume ratio of 3:7–5:5–7:3. The highest flexural strength of the 3GLs-II sample reached 13.68 MPa, increased by 116%.     

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.     

A Magnetoresistance Induced by a Nonzero Berry Phase in GeTe/Sb2Te3 Chalcogenide Superlattices

The chalcogenide alloy Ge–Sb–Te (GST) has not only been used in rewritable digital versatile discs, but also in nonvolatile electrical phase change memory as a key recording material. Although GST has been believed for a long time not to show magnetic properties unless doped with magnetic impurities, it has recently been reported that superlattices (SLs) with the structure [(GeTe)_L(Sb₂Te₃)_M]_N (where L, M, and N are usually integers) have a large magnetoresistance at room temperature for particular combinations of L and M. Here it is reported that when [(GeTe)_L(Sb₂Te₃)_M]_N chalcogenide SL films are thermally annealed at 470 K and cooled down to room temperature under an external magnetic field accompanied by current pulse injections, a large magnetoresistance change (>2500 Ω) is induced. This study shows that the phenomenon has a strong correlation with the GeTe thickness and the periodic structure of the SL films, and that it is induced by the structural phase transition between electrically nonpolar and polar phases in the GeTe layers in the SLs. This study proposes that the relationship between the polar (ferroelectric) phase and the Berry curvature in the SLs is responsible for the magnetoresistance change.     

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.     

Scanning Tunneling Microscopy in (Bi,Sb)2(Te,Se, S)3 Chalcogenide Thermoelectrics

Semiconductors - The morphology of the (0001) interlayer surface has been investigated by scanning tunneling microscopy in n-Bi1.6Sb0.4Te2.94Se0.06, n-Bi1.8Sb0.2Te2.82Se0.09S0.09,...     

Preparation and Characterization of Bi2Te3/Sb2Te3 Thermoelectric Thin-Film Devices for Power Generation

A device based on a new double-layer-leg thin-film concept has been successfully fabricated by flip-chip bonding of 242 pairs of n-type Bi₂Te₃ and p-type Sb₂Te₃ thin-film legs electrodeposited on top substrates to those processed on bottom substrates. Based on the output voltage–current curve, the internal resistance of the double-layer-leg thin-film device was measured to be 3.47 kΩ at an apparent temperature difference of 25.9 K across the device. The actual temperature difference across the thin-film legs was estimated to be 3.51 K, which is ～13% of the apparent temperature difference ΔT of 25.9 K applied across the thin-film device. The double-layer-leg thin-film device exhibited an open-circuit voltage of 0.43 V and maximum output power of 13.1 μW at an apparent temperature difference ΔT of 25.9 K.     

Highly efficient n-(Bi, Sb)2Te3 thermoelectric materials for temperatures below 200 K

The possibility of using an n-type Bi_2?x Sb_xTe₃ solid solution in thermoelectric refrigerators at T<200 K is considered. It is shown that, if the material under consideration is optimized for the above temperature region, the temperature dependence of the Seebeck coefficient α becomes less pronounced, and the crystal-lattice thermal conductivity κ_L decreases as compared to what is observed in a conventional n-Bi₂Te_3?y Se_y solid solution. These factors and a high mobility of charge carriers μ₀ bring about an increase in the parameter β ～ ZT, where Z is the thermoelectric efficiency.     

Three-Dimensional Bi2Te3 Nanocrystallites Embedded in 2D Bi2Te3 Films Grown by MOCVD

Two- (2D) and three-dimensional (3D) growth of nanostructured Bi₂Te₃ films was performed on 4° tilt (100) GaAs substrates using a metalorganic chemical vapor deposition system. To obtain 3D Bi₂Te₃ crystallites embedded in 2D planar film, we alternately changed the gas flow rate in the reactor. By repeating two steps, 3D Bi₂Te₃ crystallites embedded in 2D planar Bi₂Te₃ film were obtained. The thermoelectric properties in terms of the thermal conductivity, electrical conductivity, and Seebeck coefficient were investigated at room temperature. The thermal conductivities of the nanostructured Bi₂Te₃ films were from 0.63?W/(m?K) to 0.94?W/(m?K) at room temperature, which are low compared with that of film without nanostructure [1.62?W/(m?K)]. The thermal conductivity of the film was effectively decreased with the decrease of size and increase of density of 3D crystallites. The results of this study open up a new method to fabricate nanostructured thermoelectric films with high thermoelectric figure of merit.