Transport and Mechanical Properties of High-ZT Mg2.08Si0.4−x Sn0.6Sb x Thermoelectric Materials

Mg₂(Si,Sn) compounds are promising candidate low-cost, lightweight, nontoxic thermoelectric materials made from abundant elements and are suited for power generation applications in the intermediate temperature range of 600 K to 800 K. Knowledge on the transport and mechanical properties of Mg₂(Si,Sn) compounds is essential to the design of Mg₂(Si,Sn)-based thermoelectric devices. In this work, such materials were synthesized using the molten-salt sealing method and were powder processed, followed by pulsed electric sintering densification. A set of Mg_2.08Si_0.4?x Sn_0.6Sb _x (0 ≤ x ≤ 0.072) compounds were investigated, and a peak ZT of 1.50 was obtained at 716 K in Mg_2.08Si_0.364Sn_0.6Sb_0.036. The high ZT is attributed to a high electrical conductivity in these samples, possibly caused by a magnesium deficiency in the final product. The mechanical response of the material to stresses is a function of the elastic moduli. The temperature-dependent Young’s modulus, shear modulus, bulk modulus, Poisson’s ratio, acoustic wave speeds, and acoustic Debye temperature of the undoped Mg₂(Si,Sn) compounds were measured using resonant ultrasound spectroscopy from 295 K to 603 K. In addition, the hardness and fracture toughness were measured at room temperature.     

The Effect of Adding Nano-Bi2Te3 on Properties of GeTe-Based Thermoelectric Material

The efficient thermoelectric materials (GeTe)_0.85?x (Mn_0.6Sn_0.4Te)_0.15(Bi₂Te₃) _x (0 ≤ x ≤ 0.05), in which Bi₂Te₃ is nanopowder, were prepared by hot pressing. The effect of adding neutral nano-Bi₂Te₃ content on the thermoelectric properties of germanium telluride was investigated. With increasing x, the thermal conductivity of the prepared samples decreased significantly and the Seebeck coefficient declined slightly, while there was no obvious change in electrical conductivity. In both electrical conductivity and Seebeck coefficient curves at different x values, there are inflection points around 600 K. The maximum dimensionless figure of merit ZT of the prepared materials is 1.54, attained in the temperature range from 700 K to 750 K for x = 0.03. The x-ray diffraction (XRD) pattern shows that Bi₂Te₃ has been alloyed into the GeTe-MnTe-SnTe alloy, which is consistent with the high-resolution scanning electron microscopy (HRSEM) images. Adding nano-Bi₂Te₃ to GeTe-based materials could also increase their performance stability at high temperature as a result of decreasing the phase-transition temperature T _c.     

Manufacturing Processes for TiO x -Based Thermoelectric Modules: from Suboxide Synthesis to Module Testing

An overview of different TiO _x synthesis methods with regard to enhancement of thermoelectric properties and transfer of the synthesis process to cost-efficient methods as well as joining techniques for module manufacture is presented. Different synthesis routes were applied and investigated, namely synthesis of TiO _x via reduction with less gas formation by mixing TiO₂ and TiC [powder-derived (PD)-TiO _x ], a bottom-up approach via a precursor route for synthesizing TiO _x directly [precursor-derived (PDC)-TiO _x ], and the combination by mixing TiO₂ with precursor (PDC-TiO _x /TiO₂). All the approaches resulted in adjustable phase composition with different oxygen contents and, therefore, adjustable electrical properties as well as different microstructures to enhance the physical and thermoelectric properties. The electrical resistivity could be adjusted from 1 mΩ cm to 1000 mΩ cm through the oxygen content of TiO _x . The research included investigations of cost-efficient production processes for thermoelectric material such as spray-drying, spark plasma sintering, hot pressing or pressureless sintering in terms of shaping, sintering, and machining, as well as joining techniques to build a complete thermoelectric module. To realize thermal and electrical connections, technologies for joining and packaging were developed. For a first demonstration of the feasibility of TiO _x -based thermoelectric modules for use at high temperatures, a unileg n-type module with footprint of 30 mm × 30 mm was designed. Low-volume fabrication yielded more than 20 single modules. Finally, the modules were successfully tested under conditions close to those of the desired applications with hot-side temperature up to 600°C.     

Effects of Synthesis and Spark Plasma Sintering Conditions on the Thermoelectric Properties of Ca3Co4O9+δ

Ca₃Co₄O_9+δ samples were synthesized by solid-state (SS) and sol–gel (SG) reactions, followed by spark plasma sintering under different processing conditions. The synthesis process was optimized and the resulting materials characterized with respect to their microstructure, bulk density, and thermoelectric transport properties. High power factors of about 400 μW/m·K² and 465 μW/m·K² (at 800°C) were measured for SS and SG samples, respectively. The improved thermoelectric performance of the SG sample is believed to originate from the smaller particle sizes and better grain alignment. The SG method is suggested to be a beneficial means of obtaining high-performance thermoelectric materials of Ca₃Co₄O_9+δ type.     

Thin-Film Thermoelectric Modules for Power Generation Using Focused Solar Light

We demonstrated the fabrication of thin-film thermoelectric generators and evaluated their generation properties using solar light as a thermal source. Thin-film elements of Bi_0.5Sb_1.5Te₃ (p-type) and Bi₂Te_2.7Se_0.3 (n-type), which were patterned using the lift-off technique, were deposited on glass substrates using radiofrequency magnetron sputtering. After annealing at 300°C, the average Seebeck coefficients of p- and n-type films were 150???V/K and ?104???V/K, respectively, at 50°C to 75°C. A cylindrical lens was used to focus solar light to a line shape onto the hot side of the thin-film thermoelectric module with 15 p?Cn junctions. The minimum width of line-shaped solar light was 0.8?mm with solar concentration of 12.5 suns. We studied the properties of thermoelectric modules with different-sized p?Cn junctions on the hot side, and obtained maximum open voltage and power values of 140?mV and 0.7???W, respectively, for a module with 0.5-mm p?Cn junctions. The conversion efficiency was 8.75?×?10^?4%, which was approximately equal to the value estimated by the finite-element method.     

Thermoelectric Properties of Indium-Added Skutterudites In x Co4Sb12

The high-temperature thermoelectric properties of In _x Co₄Sb₁₂ (0.05 ≤ x ≤ 0.40) skutterudite compounds were investigated in this study. The phase states of the samples were identified by x-ray diffraction analysis and field-emission scanning electron microscopy at room temperature. InSb and CoSb₂ were found as secondary phases in samples with x = 0.10 to 0.40. The filling limit of In into the CoSb₃ cages of In _x Co₄Sb₁₂ was in the range 0.05 < x < 0.10. The electrical resistivity, Seebeck coefficient, and thermal conductivity of the In _x Co₄Sb₁₂ samples were measured from room temperature to 773 K. The Seebeck coefficient of all samples was negative. Reduction of the thermal conductivity by In addition resulted in a high thermoelectric figure of merit (ZT) of 0.67 for In_0.35Co₄Sb₁₂ at 600 K.     

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.     

Physical Properties of Single-Crystalline Ba8Ni3.5Ge42.1□0.4

Clathrates are candidate materials for thermoelectric applications because of a number of unique properties. The clathrate I phases in the Ba-Ni-Ge ternary system allow controlled variation of the charge carrier concentration by adjusting the Ni content. Depending on the Ni content, the physical properties vary from metal-like to insulator-like and show a transition from p-type to n-type conduction. Here we present first results on the characterization of millimeter-sized single crystals grown by the Bridgman technique. Single crystals with a composition of Ba₈Ni_3.5Ge_42.1□_0.4 show metallic behavior (dρ/dT > 0) albeit with high resistivity at room temperature [ρ (300 K) = 1 mΩ cm]. The charge carrier concentration at 300 K, as determined from Hall-effect measurements, is 2.3 e^?/unit cell. The dimensionless thermoelectric figure of merit estimated at 680 K is ZT ≈ 0.2.     

Thermoelectric Properties of Al-Doped ZnO Thin Films

We have prepared 2 % Al-doped ZnO (AZO) thin films on SrTiO₃ substrates by a pulsed laser deposition technique at various deposition temperatures (T _dep = 300–600 °C). The thermoelectric properties of AZO thin films were studied in a low temperature range (300–600 K). Thin film deposited at 300 °C is fully c-axis-oriented and presents electrical conductivity 310 S/cm with Seebeck coefficient ?65 μV/K and power factor 0.13 × 10^?3 Wm^?1 K^?2 at 300 K. The performance of thin films increases with temperature. For instance, the power factor is enhanced up to 0.55 × 10^?3 Wm^?1 K^?2 at 600 K, surpassing the best AZO film previously reported in the literature.     

Printed Se-Doped MA n-Type Bi2Te3 Thick-Film Thermoelectric Generators

In this work, we highlight new materials processing developments and fabrication techniques for dispenser-printed thick-film single-element thermoelectric generators (TEG). Printed deposition techniques allow for low-cost and scalable manufacturing of microscale energy devices. This work focuses on synthesis of unique composite thermoelectric systems optimized for low-temperature applications. We also demonstrate device fabrication techniques for high-density arrays of high-aspect-ratio planar single-element TEGs. Mechanical alloyed (MA) n-type Bi₂Te₃ powders were prepared by taking pure elemental Bi and Te in 36:64 molar ratio and using Se as an additive. X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques were used to characterize the as-milled powders to confirm the Bi₂Te₃ phase formation and particle size below 50???m. Thermoelectric properties of the composites were measured from room temperature to 100°C. We achieved a dimensionless figure of merit (ZT) of 0.17 at 300?K for MA n-type Bi₂Te₃?Cepoxy composites with 2?wt.% Se additive. A 20 single-leg TEG prototype with 5?mm?×?400???m?×?120???m printed element dimensions was fabricated on a polyimide substrate with evaporated gold contacts. The prototype device produced a power output of 1.6???W at 40???A and 40?mV voltage for a temperature difference of 20°C.     

Good Thermal Stability,High Permittivity,Low Dielectric Loss and Chemical Compatibility with Silver Electrodes of Low-Fired BaTiO<Subscript>3</Subscript>–Bi(Cu<Subscript>0.75</Subscript>W<Subscript>0.25</Subscript>)O<Subscript>3</Subscript> Ceramics

(1 ? x)BaTiO₃–xBi(Cu_0.75W_0.25)O₃ [(1 ? x)BT–xBCW, 0 ≤ x ≤ 0.04] perovskite solid solutions ceramics of an X8R-type multilayer ceramic capacitor with a low sintering temperature (900°C) were synthesized by a conventional solid state reaction technique. Raman spectra and x-ray diffraction analysis demonstrated that a systematically structural evolution from a tetragonal phase to a pseudo-cubic phase appeared near 0.03 < x < 0.04. X-ray photoelectron analysis confirmed the existence of Cu⁺/Cu²⁺ mixed-valent structure in 0.96BT–0.04BCW ceramics. 0.96BT–0.04BCW ceramics sintered at 900°C showed excellent temperature stability of permittivity (Δε/ε _25°C ≤ ±15%) and retained good dielectric properties (relative permittivity ～1450 and dielectric loss ≤2%) over a wide temperature range from 25°C to 150°C at 1 MHz. Especially, 0.96BT–0.04BCW dielectrics have good compatibility with silver powders. Dielectric properties and electrode compatibility suggest that the developed materials can be used in low temperature co-fired multilayer capacitor applications.     

Fabrication of Multilayer-Type Mn-Si Thermoelectric Device

This research aims to develop a direct-contact manganese silicon p/n multilayer-type thermoelectric power generation block. p-type MnSi_1.74 and n-type Mn_0.7Fe_0.3Si_1.68 ball-milled powders with diameter of about 10 μm or less were mixed with polyvinyl butyl alcohol diluted with methylbenzene at pigment volume concentration of approximately 70%. The doctor-blade method produced 45-μm-thick p- and n-type pigment plates. The insulator, i.e., powdered glass, was mixed with cellulose to form insulator slurry. Lamination of manganese silicide pigment layers and screen-printed insulator layers was carried out to fabricate multilayer direct-contact thermoelectric devices. Hot pressing and spark plasma sintering were carried out at 450°C and 900°C, respectively. Four to 30 thermoelectric (TE) p/n pairs were fabricated in a 10 mm × 10 mm × 10 mm sintered TE block. The maximum output was 11.7 mW/cm² at a temperature difference between 20°C and 700°C, which was about 1/85 of the ideal power generation estimated from the thermoelectric data of the bulk MnSi_1.74 and Mn_0.7Fe_0.3Si_1.68 materials. A power generation test using an engine test bench was also carried out.     

Low-Temperature,Solution-Based,Scalable Synthesis of Sb2Te3 Nanoparticles with an Enhanced Power Factor

Nanostructured thermoelectric (TE) materials, for example Sb₂Te₃, PbTe, and SiGe-based semiconductors, have excellent thermoelectric transport properties and are promising candidates for next-generation TE commercial application. However, it is a challenge to synthesize the corresponding pure nanocrystals with controlled size by low-temperature wet-chemical reaction. Herein, we report an alternative versatile solution-based method for synthesis of plate-like Sb₂Te₃ nanoparticles in a flask using SbCl₃ and Te powders as raw materials, EDTA-Na₂ as complexing agent, and NaBH₄ as reducing agent in the solvent (distilled water). To investigate their thermoelectric transport properties, the obtained powders were cold compacted into cuboid prisms then annealed under a protective N₂ atmosphere. The results showed that both the electrical conductivity (σ) and the power factor (S ² σ) can be enhanced by improving the purity of the products and by increasing the annealing temperature. The highest power factor was 2.04 μW cm^?1 K^?2 at 140°C and electrical conductivity remained in the range 5–10 × 10³ S m^?1. This work provides a simple and economic approach to preparation of large quantities of nanostructured Sb₂Te₃ with excellent TE performance, making it a fascinating candidate for commercialization of cooling devices.     

Phase Stability and Thermoelectric Properties of CuFeS2-Based Magnetic Semiconductor

Recently, based on measurement results below 400 K, we suggested that chalcopyrite CuFeS₂-based alloys hold promise as thermoelectric materials. In this study, we have investigated the phase stability of such compounds and measured their thermoelectric properties at temperatures above 400 K. Thermogravimetric data indicate that the samples synthesized by a spark plasma sintering method were stable up to 700 K, above which sulfur deficiency becomes prominent. The electrical resistivity of the electron-doped samples showed metallic behavior up to 700 K. The Seebeck coefficients show large negative values of about ?300 μV/K above 400 K. As a result, the power factor of Cu_0.97Fe_1.03S₂ is ~1 mW/K²m in the temperature range of 400 K to 600 K.     

Titanium Disilicide as High-Temperature Contact Material for Thermoelectric Generators

Thermoelectric devices can be used to capture electric power from waste heat in a variety of applications. The theoretical efficiency rises with the temperature difference across the thermoelectric generator (TEG). Therefore, we have investigated contact materials to maximize the thermal stability of a TEG. A promising candidate is titanium disilicide (TiSi₂), which has been well known as a contact material in silicon technology for some time, having low resistivity and thermal stability up to 1150 K. A demonstrator using highly doped silicon as the thermoelectric material has been integrated. A p- and an n-type wafer were oxidized and bonded. After cutting the wafer into pieces, a 200-nm-thick titanium layer was sputtered onto the edges. After a 750°C rapid thermal annealing step, the TEG legs were connected by a highly conductive TiSi₂ layer. A TEG with 12 thermal couples was integrated, and its joint resistance was found to be 4.2 Ω. Hence, we have successfully demonstrated a functional high-temperature contact for TEGs up to at least 900 K. Nevertheless, the actual thermal stability will be even higher. The process could be transfered to other substrates by using amorphous silicon deposited by plasma-enhanced chemical vapor deposition.     

Stress Analysis and Output Power Measurement of an n-Mg2Si Thermoelectric Power Generator with an Unconventional Structure

We examine the mechanical stability of an unconventional Mg₂Si thermoelectric generator (TEG) structure. In this structure, the angle θ between the thermoelectric (TE) chips and the heat sink is less than 90°. We examined the tolerance to an external force of various Mg₂Si TEG structures using a finite-element method (FEM) with the ANSYS code. The output power of the TEGs was also measured. First, for the FEM analysis, the mechanical properties of sintered Mg₂Si TE chips, such as the bending strength and Young’s modulus, were measured. Then, two-dimensional (2D) TEG models with various values of θ (90°, 75°, 60°, 45°, 30°, 15°, and 0°) were constructed in ANSYS. The x and y axes were defined as being in the horizontal and vertical directions of the substrate, respectively. In the analysis, the maximum tensile stress in the chip when a constant load was applied to the TEG model in the x direction was determined. Based on the analytical results, an appropriate structure was selected and a module fabricated. For the TEG fabrication, eight TE chips, each with dimensions of 3 mm × 3 mm × 10 mm and consisting of Sb-doped n-Mg₂Si prepared by a plasma-activated sintering process, were assembled such that two chips were connected in parallel, and four pairs of these were connected in series on a footprint of 46 mm × 12 mm. The measured power generation characteristics and temperature distribution with temperature differences between 873 K and 373 K are discussed.     

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.     

Influence of Sedimentation of Atoms on Structural and Thermoelectric Properties of Bi-Sb Alloys

Functionally graded thermoelectric materials (FGTMs) have been prepared by sedimentation of atoms under a strong gravitational field. Starting samples of Bi _x Sb_1?x alloys with different composition x were synthesized by melting of metals and subsequent annealing of quenched samples. The thermoelectric properties (Seebeck coefficient, electrical conductivity) of the starting materials were characterized over the temperature range from 300 K to 525 K. Strong gravity experiments were performed in a unique ultracentrifuge apparatus under acceleration of over 0.5 × 10⁶ G at temperatures of 538 K and 623 K. Changes of the microstructure and chemical composition were analyzed using scanning electron microscopy with energy-dispersive x-ray spectroscopy analysis. The distribution of the Seebeck coefficient of the Bi-Sb alloys was characterized by scanning thermoelectric microprobe. As a result of sedimentation, large changes in chemical composition (x = 0.45 to 1) were obtained. It was found that the changes in chemical composition were correlated with alterations of the Seebeck coefficient. The obtained experimental data allowed the development of a semiempirical model for the selection of optimal processing parameters for preparation of Bi-Sb alloys with required thermoelectric properties.     

Synthesis and Thermoelectric Properties of In and Pr Double-Filled Skutterudites In x Pr y Co4Sb12

Double-filled skutterudites In _x Pr _y Co₄Sb₁₂, which are currently being investigated for potential applications as thermoelectric materials, have been successfully prepared by inductive melting and annealing. Our results showed that In and Pr double filling effectively improves both electrical conductivity and Seebeck coefficient compared with pristine or single-filled CoSb₃, giving rise to a respectable power factor. The largest power factor, 2.33 m Wm^?1 K^?2, was achieved at 609 K for In_0.05Pr_0.05Co₄Sb₁₂; this value is approximately three times that for In _x Co₄Sb₁₂ (x ≤ 0.3) skutterudites. These results imply that In and Pr double filling are better than In single filling for efficient improvement of the thermoelectric properties of CoSb₃ skutterudite.     

Synthesis and Characterization of Al-Doped Mg2Si Thermoelectric Materials

Magnesium silicide (Mg₂Si)-based alloys are promising candidates for thermoelectric (TE) energy conversion for the middle to high range of temperature. These materials are very attractive for TE research because of the abundance of their constituent elements in the Earth’s crust. Mg₂Si could replace lead-based TE materials, due to its low cost, nontoxicity, and low density. In this work, the role of aluminum doping (Mg₂Si:Al = 1:x for x = 0.005, 0.01, 0.02, and 0.04 molar ratio) in dense Mg₂Si materials was investigated. The synthesis process was performed by planetary milling under inert atmosphere starting from commercial Mg₂Si pieces and Al powder. After ball milling, the samples were sintered by means of spark plasma sintering to density >95%. The morphology, composition, and crystal structure of the samples were characterized by field-emission scanning electron microscopy, energy-dispersive spectroscopy, and x-ray diffraction analyses. Moreover, Seebeck coefficient analyses, as well as electrical and thermal conductivity measurements were performed for all samples up to 600°C. The resultant estimated ZT values are comparable to those reported in the literature for these materials. In particular, the maximum ZT achieved was 0.50 for the x = 0.01 Al-doped sample at 600°C.