Porous Materials in Synthetic Transverse Thermoelements

Substantial transverse Peltier cooling has been reported for synthetic composites consisting of layers of bismuth telluride and either bismuth or lead. Ideally, the two materials in such a composite should have very different values for the electrical and thermal conductivities. If this condition is satisfied, the transverse figure of merit, Z _ϕ , for the optimum orientation is not much smaller than the longitudinal figure of merit, Z, for the two materials when used as a conventional thermocouple. A second condition is that Z should be as large as possible. We have shown that the two conditions can be met simultaneously if one of the components is porous or otherwise discontinuous. Thus, a highly efficient transverse thermoelement could be made from porous p-type and dense n-type bismuth telluride. Effective transverse thermoelements could also be made from less porous p-type bismuth telluride in conjunction with either single crystal bismuth or YbAl_2.96Mn_0.04. It is shown that a dimensionless transverse figure of merit, Z _ϕ T, in excess of 0.6 should easily be obtained with these configurations. It should be possible to observe temperature depressions in excess of 100° by the use of suitably shaped synthetic transverse thermoelements.     

Use of a Soluble Anode in Electrodeposition of Thick Bismuth Telluride Layers

Integration of thermoelectric devices within an automotive heat exchanger could enable conversion of lost heat into electrical energy, contributing to improved total output from the engine. For this purpose, synthesis of thick bismuth telluride (Bi₂Te₃) films is required. Bismuth telluride has been produced by an electrochemical method in nitric acid with a sacrificial bismuth telluride anode as the source of cations. The binary layer grows on the working electrode while the counter-electrode, a Bi₂Te₃ disk obtained by high frequency melting, is oxidized to Bi^III and Te^IV. This process leads to auto-regeneration of the solution without modification of its composition. The thickness of films deposited by use of the Bi₂Te₃ anode was approximately 10 times that without. To demonstrate the utility of a soluble anode in electrochemical deposition, we report characterization of the composition and morphology of the films obtained under different experimental conditions. Perfectly dense and regular Bi₂Te₃ films (～400 μm) with low internal stress and uniform composition across the cross-section were prepared. Their thermoelectric properties were assessed.     

Molecular Dynamics Simulation of Mechanical Properties of Single-Crystal Bismuth Telluride Nanowire

The mechanical properties of single-crystal bismuth telluride nanowires have been studied by molecular dynamics methods. The mechanical behavior of the Bi₂Te₃ nanowire for two principal axes was simulated under different strain rates at low temperature and the results compared with those of bulk Bi₂Te₃. The simulation results show that, due to its marked anisotropy, the nanowire shows quite different failure behaviors in the two directions, with the failure stress for the a-axis (4.7 GPa) being three times that for the c-axis (1.4 GPa). The stress–strain curve of the nanowire is different from that for Bi₂Te₃ bulk, as surface stress induced by atomic rearrangement significantly reduces the strength of the nanowire. The effect of strain rate on the mechanical properties of the nanowire has also been analyzed, showing that the failure stress and failure strain decrease with decreasing strain rate, a behavior not apparent in the bulk Bi₂Te₃ simulation.     

Fabrication of Bismuth Telluride Thermoelectric Films Containing Conductive Polymers Using a Printing Method

We prepared a mixture of thermoelectric bismuth telluride particles, a conductive polymer [poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)], poly(acrylic acid) (PAA), and several organic additives to fabricate thermoelectric films using printing or coating techniques. In the mixture, the organic components (PEDOT:PSS, PAA, and an additive) act as a binder to connect bismuth telluride particles mechanically and electrically. Among the organic additives used, glycerol significantly enhanced the electrical conductivity and bismuth telluride particle dispersibility in the mixture. Bi_0.4Te_3.0Sb_1.6 films fabricated by spin-coating the mixture showed a thermoelectric figure of merit (ZT) of 0.2 at 300 K when the Bi_0.4Te₃Sb_1.6 particle diameter was 2.8 μm and its concentration in the elastic films was 95 wt.%.     

Effect of Processing Route on the Microstructure and Thermoelectric Properties of Bismuth Telluride-Based Alloys

Considerable work has been done to engineer materials with high efficiencies of thermoelectric heat-to-electricity conversion and the mechanical strength necessary to withstand the demands of practical applications. In particular, in the bismuth telluride system, extrusion pressing has been found to be effective for improving the mechanical strength of alloys via grain refinement. We review some of the literature relating to processing approaches for the bismuth telluride system. We also present preliminary data for a series of samples obtained by incorporating C₆₀ via ball milling and spark plasma sintering into a matrix consisting of a (Bi,Sb)₂Te₃ alloy, with a focus on the texture of the composites and its relation to thermoelectric transport properties, in comparison to the parent material. The viability of improving the thermoelectric performance of bismuth telluride alloys by the insertion of nanoparticles into a composite is also considered.     

Thermoelectric Coolers with Sintered Silver Interconnects

The fabrication and performance of a sintered Peltier cooler (SPC) based on bismuth telluride with sintered silver interconnects are described. Miniature SPC modules with a footprint of 20 mm² were assembled using pick-and-place pressure-assisted silver sintering at low pressure (5.5 N/mm²) and moderate temperature (250°C to 270°C). A modified flip-chip bonder combined with screen/stencil printing for paste transfer was used for the pick-and-place process, enabling high positioning accuracy, easy handling of the tiny bismuth telluride pellets, and immediate visual process control. A specific contact resistance of (1.4 ± 0.1) × 10^?5 Ω cm² was found, which is in the range of values reported for high-temperature solder interconnects of bismuth telluride pellets. The realized SPCs were evaluated from room temperature to 300°C, considerably outperforming the operating temperature range of standard commercial Peltier coolers. Temperature cycling capability was investigated from 100°C to 235°C over more than 200 h, i.e., 850 cycles, during which no degradation of module resistance or cooling performance occurred.     

High Performance BiSbTe Alloy for Superior Thermoelectric Cooling

At present, the weak thermoelectric and mechanical performance of zone-melting bismuth telluride alloys cannot support the further improvement of cooling and processing performance of semiconductor refrigeration devices. Here, MnO₂ is added into high-strength Bi_0.4Sb_1.6Te₃ prepared by ball milling method to optimize its thermoelectric transport properties. Via in situ reaction, Sb₂O₃ nano-precipitates are formed in the matrix, which also leads to the surplus of Te element. As results, the donor-like effect is suppressed, thereby increasing carrier concentration and power factor. Besides, volatilization of Te-rich phases during sintering leaves plentiful nanopores, which together with Sb₂O₃ nano-precipitates significantly decrease the lattice thermal conductivity. Eventually, the maximum ZT reaches 1.43 at 75 °C for the Bi_0.4Sb_1.6Te₃+0.01MnO₂ sample. On this basis, a 31-pairs module made of the material and commercial n-type BiTeSe produces large temperature differences (ΔT) of 70.1, 80.8, and 89.4 K at the hot-side temperature (T_h) of 300, 325, and 350 K respectively, which are highly competitive. The maximum coefficient of performance of 8.6 and cooling capacity of 7 W are achieved when T_h is set as 325 K. This excellent progress will promote the further development of bismuth telluride refrigeration modules.     

Synthesis and Characterization of Polythiophene/Bi2Te3 Nanocomposite Thermoelectric Material

To achieve low thermal conductivity, polythiophene (PTh)/bismuth telluride (Bi₂Te₃) nanocomposite has been prepared by spark plasma sintering using a mixture of nanosized Bi₂Te₃ and PTh powders. Bi₂Te₃ powder with spherical-shaped particles of 30 nm diameter and PTh nanosheet powder were first prepared by hydrothermal synthesis and chemical oxidation, respectively. X-ray diffraction analysis and scanning electron microscopy observations revealed that the hybrid composite consists of PTh nanosheets and spherical Bi₂Te₃. The organic PTh acts as an adhesive in the composite. Transport measurements showed that the PTh in the Bi₂Te₃ matrix can reduce its thermal conductivity significantly, but also dramatically reduces its electrical conductivity. As a result, the figure of merit of the composite is lower than that of pure Bi₂Te₃ prepared under the same conditions. The maximum value of ZT for the sample with 5% PTh (by weight) was 0.18 at 473 K, which is rather high compared with other polymer/inorganic thermoelectric material composites.     

Fabrication and Evaluation of a Thermoelectric Microdevice on a Free-Standing Substrate

Using shadow masks prepared by standard microfabrication processes, we fabricated in-plane thermoelectric microdevices (4 mm × 4 mm) made of bismuth telluride thin films, and evaluated their performance. We used Bi_0.4Te_3.0Sb_1.6 as the p-type semiconductor and Bi_2.0Te_2.7Se_0.3 as the n-type semiconductor. We deposited p- and n-type thermoelectric thin films on a free-standing thin film of Si₃N₄ (4 mm × 4 mm × 4 μm) on a Si wafer, and measured the output voltages of the microdevices while heating at the bottom of the Si substrate. The maximum output voltage of the thermoelectric device was 48 mV at 373 K.     

Pulsed Electroplating: a Derivate Form of Electrodeposition for Improvement of (Bi1?xSbx)2Te3 Thin Films

Bismuth antimony telluride (Bi_1−x Sb _x )₂Te₃ thermoelectric compounds were synthesized by pulse plating. Due to the large number of parameters available (pulse waveform, on/off pulse time, applied current density), this advanced form of electrodeposition allows better control of the interfacial supply and electrochemical reactions and offers effective ways to improve macroscopic properties such as adhesion and to produce crack-free hard deposits and fine-grained films with higher uniformity and lower porosity. The influence of pulse parameters (pulse time t _on, cathodic current density J _c) on the stoichiometry, roughness, and crystallography of deposits was studied. The thermoelectric properties (electrical resistivity and Seebeck coefficient) of the films were measured. The results revealed that deposits have p-type conductivity directly after electroplating (Seebeck coefficient around 150 μV K⁻¹), in contrast to films synthesized by direct current, which require annealing. An improvement of resistivity was observed: for a direct-current-deposited film the resistivity is around 5000 μΩ m, whereas for a pulse-deposited film the resistivity was around 200 μΩ m.     

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.     

Vapor Annealing as a Post-Processing Technique to Control Carrier Concentrations of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> Thin Films

This article demonstrates that carrier concentrations in bismuth telluride films can be controlled through annealing in controlled vapor pressures of tellurium. For the bismuth telluride source with a small excess of tellurium, all the films reached a steady state carrier concentration of 4 × 10¹⁹ carriers/cm³ with Seebeck coefficients of −170 μV K⁻¹. For temperatures below 300°C and for film thicknesses of 0.4 μm or less, the rate-limiting step in reaching a steady state for the carrier concentration appeared to be the mass transport of tellurium through the gas phase. At higher temperatures, with the resulting higher pressures of tellurium or for thicker films, it was expected that mass transport through the solid would become rate limiting. The mobility also changed with annealing, but at a rate different from that of the carrier concentration, perhaps as a consequence of the non-equilibrium concentration of defects trapped in the films studied by the low temperature synthesis approach.     

Fabrication by Coaxial-Type Vacuum Arc Evaporation Method and Characterization of Bismuth Telluride Thin Films

We prepared both n- and p-type bismuth telluride thin films by using a coaxial-type vacuum arc evaporation method. The atomic compositions of the as-grown thin films and several annealed thin films were comparable to that of bulk bismuth telluride. Their thermoelectric properties were measured and found to be comparable to those of bulk materials. The Seebeck coefficient and electrical conductivity of the as-grown thin films were improved by the annealing process. The measured figures of merit (ZT) of the films were 0.86 for the n-type and 0.41 for the p-type at 300 K for annealing temperatures of 573 K and 523 K, respectively.     

Performance of MnO<Subscript>2</Subscript> Crystallographic Phases in Rechargeable Lithium-Air Oxygen Cathode

Manganese dioxide (MnO₂) has been shown to be effective for improving the efficiency of cathodes in lithium-air cells. Different crystallographic phases including α-, β-, and γ-MnO₂ nanowires, α-MnO₂ nanospheres, and α-MnO₂ nanowires on carbon (α-MnO₂/C) were synthesized using the hydrothermal method. Their physical properties were examined using x-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) surface area measurements, and scanning electron microscopy (SEM) and found to be in agreement with the literature. Electrochemical properties of the synthesized catalyst particles were investigated by fabricating cathodes and testing them in a lithium-air cell with lithium hexafluorophosphate in propylene carbonate (LiPF₆/PC) and tetra(ethylene glycol)dimethyl ether (LiTFSi/TEGDME) electrolytes. α-MnO₂ had the highest discharge capacity in the LiTFSi/TEGDME electrolyte (2500 mAh/g), whilst α-MnO₂/C in LiPF₆/PC showed a significantly higher discharge capacity of 11,000 mAh/g based on total mass of the catalytic cathode. However, the latter showed poor capacity retention compared with γ-MnO₂ nanowires, which was stable for up to 30 cycles. The reported discharge capacity is higher than recorded in previous studies on lithium-air cells.     

Effect of the deposition rate on the phase transition in silver telluride thin films

Silver telluride thin films of thickness 50 nm have been deposited at different deposition rates on glass substrates at room temperature and at a pressure of 2×10⁻⁵ mbar. The electrical resistivity was measured in the temperature range 300–430 K. The temperature dependence of the electrical resistance of Ag₂Te thin films shows structural phase transition and coexistence of low temperature monoclinic phase and high temperature cubic phase. The effect of deposition rate on the phase transition and the electrical resistivity of silver telluride thin films in relation to carrier concentration and mobility are discussed.     

Pulsed Laser Deposition of Bismuth Telluride Thin Films for Microelectromechanical Systems Thermoelectric Energy Harvesters

This article reports on the development of thin films of p- and n-type bismuth telluride compounds which are suitable for microelectromechanical systems (MEMS) thermoelectric energy harvesters. Films were prepared by the pulsed laser deposition technique. It is shown that the thin films of binary Bi-Te alloys outperformed considerably their ternary counterparts. Furthermore, the highest thermoelectric figure of merit (ZT) was found to be 0.39 for the p-type Bi₃₂Te₆₈ alloy, whereas the optimal n-type alloy was Bi₂₅Te₇₅, which was characterized by a relatively low stress gradient.     

Intrinsic and Doped Zinc Oxide Nanowires for Transparent Electrode Fabrication via Low-Temperature Solution Synthesis

Undoped and doped zinc oxide (ZnO) nanowires were synthesized by decomposing metal salts in trioctylamine at 300°C. By adding metal salts during the formation of the wires, effective incorporation of Ga and Al up to 5% was achieved, as measured by energy-dispersive x-ray spectroscopy and Auger electron spectroscopy. No secondary phase was detected by high-resolution transmission electron microscopy and x-ray diffraction. The nanowires were single-crystalline with a wurtzite lattice structure. Films made with doped wires show a complex dependence of the sheet resistance on processing conditions and dopant concentration. Thermal annealing treatment reduced the sheet resistance to values of 10³ Ω/square.     

Electrical transport properties of single GaN and InN nanowires

The transport properties of single GaN and InN nanowires grown by thermal catalytic chemical vapor deposition were measured as a function of temperature, annealing condition (for GaN) and length/square of radius ratio (for InN). The as-grown GaN nanowires were insulating and exhibited n-type conductivity (n ≈ 2×10¹⁷ cm⁻³, mobility of 30 cm²/V s) after annealing at 700°C. A simple fabrication process for GaN nanowire field-effect transistors on Si substrates was employed to measure the temperature dependence of resistance. The transport was dominated by tunneling in these annealed nanowires. InN nanowires showed resistivity on the order of 4×10⁻⁴ Ω cm and the specific contact resistivity for unalloyed Pd/Ti/Pt/Au ohmic contacts was near 1.09×10⁻⁷ Ω cm². For In N nanowires with diameters <100 nm, the total resistance did not increase linearly with length/square of radius ratio but decreased exponentially, presumably due to more pronounced surface effect. The temperature dependence of resistance showed a positive temperature coefficient and a functional form characteristic of metallic conduction in the InN nanowires.     

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.     

Enhancement in Figure of Merit (ZT) by Annealing of BiTe Nanostructures Synthesized by Microwave-Assisted Flash Combustion

Uniform polycrystalline bismuth telluride (BiTe) nanowires of diameter 100 nm to 150 nm and hexagonal nanoplates with thickness of 50 nm to 100 nm have been successfully synthesized by the microwave-assisted flash combustion technique. The formation of BiTe nanostructures depends on the type of fuel and the oxidant-to-fuel ratio, which in turn affect the reaction time and reaction temperature. Spark plasma sintering has been employed for compaction and sintering of both as-synthesized as well as annealed BiTe powders. Increasing the sintering temperature while using faster sintering cycles reduced the porosity, resulting in high densification while preserving the nanostructures. The dimensionless figure of merit (ZT) was evaluated from the Seebeck coefficient, electrical resistivity, and thermal conductivity values over the range from 300 K to 600 K. The effect of annealing on the enhancement of ZT is discussed. These evaluations suggest that the rarely studied BiTe is a potential candidate for thermoelectric applications at low temperatures.