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.     

Lpe growth of Hgl−xCdxTe using conventional slider boat and effects of annealing on properties of the epilayers

The epitaxial layers of Hg_1−xCd_xTe (0.17≦×≦0.3) were grown by liquid phase epitaxy on CdTe (111)A substrates using a conventional slider boat in the open tube H₂ flow system. The as-grown layers have hole concentrations in the 10¹⁷− 10¹⁸ cm⁻³ range and Hall mobilities in the 100−500 cm²/Vs range for the x=0.2 layers. The surfaces of the layers are mirror-like and EMPA data of the layers show sharp compositional transition at the interface between the epitaxial layer and the substrate. The effects of annealing in Hg over-pressure on the properties of the as-grown layers were also investigated in the temperature range of 250−400 °C. By annealing at the temperature of 400 °C, a compositional change near the interface is observed. Contrary to this, without apparent compositional change, well-behaved n-type layers are obtained by annealing in the 250−300 °C temperature range. Sequential growth of double heterostructure, Hg_l−xCd_xTe/Hg_l−yCd_yTe on a CdTe (111)A substrate was also demonstrated.     

Preparation and Thermoelectric Properties of Ag<Subscript>0.5</Subscript>In<Subscript>0.5−<Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript>5</Subscript>Sn<Subscript>4</Subscript>Te<Subscript>10</Subscript>

A series of compounds with composition Ag_0.5In_0.5−x Pb₅Sn₄Te₁₀ (x = 0.05 to 0.20) were prepared by slowly cooling the melts of the corresponding elements, and the effect of In content on the thermoelectric transport properties of these compounds has been investigated. Results indicate that the compounds’ electronic structure is sensitive to In content, and that the carrier concentration of these compounds at room temperature increases from 4.86 × 10¹⁸ cm⁻³ to 3.85 × 10²¹ cm⁻³ as x increases from 0.05 to 0.20. For these compounds, electrical conductivity decreases and Seebeck coefficient increases with increasing In content. Ag_0.05In_0.03Pb_0.5Sn_0.4Te₁₀ shows very low lattice thermal conductivity, and has a maximum dimensionless figure of merit ZT of 1.2 at 800 K.     

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.     

Influence of Substrate Temperature on Structural and Thermoelectric Properties of Antimony Telluride Thin Films Fabricated by RF and DC Cosputtering

Antimony and tellurium were deposited on BK7 glass using direct-current magnetron and radiofrequency magnetron cosputtering. Antimony telluride thermoelectric thin films were synthesized with a heated substrate. The effects of substrate temperature on the structure, surface morphology, and thermoelectric properties of the thin films were investigated. X-ray diffraction patterns revealed that the thin films were well crystallized. c-Axis preferred orientation was observed in thin films deposited above 250°C. Scanning electron microscopy images showed hexagonal crystallites and crystal grains of around 500 nm in thin film fabricated at 250°C. Energy-dispersive spectroscopy indicated that a temperature of 250°C resulted in stoichiometric Sb₂Te₃. Sb₂Te₃ thin film deposited at room temperature exhibited the maximum Seebeck coefficient of 190 μV/K and the lowest power factor (PF), S ² σ, of 8.75 × 10⁻⁵ W/mK². When the substrate temperature was 250°C, the PF increased to its highest value of 3.26 × 10⁻³ W/mK². The electrical conductivity and Seebeck coefficient of the thin film were 2.66 × 10⁵ S/m and 113 μV/K, respectively.     

Refractory metal boride ohmic contacts to P-type 6H-SiC

Ohmic contacts have been fabricated on p-type 6H-SiC (1.3×10¹⁹ cm⁻³) using CrB₂, W₂B, and TiB₂. The boride layers (∼100–200 nm) were sputter-deposited in a system with a base pressure of 3×10⁻⁷ Torr. Specific contact resistances were measured using the linear transmission line method, and the physical properties of the contacts were examined using Rutherford backscattering spectrometry. All as-deposited contacts exhibited rectifying characteristics. Ohmic behavior was observed following short anneals (2–10 min) at 1100°C and 5×10⁻⁷ Torr. Current-voltage characteristics were linear for CrB₂ and W₂B and quasi-linear for TiB₂. The lowest values of the specific contact resistance (r_c in Ω-cm²) measured at room temperature for CrB₂ and W₂B were 8.2×10⁻⁵ and 5.8×10⁻⁵, respectively. The specific contact resistance for TiB₂ was not determined accurately. Longer anneals (30 min for W₂B and 90 min for CrB₂) reduced the room temperature values of r_c to 6.1×10⁻⁵ for W₂B and 1.9×10⁻⁵ for CrB₂. Backscattering spectra revealed substantial concentrations of oxygen in all as-deposited boride films. The short anneal cycle removed the oxygen in the CrB₂ films and reduced the concentration substantially in the W₂B films; however, annealing had no affect on the oxygen concentration in the TiB₂ films. The CrB₂/SiC interface remained stable during annealing; i.e., Si and carbon were not observed in the boride layers after annealing. In contrast, W₂B and TiB₂ reacted with the SiC epilayers, and after annealing, Si and carbon were observed at the surface of each boride layer.     

Microstructure coarsening during static annealing of 60Sn40Pb solder joints: III intermetallic compound growth kientics

The growth of the total (Cu₃Sn+Cu₆Sn) intermetallic compound layer in Cu-60Sn40Pb solder joints during static annealing at 50°C to 150°C was described by the equation hi=h_o+A_o exp(−Q_a/RT)t^p with h_o=0–0.3 μm, p=0.38–0.70, A_o=1.9×10⁻⁴–3.4×10⁻⁴ m/s^p, and Q_a=25.5–30.9 kJ/mole. These constants are within the range of those obtained by others and give values of D_o and Q which are in reasonable accord with those for the diffusion coefficients in Cu₃Sn and Cu₆Sn₅ determined in diffusion couples. The deviation of the values of the time exponent p from the ideal of 0.5 for diffusion growth may be due to inaccuracies or errors pertaining to the measured thickness (especially h_o) and the complex nature of the diffusion process.     

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.     

Enhanced Thermoelectric Properties Obtained by Compositional Optimization in p-Type BixSb2?xTe3 Fabricated by Mechanical Alloying and Spark Plasma Sintering

Bi _x Sb_2−x Te₃ bulk alloys are known as the best p-type thermoelectric materials near room temperature. In this work, single-phase Bi _x Sb_2−x Te₃ (x = 0.2, 0.25, 0.3, 0.34, 0.38, 0.42, 0.46, and 0.5) alloys were prepared by spark plasma sintering (SPS) using mechanical alloying (MA)-derived powders. A small amount (0.1 vol.%) of SiC nanoparticles was added to improve the mechanical properties and to reduce the thermal conductivity of the alloys. The electrical resistivity decreases significantly with increasing ratio of Sb to Bi in spite of the weaker decreasing trend in Seebeck coefficient, whereby the power factor at 323 K reaches 3.14 × 10⁻³ W/mK² for a sample with x = 0.3, obviously higher than that at x = 0.5 (2.27 × 10⁻³ W/mK²), a composition commonly used for ingots. Higher thermal conductivities at low temperatures are obtained at the compositions with lower x values, but they tend to decrease with temperature. As a result, higher ZT values are obtained for Bi_0.3Sb_1.7Te₃, with a maximum ZT value of 1.23 at 423 K, about twice the ZT value (about 0.6) of Bi_0.5Sb_1.5Te₃ at the same temperature.     

Thin-Film Thermoelectric Module for Power Generator Applications Using a Screen-Printing Method

A new process for fabricating a low-cost thermoelectric module using a screen-printing method has been developed. Thermoelectric properties of screen-printed ZnSb films were investigated in an effort to develop a thermoelectric module with low cost per watt. The screen-printed Zn _x Sb_1−x films showed a low carrier concentration and high Seebeck coefficient when x was in the range of 0.5 to 0.57 and the annealing temperature was kept below 550°C. When the annealing temperature was higher than 550°C, the carrier concentration of the Zn _x Sb_1−x films reached that of a metal, leading to a decrease of the Seebeck coefficient. In the present experiment, the optimized carrier concentration of screen-printed ZnSb was 7 × 10¹⁸/cm³. The output voltage and power density of the ZnSb film were 10 mV and 0.17 mW/cm², respectively, at ΔT = 50 K. A thermoelectric module was produced using the proposed screen-printing approach with ZnSb and CoSb₃ as p-type and n-type thermoelectric materials, respectively, and copper as the pad metal.     

Two Layer Surface Exfoliation on Si3N4/Si by Sequential Implantation of He and H Ions

n-Type Si(100) wafers with a thermally grown Si₃N₄ layer (∼170 nm) were sequentially implanted with 160 keV He ions at a dose of 5 × 10¹⁶ cm⁻² and 110 keV H ions at a dose of 1 × 10¹⁶ cm⁻². Depending on the annealing temperature, surface exfoliations of two layers were observed by optical microscopy and atomic force microscopy. The first layer exfoliation was found to correspond to the top Si₃N₄ layer, which was produced at lower annealing temperatures. The other was ascribed to the implanted Si layer, which was formed at higher temperatures. The possible exfoliation processes are tentatively discussed, and potential applications of such phenomena are also suggested.     

Properties of Zn-doped P-type In0.53Ga0.47as grown by vapor phase epitaxy (VPE) on InP substrates

Electrical properties of Zn-doped, p-type In_0.53Ga_0.47As grown by the vapor phase epitaxy (VPE) technique are presented. High (p ∼ 4.0 × 10¹⁹ cm⁻³) p-type doping and low resistivity (ρ ∼ 2.8 × 10⁻³ Ωsu−cm) was obtained. These propertie's are useful in the formation of ohmic contacts in laser diodes and photodiodes fabricated from the quaternary and ternary alloy systems. A calibration curve for the non-destructive determination of carrier concentration from photoluminescence linewidths has been obtained.     

Effects of Double Substitution with Ge and Te on Thermoelectric Properties of a Skutterudite Compound

Studies have shown that the thermoelectric properties of CoSb₃ could be improved by the substitution of group IVB or VIB elements for Sb. However, the substitution volume is limited. To get a better picture of the substitution volume in view of thermoelectric properties, Ge and Te double-substituted skutterudite materials were prepared with the nominal composition of Co₄Sb _x Ge_5.9−0.5x Te_6.1−0.5x (x = 11, 10, 9, 8) by the traditional solid-state reaction method and spark plasma sintering, and Rietveld analysis was employed to refine the crystal structure. The results showed that the lattice parameter decreased linearly and the solubility limitations of group IVB and VIB elements were greatly alleviated by the Ge and Te codoping. Besides, the thermoelectric properties were analyzed through measurements of electrical and thermal conductivities as well as room-temperature electrical transport properties. The results showed that the substitution volume of Ge and Te could play an important role in the thermoelectric properties, and a minimum lattice thermal conductivity value of 1.56 W m⁻¹ K⁻¹ was obtained at around 673 K for Co₄Sb₈Ge_1.9Te_2.1. Co₄Sb₁₁Ge_0.4Te_0.6 achieved the best figure of merit of 0.89 at around 773 K, which was remarkably improved over that of untreated CoSb₃.     

Microgenerator Using BiSbTe-Pt Thermopile and Pt-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Ceramic Combustor

The performance of a microcombustor thermoelectric generator device based on a thermopile using p-type Bi_0.3Sb_1.7Te₃ (BST) and n-type Pt films has been investigated. The BST films were prepared by two different methods—pulsed laser deposition (PLD) and sputter deposition—on Si₃N₄/SiO₂ multilayers on Si substrate. The ceramic catalyst combustor was patterned on the thermopile end on a thin membrane fabricated by back-side bulk etching of the silicon substrate. At 138°C the thermoelectric power factors of the PLD and sputter-deposited films were 3.6 × 10⁻³ W/mK² and 0.22 × 10⁻³ W/mK², respectively. The power from the generator with the sputter-deposited film was 0.343 μW, which was superior to that of the device with the PLD film, which provided 0.1 μW, for combustion of a 200 sccm flow of 3 v/v% hydrogen in air.     

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.     

Plasma anodization of evaporated Al-InP systems

Aluminium oxide-InP structures were fabricated by plasma anodization of evaporated Al-InP systems with intention of fabricating InP MISFETS. It was found that the resistivity and break-down strength of the A1₂O₃ film were influenced by the selection of the end point of the anodization. At appropriate conditions the resistivity of 5 × 10¹⁰ − 10¹²Ω cm for the anodic Al₂O₃ and the minimum density of the interface trap states of 4 × 10¹¹ cm⁻² ev⁻¹ for Al₂ O₃ -InP systems were obtained.     

Interface Microstructure and Performance of Sb Contacts in Bismuth Telluride-Based Thermoelectric Elements

A thermoelectric joint composed of p-type Bi_0.5Sb_1.5Te₃ (BiSbTe) material and an antimony (Sb) interlayer was fabricated by spark plasma sintering. The reliability of the thermoelectric joints was investigated using electron probe microanalysis for samples with different accelerated isothermal aging time. After aging for 30 days at 300°C in vacuum, the thickness of the diffusion layer at the BiSbTe/Sb interface was about 30 μm, and Sb₂Te₃ was identified to be the major interfacial compound by element analysis. The contact resistivity was 3 × 10^?6 ohm cm² before aging and increased to 8.5 × 10^?6 ohm cm² after aging for 30 days at 300°C, an increase associated with the thickness of the interfacial compound. This contact resistivity is very small compared with that of samples with solder alloys as the interlayer. In addition, we have also investigated the interface behavior of Sb layers integrated with n-type Bi₂Se_0.3Te_2.7 (BiSeTe) material, and obtained similar results as for the p-type semiconductor. The present study suggests that Sb may be useful as a new interlayer material for bismuth telluride-based power generation devices.     

Efficient Outdiffusion of Hydrogen from Mg-Doped Nitrides by NF<Subscript>3</Subscript> Annealing

High concentration (more than 1 × 10¹⁸ cm⁻³) of hydrogen atoms remaining in Mg-doped GaN epitaxial layers grown by metalorganic chemical vapor deposition even after conventional annealing in N₂ ambient could induce degradation in GaN-based devices containing Mg-doped layers. In this study, by annealing Mg-doped nitrides in NF₃ ambient, we successfully reduced residual hydrogen below mid-10¹⁷ cm⁻³, which is much smaller than by N₂ annealing. NF₃ annealing enhances outdiffusion of hydrogen from the bulk, which is possibly because the nitrogen and fluorine radicals decomposed from NF₃ accelerate desorption of hydrogen adatoms from the surface. The proposed method for Mg activation would improve the reliability of GaN-based light-emitting diodes and laser diodes.     

N-Type Hg1−xCdxTe: Undoped x = 0.3 LPE material for sprite IR detectors

The requirement for two color Sprite detectors, with elements sensitive in the ranges 3-5 μn (MW) and 8-14 μn (LW) at 77K, is met using Hg_1−xCd_xTe elements of composition x = 0.3 and x = 0.2, respectively. The need for low defect levels for increased performance indicates the use of liquid phase epitaxy (LPE). While LW material is fairly well characterized, the growth and conversion to n-type of MW LPE has proved more difficult. Reported work shows limited data and limited success in converting MW LPE to n-type, and this primarily in donor-doped material. This paper describes the growth, annealing to n-type and characterization of Hg_0.7Cd_0.3Te. High n-type conversion yields were obtained, with low donor levels (mid-10¹³ to mid-10¹⁴ cm⁻³), high mobility (>10⁴ cm² (Vs)⁻¹) and long minority carrier lifetime (>10 us).     

Effect of Rapid Thermal Annealing on Sputtered CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> Thin Films

Calcium copper titanium oxide (CaCu₃Ti₄O₁₂, abbreviated to CCTO) films were deposited on Pt/Ti/SiO₂/Si substrates at room temperature (RT) by radiofrequency magnetron sputtering. As-deposited CCTO films were treated by rapid thermal annealing (RTA) at various temperatures and in various atmospheres. X-ray diffraction patterns and scanning electron microscope (SEM) images demonstrated that the crystalline structures and surface morphologies of CCTO thin films were sensitive to the annealing temperature and ambient atmosphere. Polycrystalline CCTO films could be obtained when the annealing temperature was 700°C in air, and the grain size increased signifi- cantly with annealing in O₂. The 0.8-μm CCTO thin film that was deposited at RT for 2 h and then annealed at 700°C in O₂ exhibited a high dielectric constant (ε′) of 410, a dielectric loss (tan δ) of 0.17 (at 10 kHz), and a leakage current density (J) of 1.28 × 10⁻⁵ A/cm² (at 25 kV/cm).