Power Factor Anisotropy of <Emphasis Type="Italic">p</Emphasis>-Type and <Emphasis Type="Italic">n</Emphasis>-Type Conductive Thermoelectric Bi-Sb-Te Thin Films

The best films for thermoelectric applications near room temperature are based on the compounds Bi₂Te₃, Sb₂Te₃, and Bi₂Se₃, which as single crystals have distinct anisotropy in their electrical conductivity σ regarding the trigonal c-axis, whereas the Seebeck coefficient S is nearly isotropic. For p- and n-type alloys, P _⊥c > P _||c, and the power factors P _⊥c of single crystals are always higher compared with polycrystalline films, where the power factor is defined as P = S ² σ, ⊥c and ||c are the direction perpendicular and parallel to the c-axis, respectively. For the first time in sputter-deposited p-type (Bi_0.15Sb_0.85)₂Te₃ and n-type Bi₂(Te_0.9Se_0.1)₃ thin films, the anisotropy of the electrical conductivity has been measured directly as it depends on the angle φ between the electrical current and the preferential orientation of the polycrystals (texture) using a standard four-probe method. The graphs of σ(φ) show the expected behavior, which can be described by a weighted mixture of σ _⊥c and σ _||c contributions. Because (σ _⊥c/σ _||c) _p  < (σ _⊥c/σ _||c) _n , the n-type films have stronger anisotropy than the p-type films. For this reason, the angular weighted contributions of P _||c lead to a larger drop in the power factor of polycrystalline n-type films compared with p-type films.     

Effects of Cooling Rate on Thermoelectric Properties of <Emphasis Type="Italic">n</Emphasis>-Type Bi<Subscript>2</Subscript>(Se<Subscript>0.4</Subscript>Te<Subscript>0.6</Subscript>)<Subscript>3</Subscript> Compounds

A series of Bi₂(Se_0.4Te_0.6)₃ compounds were synthesized by a rapid route of melt spinning (MS) combined with a subsequent spark plasma sintering (SPS) process. Measurements of the Seebeck coefficient, electrical conductivity, and thermal conductivity were performed over the temperature range from 300 K to 520 K. The measurement results showed that the cooling rate of melt spinning had a significant impact on the transport properties of electrons and phonons, effectively enhancing the thermoelectric properties of the compounds. The maximum ZT value reached 0.93 at 460 K for the sample prepared with the highest cooling rate, and infrared spectrum measurement results showed that the compound with lower tellurium content, Bi₂(Se_0.4Te_0.6)₃, possesses a larger optical forbidden gap (E _g) compared with the traditional n-type zone-melted material with formula Bi₂(Se_0.07Te_0.93)₃. Our work provides a new approach to develop low-tellurium-bearing Bi₂Te₃-based compounds with good thermoelectric performance.     

Influence of Nanoinclusions on Thermoelectric Properties of <Emphasis Type="Italic">n</Emphasis>-Type Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> Nanocomposites

n-Type Bi₂Te₃ nanocomposites with enhanced figure of merit, ZT, were fabricated by a simple, high-throughput method of mixing nanostructured Bi₂Te₃ particles obtained through melt spinning with micron-sized particles. Moderately high power factors were retained, while the thermal conductivity of the nanocomposites was found to decrease with increasing weight percent of nanoinclusions. The peak ZT values for all the nanocomposites were above 1.1, and the maximum shifted to higher temperature with increasing amount of nanoinclusions. A maximum ZT of 1.18 at 42°C was obtained for the 10 wt.% nanocomposite, which is a 43% increase over the bulk sample at the same temperature. This is the highest ZT reported for n-type Bi₂Te₃ binary material, and higher ZT values are expected if state-of-the-art Bi₂Te_3−x Se _x materials are used.     

Electrodeposition of <Emphasis Type="Italic">p</Emphasis>-Type Sb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Te<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript> Thermoelectric Films

Thermoelectric Sb _x Te _y films were potentiostatically electrodeposited in aqueous nitric acid electrolyte solutions containing different concentrations of TeO₂. Stoichiometric Sb _x Te _y films were obtained by applying a voltage of −0.15 V versus saturated calomel electrode (SCE) using a solution consisting of 2.4 mM TeO₂, 0.8 mM Sb₂O₃, 33 mM tartaric acid, and 1 M HNO₃. The nearly stoichiometric Sb₂Te₃ films had a rhombohedral structure, R[`3]m R\bar{3}m , with a preferred orientation along the (015) direction. The films had hole concentration of 5.8 × 10¹⁸/cm³ and exhibited mobility of 54.8 cm²/Vs. A more negative potential resulted in higher Sb content in the deposited Sb _x Te _y films. Furthermore, it was observed that the hole concentration and mobility decreased with increasingly negative deposition potential, and eventually showed insulating properties, possibly due to increased defect formation. The absolute value of the Seebeck coefficient of the as-deposited Sb₂Te₃ thin film at room temperature was 118 μV/K.     

Improved Thermoelectric Performance of <Emphasis Type="Italic">p</Emphasis>-Type Bismuth Antimony Telluride Bulk Alloys Prepared by Hot Forging

The thermoelectric (TE) performance of Bi_0.5Sb_1.5Te₃ polycrystalline alloys has been improved by a simple hot-forging process. No obvious texture was observed in the x-ray diffraction (XRD) patterns of the hot-forged samples. Transport property measurements indicated that the hot-forged samples possessed extremely low thermal conductivities. A maximum ZT value of ∼1.1 at room temperature was obtained for the sample forged under 30 MPa pressure, being almost 50% more than that of the initial unforged alloy. High-resolution transmission electron microscopy (HRTEM) observations suggested that the high density of lattice defects of the hot-forged samples could be responsible for the extremely low thermal conductivities.     

Influence of Element Substitution on Corrosion Behavior of Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Based Compounds

Atmospheric water may condense on the surface of Bi₂Te₃-based compounds constituting the Peltier module, depending on the operating environment used. In the stage of disposal, Bi₂Te₃-based compounds may come into contact with water in waste disposal sites. There are very few publications about the influence of condensed water on Peltier modules. Bi₂Te₃-Sb₂Te₃ or Bi₂Te₃-Bi₂Se₃ pseudo binary system compounds are used as p-type material or n-type material, respectively. The lattice distortion will be induced in the crystal of Bi₂Te₃-based compounds by element substitution due to the reduction in their thermal conductivity. However, the influence of element substitution on the corrosion behavior of Bi₂Te₃-based compounds remains unclear. In this study, the influence of element substitution on the corrosion behavior of Bi₂Te₃-based compounds with practical compositions has been investigated. Bi_0.5Sb_1.5Te₃ or Bi₂Te_2.85Se_0.15 was prepared by the vertical Bridgman method. The electrochemical properties at room temperature were evaluated by cyclic voltammetry in a standard three-electrode cell. The working electrolyte was a naturally aerated 0.6 or 3.0 mass% NaCl solution. From the tendency for corrosion potential for all the samples, the corrosion sensitivity of ternary compounds was slightly higher than that of binary compounds. From the trend of current density, it was found that Bi_0.5Sb_1.5Te₃ had a corrosion resistance intermediate between Bi₂Te₃ and Sb₂Te₃. On the other hand, corrosion resistance was affected despite a small amount of Se substitution, and the corrosion resistance of Bi₂Te_2.85Se_0.15 was close to or lower than that of Bi₂Se₃. From the observation results of the corrosion products, the trends of morphology and composition of corrosion products for Bi_0.5Sb_1.5Te₃ or Bi₂Te_2.85Se_0.15 were consistent with those of Sb₂Te₃ or Bi₂Se₃, respectively. From the results of x-ray photoelectron spectroscopy for the electrolyte after testing, the possibility that a corrosion product diffuses to the environment including the salt was suggested in Bi_0.5Sb_1.5Te₃. However, the amount of dissolved corrosion product was very low, and the chemical stability of the corrosion product was not changed or improved by element substitution.     

Thermoelectric Characteristics of <Emphasis Type="Italic">p</Emphasis>-Type (Bi,Sb)<Subscript>2</Subscript>Te<Subscript>3</Subscript>/(Pb,Sn)Te Functional Gradient Materials with Variation of the Segment Ratio

The p-type (Bi,Sb)₂Te₃/(Pb,Sn)Te functional gradient materials (FGMs) were fabricated by hot-pressing mechanically alloyed (Bi_0.2Sb_0.8)₂Te₃ and 0.5 at.% Na₂Te-doped (Pb_0.7Sn_0.3)Te powders together at 500°C for 1 h in vacuum. Segment ratios of (Bi,Sb)₂Te₃ to (Pb,Sn)Te were varied as 3:1, 1.3:1, and 1:1.6. A reaction layer of about 350-μm thickness was formed at the (Bi,Sb)₂Te₃/(Pb,Sn)Te FGM interface. Under temperature differences larger than 340°C applied across a specimen, superior figures of merit were predicted for the (Bi,Sb)₂Te₃/(Pb,Sn)Te FGMs to those of (Bi_0.2Sb_0.8)₂Te₃ and (Pb_0.7Sn_0.3)Te. With a temperature difference of 320°C applied across a specimen, the (Bi,Sb)₂Te₃/(Pb,Sn)Te FGMs with segment ratios of 3:1 and 1.3:1 exhibited the maximum output powers of 72.1 mW and 72.6 mW, respectively, larger than the 63.9 mW of (Bi_0.2Sb_0.8)₂Te₃ and the 26 mW of 0.5 at.% Na₂Te-doped (Pb_0.7Sn_0.3)Te.     

Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript>-Sb<Subscript>2</Subscript>Te<Subscript>3</Subscript> Superlattices Grown by Nanoalloying

In this work, Bi₂Te₃-Sb₂Te₃ superlattices were prepared by the nanoalloying approach. Very thin layers of Bi, Sb, and Te were deposited on cold substrates, rebuilding the crystal structure of V₂VI₃ compounds. Nanoalloyed super- lattices consisting of alternating Bi₂Te₃ and Sb₂Te₃ layers were grown with a thickness of 9 nm for the individual layers. The as-grown layers were annealed under different conditions to optimize the thermoelectric parameters. The obtained layers were investigated in their as-grown and annealed states using x-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive x-ray (EDX) spectroscopy, transmission electron microscopy (TEM), and electrical measurements. A lower limit of the elemental layer thickness was found to have c-orientation. Pure nanoalloyed Sb₂Te₃ layers were p-type as expected; however, it was impossible to synthesize p-type Bi₂Te₃ layers. Hence the Bi₂Te₃-Sb₂Te₃ superlattices consisting of alternating n- and p-type layers showed poor thermoelectric properties.     

Thermoelectric Properties of <Emphasis Type="Italic">n</Emphasis>-Type Multiple-Filled Skutterudites

Filled skutterudites are prospective intermediate temperature materials for␣thermoelectric power generation. CoSb₃-based n-type filled skutterudites have good electrical transport properties with power factor values over 40 μW/cm K² at elevated temperatures. Filling multiple fillers into the crystallographic voids of skutterudites would help scatter a broad range of lattice phonons, thus resulting in lower lattice thermal conductivity values. We report the thermoelectric properties of n-type multiple-filled skutterudites between 5 K and 800 K. The combination of different fillers inside the voids of the skutterudite structure shows enhanced phonon scattering, and consequently a strong suppression of the lattice thermal conductivity. Very good power factor values are achieved in multiple-filled skutterudite compared with single-element-filled materials. The dimensionless thermoelectric figure of merit for n-type filled skutterudites is improved through multiple-filling in a wide temperature range.     

Features of the Behavior of the Figure of Merit for <Emphasis Type="Italic">p</Emphasis>-Type Solid Solutions Based on Bismuth and Antimony Chalcogenides

Thermoelectric and galvanomagnetic properties of p-type solid solutions based on bismuth and antimony chalcogenides (Bi,Sb)₂(Te,Se)₃ have been studied to analyze the features of the figure of merit Z. The increase of Z and ZT for the p-Bi_2−x Sb _x Te₃ composition at x = 1.6 in the temperature interval of 370 K to 550 K was shown to be defined by the increase of the density-of-states effective mass, the slope of the temperature dependence of the carrier mobility, and the reduction of the lattice thermal conductivity for optimal charge carrier concentration. High carrier mobility and low lattice thermal conductivity provide the increase of Z and ZT in the p-Bi_2−x Sb _x Te_3−y Se _y (x = 1.3, y = 0.06) solid solution in the interval from 300 K to 370 K. The growth of Z in these compositions is determined by the increase of the compression of the constant-energy ellipsoids along binary and bisector directions, and by the change of the tilt angle Θ between the principal axes of the ellipsoids and the crystallographic axes.     

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.     

Micro- and Nano-Technology: A Critical Design Key in Advanced Thermoelectric Cooling Systems

Advanced thermoelectric (TE) cooling technologies are now receiving more research attention, to provide cooling in advanced vehicles and residential systems to assist in increasing overall system energy efficiency and reduce the impact of greenhouse gases from leakage by current R-134a systems. This work explores the systems-related impacts, barriers, and challenges of using micro-technology solutions integrated with advances in nano-scale thermoelectric materials in advanced TE cooling systems. Integrated system-level analyses that simultaneously account for thermal energy transport into and dissipation out of the TE device, environmental effects, temperature- dependent TE and thermo-physical properties, thermal losses, and thermal and electrical contact resistances are presented, to establish accurate optimum system designs using both p-type nanocrystalline-powder-based (NPB) Bi _x Sb_2−x Te₃/n-type Bi₂Te₃-Bi₂Se₃ TE systems and conventional p-type Bi₂Te₃-Sb₂Te₃/n-type Bi₂Te₃-Bi₂Se₃ TE systems. This work established the design trends and identified optimum design regimes and metrics for these types of systems that will minimize system mass, volume, and cost to maximize their commercialization potential in vehicular and residential applications. The relationships between important design metrics, such as coefficient of performance, specific cooling capacity, and cooling heat flux requirements, upper limits, and critical differences in these metrics in p-type NPB Bi _x Sb_2−x Te₃/ n-type Bi₂Te₃-Bi₂Se₃ TE systems and p-type Bi₂Te₃-Sb₂Te₃/n-type Bi₂Te₃-Bi₂Se₃ TE systems, are explored and quantified. Finally, the work discusses the critical role that micro-technologies and nano-technologies can play in enabling miniature TE cooling systems in advanced vehicle and residential applications and gives some key relevant examples. Pacific Northwest National Laboratory—operated for the U.S. Department of Energy by Battelle Memorial Institute under contract DE-AC05-76RLO1830.     

Electrical and photoelectric properties of <Emphasis Type="Italic">n</Emphasis>-TiN/<Emphasis Type="Italic">p</Emphasis>-Hg<Subscript>3</Subscript>In<Subscript>2</Subscript>Te<Subscript>6</Subscript> heterostructures

n-TiN/p-Hg₃In₂Te₆ heterostructures are fabricated by depositing a thin n-type titanium nitride (TiN) film onto prepared p-type Hg₃In₂Te₆ plates using reactive magnetron sputtering. Their electrical and photoelectric properties are studied. Dominant charge-transport mechanisms under forward bias are analyzed within tunneling-recombination and tunneling models. The fabricated n-TiN/p-Hg₃In₂Te₆ structures have the following photoelectric parameters at an illumination intensity of 80 mW/cm²: the open-circuit voltage is V_OC = 0.52 V, the short-circuit current is I_SC = 0.265 mA/cm², and the fill factor is FF = 0.39.     

A DLTS study of 4<Emphasis Type="Italic">H</Emphasis>-SiC-based <Emphasis Type="Italic">p</Emphasis>-<Emphasis Type="Italic">n</Emphasis> junctions fabricated by boron implantation

Deep-level transient spectroscopy (DLTS) has been used to study p-n junctions fabricated by implantation of boron into epitaxial 4H-SiC films with n-type conductivity and the donor concentration (8–9) × 10¹⁴ cm⁻³. A DLTS signal anomalous in sign is observed; this signal is related to recharging of deep compensating boron-involved centers in the n-type region near the metallurgical boundary of the p-n junction.     

Features of the charge-transport mechanism in layered Bi<Subscript>2</Subscript>Te<Subscript>3</Subscript> single crystals doped with chlorine and terbium

The temperature dependences (T = 5−300 K) of the resistivity in the plane of layers and in the direction perpendicular to the layers, as well as the Hall effect and the magnetoresistance (H < 80 kOe, T = 0.5−4.2 K) in Bi₂Te₃ single crystals doped with chlorine and terbium, are investigated. It is shown that the doping of Bi₂Te₃ with terbium atoms results in p-type conductivity and in increasing hole concentration. The doping of Bi₂Te₃ with chlorine atoms modifies also the character of its conductivity instead of changing only the type from p to n. In the temperature dependence of the resistivity in the direction perpendicular to layers, a portion arises with the activation conductivity caused by the hopping between localized states. The charge-transport mechanism in Bi₂Te₃ single crystals doped with chlorine is proposed.     

Thermoelectric Properties of <Emphasis Type="Italic">p</Emphasis>-Type Mg<Subscript>2.00</Subscript>Si<Subscript>0.25</Subscript>Sn<Subscript>0.75</Subscript> with Li and Ag Double Doping

Mg₂Si_1−x Sn _x -system solid solutions are ecofriendly semiconductors that are promising materials for thermoelectric generators in the middle temperature range. To produce a thermoelectric device, high-performance p- and n-type materials must be balanced. In this paper, p-type Mg_2.00Si_0.25Sn_0.75 with Li and Ag double doping was prepared by the liquid–solid reaction method and hot-pressing. Effects of Li and Ag double doping on thermoelectric properties were investigated in the temperature range from room temperature to 850 K. All sintered compacts were identified as single-phase solid solutions with anti-fluorite structure. The carrier concentration increased with the double doping. The temperature dependence of resistivity of the double-doped samples was similar to that of a metal. The seebeck coefficient increased with temperature to a maximum value and then decreased in the intrinsic region. Thermal conductivity decreased linearly with increasing temperature, reaching a minimum near the intrinsic region, and then increased rapidly because of the contribution of the bipolar component. The dimensionless figure of merit reached 0.32 at 610 K for Mg_2.00Si_0.25Sn_0.75 double-doped with Li-5000 ppm and Ag-20000 ppm.     

Microstructure and Thermoelectric Properties of <Emphasis Type="Italic">n</Emphasis>- and <Emphasis Type="Italic">p</Emphasis>-Type Doped Mg<Subscript>2</Subscript>Sn Compounds Prepared by the Modified Bridgman Method

Mg₂Sn compounds were prepared by the modified vertical Bridgman method, and were doped with Bi and Ag to obtain n- and p-type materials, respectively. Excess Mg was also added to some of the ingots to compensate for the loss of Mg during the preparation process. The Mg₂Sn samples were characterized by x-ray diffraction (XRD) and scanning electron microscopy (SEM), and their power factors were calculated from the Seebeck coefficient and electrical conductivity, measured from 80 K to 700 K. The sample prepared with 4% excess Mg, which contains a small amount of Mg₂Sn + Mg eutectic phase, had the highest power factor of 12 × 10⁻³ W m⁻¹ K⁻² at 115 K, while the sample doped with 2% Ag, in which a small amount of eutectics also exists, has a power factor of 4 × 10⁻³ W m⁻¹ K⁻² at 420 K.     

Thermoelectric Behavior of Sb- and Al-Doped <Emphasis Type="Italic">n</Emphasis>-Type Mg<Subscript>2</Subscript>Si Device Under Large Temperature Differences

The thermoelectric (TE) characteristics of Sb- and Al-doped n-type Mg₂Si elemental devices fabricated using material produced from molten commercial doped polycrystalline Mg₂Si were examined. The TE devices were prepared using a plasma-activated sintering (PAS) technique. To complete the devices, Ni electrodes were fabricated on each end of them during the sintering process. To realize durable devices for large temperature differences, thermodynamically stable Sb-doped Mg₂Si (Sb-Mg₂Si) was exposed to the higher temperature and Al-doped Mg₂Si (Al-Mg₂Si) was exposed to the cooler temperature. The devices consisted of segments of Sb-Mg₂Si and Al-Mg₂Si with sizes in the following ratios: Sb-Mg₂Si:Al-Mg₂Si = 4:1, 1:1, and 1:4. A device specimen composed solely of Sb-Mg₂Si showed no notable deterioration even after aging for 1000 h, while some segmented specimens, such as those with Sb-Mg₂Si:Al-Mg₂Si = 1:1 and 1:4, suffered from a considerable drop in output current over the large ΔT range. The observed power generated by specimens with Sb-Mg₂Si:Al-Mg₂Si = 1:1 and 1:4 and sizes of 2 mm × 2 mm × 10 mm were 50.7 mW and 49.5 mW, respectively, with higher and lower temperatures of 873 K and 373 K, respectively. For the sample composed solely of Sb-Mg₂Si, a power of 55 mW was demonstrated. An aging test for up to 1000 h for the same ΔT range indicated drops in output power of between ∼3% and 20%.     

Preparation and Thermoelectric Properties of LaGd<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>3</Subscript> and SmGd<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>3</Subscript>

Thermoelectric materials are attractive since they can recover waste heat directly in the form of electricity. In this study, the thermoelectric properties of ternary rare-earth sulfides LaGd_1+x S₃ (x = 0.00 to 0.03) and SmGd_1+x S₃ (x = 0.00 to 0.06) were investigated over the temperature range of 300 K to 953 K. These sulfides were prepared by CS₂ sulfurization, and samples were consolidated by pressure-assisted sintering to obtain dense compacts. The sintered compacts of LaGd_1+x S₃ were n-type metal-like conductors with a thermal conductivity of less than 1.7 W K⁻¹ m⁻¹. Their thermoelectric figure of merit ZT was improved by tuning the chemical composition (self-doping). The optimized ZT value of 0.4 was obtained in LaGd_1.02S₃ at 953 K. The sintered compacts of SmGd_1+x S₃ were n-type hopping conductors with a thermal conductivity of less than 0.8 W K⁻¹ m⁻¹. Their ZT value increased significantly with temperature. In SmGd_1+x S₃, the ZT value of 0.3 was attained at 953 K.