High thermoelectric figures of merit in PbTe quantum wells

High-quality Pb_1−xEu_xTe/PbTe multiple quantum wells (MQWs) have been grown by molecular beam epitaxy. The measured 300K thermoelectric properties have been compared with that of the best bulk PbTe. This experimental investigation is the first detailed study of MQW structures designed to improve ZT of thermoelectric materials and has resulted in a breakthrough in the decades-long ZT ≅ 1 barrier for a room-temperature thermoelectric material. A value of Z_2DT >1.2 has been achieved for these PbTe quantum wells.     

Nanostructured thermoelectric materials

High values of thermoelectric figures of merit ZT, ranging from ZT=1.6 at 300 K to ZT=3 at 550 K, are reported for Bi-doped n-type PbSeTe/PbTe quantum-dot superlattice (QDSL) samples grown by molecular beam epitaxy (MBE). These ZT values were determined by directly measuring Seebeck coefficients and electrical conductivities and using the low lattice thermal conductivity value (∼3.3 mW/cm-K) determined experimentally from measurements of a one-legged thermoelectric cooler. Initial experiments have also shown that high values of ZT (∼1.1 at 300 K) are achievable for complementary Na-doped p-type PbSeTe/PbTe QDSL samples, in which the conduction and valence bands mirror those in the Bi-doped Pb chalcogenides.     

Effect of Ce-Doping on Thermoelectric Properties in PbTe Alloys Prepared by Spark Plasma Sintering

Ce-doped Pb_1−x Ce _x Te alloys with x = 0, 0.005, 0.01, 0.015, 0.03, and 0.05 were prepared by induction melting, ball milling, and spark plasma sintering techniques. The structure and thermoelectric properties of the samples were investigated. X-ray diffraction (XRD) analysis indicated that the samples were of single phase with NaCl-type structure for x less than 0.03. The lattice parameter a increases with increasing Ce content. The lower Ce-doped samples (x = 0.005 and 0.01) showed p-type conduction, whereas the pure PbTe and the higher doped samples (x = 0, 0.015, 0.03, and 0.05) showed n-type conduction. The lower Ce-doped samples exhibited a much higher absolute Seebeck coefficient, but the higher electrical resistivity and higher thermal conductivity compared with pure PbTe resulted in a lower figure of merit ZT. In contrast, the higher Ce-doped samples exhibited a lower electrical resistivity, together with a lower absolute Seebeck coefficient and comparable thermal conductivity, leading to ZT comparable to that of PbTe. The lowest thermal conductivity (range from 0.99 W m⁻¹ K⁻¹ at 300 K to 0.696 W m⁻¹ K⁻¹ at 473 K) was found in the alloy Pb_0.95Ce_0.05Te due to the presence of the secondary phases, leading to a ZT higher than that of pure PbTe above 500 K. The maximum figure of merit ZT, in the alloy Pb_0.95Ce_0.05Te, was 0.88 at 673 K.     

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.     

Thermoelectric Properties and Electronic Structure of Bi- and Ag-Doped Mg<Subscript>2</Subscript>Si<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Ge<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Compounds

Mg₂Si_1−x Ge _x compounds were prepared from pure elements by melting in tantalum crucibles. The reaction was conducted under an inert gas in a special laboratory setup. Samples for thermoelectric measurements were formed by hot pressing. Structure and phase composition of the obtained materials were investigated by x-ray diffraction (XRD). Morphology and chemical composition were examined by scanning electron microscopy (SEM) and energy-dispersive x-ray spectroscopy (EDS), respectively. Thermoelectric properties, i.e., the Seebeck coefficient, the electrical conductivity, and the thermal conductivity, were measured in the temperature range of 500 K to 900 K. The effect of Bi and Ag doping on the thermoelectric performance of Mg-Si-Ge ternary compounds was investigated. The electronic structures of binary compounds were calculated using the Korringa–Kohn–Rostoker (KKR) method. The effects of disorder, including Ge substitution and Bi or Ag doping, were accounted for in the KKR method with coherent potential approximation calculations. The thermoelectric properties of doped Mg₂Si_1−x Ge _x are discussed with reference to computed density of states as well as the complex energy band structure.     

Thermoelectric Characteristics in MBE-Grown HgCdTe-Based Superlattices

We present a study on the thermoelectric properties of n-type Hg_0.75Cd_0.25 Te/Hg_0.7Cd_0.3Te superlattices (SLs). This material system was chosen because HgCdTe is the primary material used in high-performance infrared imaging applications. HgCdTe-based devices can be directly grown on Hg_1−x Cd _x Te/Hg_1−y Cd _y Te SL coolers using advanced growth methods such as molecular-beam epitaxy (MBE), making the monolithic integration of infrared sensors and thermoelectric elements possible. Also, the thermoelectric figure of merit ZT for Hg_0.75Cd_0.25Te/Hg_0.7Cd_0.3Te SLs is predicted to reach values of 2.09, more than two times greater than that achieved in the best thermoelectric devices based on bulk Bi₂Te₃. This large ZT is due to the unique and superior electrical and thermal properties of the HgCdTe system, which has not yet been experimentally explored in any great depth as a thermoelectric material. We used a Riber 32P MBE system equipped with a Hg valved cell, reflection high-energy electron diffraction, infrared pyrometer and in situ spectroscopic ellipsometry to grow the thermoelectric structures. MBE was chosen as a growth technique since it allows for the lowest growth temperature compared with other methods, which limits interdiffusion at the interfaces, thereby allowing for a precise control over electrical and thermal properties. Thermal devices were fabricated using standard photolithography and etching techniques. Thermal properties were evaluated using a differential technique. A thermal conductivity of 0.82 ± 0.07 W/m K and a Seebeck coefficient of 811 ± 150 μV/K were measured. Using a measured value of 0.017 Ω cm for the resistivity, an upper bound ZT of 1.4 is estimated. An erratum to this article can be found at     

Development of (Bi,Sb)<Subscript>2</Subscript>(Te,Se)<Subscript>3</Subscript>-Based Thermoelectric Modules by a Screen-Printing Process

In major applications, optimal power will be achieved when thermoelectric films are at least 100 μm thick. In this paper we demonstrate that screen-printing is an ideal method to deposit around 100 μm of (Bi,Sb)₂(Te,Se)₃-based films on a rigid or flexible substrate with high Seebeck coefficient value (90 μV K⁻¹ to 160 μV K⁻¹) using a low-temperature process. Conductive films have been obtained after laser annealing and led to acceptable thermoelectric performance with a power factor of 0.06 μW K⁻² cm⁻¹. While these initial material properties are not at the level of bulk materials, the complete manufacturing process is cost-effective, compatible with large surfaces, and affords a mass-production technique.     

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.     

Thermoelectric Properties of In<Subscript>0.3</Subscript>Ga<Subscript>0.7</Subscript>N Alloys

We report on the experimental investigation of the potential of InGaN alloys as thermoelectric (TE) materials. We have grown undoped and Si-doped In_0.3Ga_0.7N alloys by metalorganic chemical vapor deposition and measured the Seebeck coefficient and electrical conductivity of the grown films with the aim of maximizing the power factor (P). It was found that P decreases as electron concentration (n) increases. The maximum value for P was found to be 7.3 × 10⁻⁴ W/m K² at 750 K in an undoped sample with corresponding values of Seebeck coefficient and electrical conductivity of 280 μV/K and 93␣(Ω cm)⁻¹, respectively. Further enhancement in P is expected by improving the InGaN material quality and conductivity control by reducing background electron concentration.     

Electronic Structure and Thermoelectric Properties of Al-Mn-Fe-Si Alloys

In order to develop practical thermoelectric materials consisting solely of environmentally friendly elements, we investigated the thermoelectric properties of the Al₁₀Mn₃-type (P6₃/mmc, hp26) Al_77−x Mn₂₃Si _x alloys and the Al₁₀₂Mn₂₄Si₁₂-type (Pm-3, cP138) Al_82−x Mn_5.5Fe_12.5Si _x alloys, both of which possess a pseudogap at the Fermi level. The formation range in which the single phase is obtained was determined for these two phases. The electrical resistivity, Seebeck coefficient, and thermal conductivity of the samples involving no secondary phase were measured over the temperature range of 2 K to 300 K. It is found that the thermoelectric properties of these phases are qualitatively accounted for in terms of the pseudogap at the Fermi level in the electronic density of states and the disordering in local atomic arrangements.     

Synthesis and Characterization of <Emphasis Type="Italic">p</Emphasis>-Type Pb<Subscript>0.5</Subscript>Sn<Subscript>0.5</Subscript>Te Thermoelectric Power Generation Elements by Mechanical Alloying

A mechanical alloying (MA) process to transform elemental powders into solid Pb_0.5Sn_0.5Te with thermoelectric functionality comparable to melt-alloyed material is described. The room-temperature doping level and mobility as well as temperature-dependent electrical conductivity, Seebeck coefficient, and thermal conductivity are reported. Estimated values of lattice thermal conductivity (0.7 W m⁻¹ K⁻¹) are lower than some reports of functional melt-alloyed PbSnTe-based material, providing evidence that MA can engender the combination of properties resulting in highly functional thermoelectric material. Though doping level and Sn composition have not been optimized, this material exhibits a ZT value >0.5 at 550 K.     

Oscillatory Behavior of Thermoelectric Properties in <Emphasis Type="Italic">p</Emphasis>-PbTe Quantum Wells

The room-temperature dependences of the Seebeck coefficient, Hall coefficient, electrical conductivity, charge carrier mobility, and thermoelectric power factor were obtained as a function of thickness d (d = 8 nm to 400 nm) of PbTe epitaxial layers grown by thermal evaporation in vacuum of PbTe polycrystals doped with Na onto (100)KCl surfaces and covered with an Al₂O₃ layer. Distinct oscillations in the d-dependences of the properties were observed and attributed to the size quantization of the energy spectra in PbTe layers. The experimental values of the oscillation period are in good agreement with the results of theoretical calculations using the effective-mass approximation and a model for a rectangular potential well with infinitely high walls. It follows from the obtained results that quantization of the energy spectrum in PbTe thin-film structures occurs not only for the electron gas but also for the hole gas.     

Thermoelectric Properties of Heavily Doped <Emphasis Type="Italic">n</Emphasis>-Type SrTiO<Subscript>3</Subscript> Bulk Materials

Three Ta-doped strontium titanates were prepared as potential candidates for n-type thermoelectric oxides. The purity of the polycrystalline samples of SrTi_1−x Ta _x O₃ (x = 0.05 to 0.14) were characterized by means of powder x-ray diffraction and electron probe micro analysis (EPMA). We present the results of Seebeck coefficient, electrical conductivity, and thermal conductivity measurements performed at high temperatures.     

Thermoelectric Properties of Ca-Filled CoSb<Subscript>3</Subscript>-Based Skutterudites Synthesized by Mechanical Alloying

Ca _z Co_4−x (Fe/Mn) _x Sb₁₂ skutterudites were prepared by mechanical alloying and hot pressing. The phases of mechanically alloyed powders were identified as γ-CoSb₂ and Sb, but they were transformed to δ-CoSb₃ by annealing at 873 K for 100 h. All specimens had a positive Hall coefficient and Seebeck coefficient, indicating p-type conduction by holes as majority carriers. For the binary CoSb₃, the electrical conductivity behaved like a nondegenerate semiconductor, but Ca-filled and Fe/Mn-doped CoSb₃ showed a temperature dependence of a degenerate semiconductor. While the Seebeck coefficient of intrinsic CoSb₃ increased with temperature and reached a maximum at 623 K, the Seebeck coefficient increased with increasing temperature for the Ca-filled and Fe/Mn-doped specimens. Relatively low thermal conductivity was obtained because fine particles prepared by mechanical alloying lead to phonon scattering. The thermal conductivity was reduced by Ca filling and Fe/Mn doping. The electronic thermal conductivity was increased by Fe/Mn doping, but the lattice thermal conductivity was decreased by Ca filling. Reasonable thermoelectric figure-of-merit values were obtained for Ca-filled Co-rich p-type skutterudites.     

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.     

Preparation of Mg<Subscript>2</Subscript>Si<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Sn<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> by Induction Melting and Spark Plasma Sintering,and Thermoelectric Properties

Sn-doped, Mg₂Si_1−x Sn _x (x = 0 to 0.6) bulk alloys were prepared using Mg and Sn ingots as raw materials by suspended induction melting combined with the spark plasma sintering method, and the effects of Sn doping on thermoelectric transport properties were studied systematically. The results showed that Mg site vacancies caused by evaporation during the reaction process were filled by excess Mg addition (108 wt.% of the stoichiometric ratio of Mg₂Si). The resulting alloy samples were found to be single phase and relatively dense (above 98%). n-Type semiconducting characteristic of Sn-doped Mg₂Si_1−x Sn _x alloy was observed, and the electrical resistivity of all samples decreased with increasing temperature. The absolute Seebeck coefficient increased and the thermal conductivity was not changed significantly within the experimental Sn doping range. The dimensionless figure of merit (ZT) for Mg₂Si_0.4Sn_0.6 alloy reached its highest value of 0.25 at 400°C.     

Coherent Sb/CuTe Core/Shell Nanostructure with Large Strain Contrast Boosting the Thermoelectric Performance of n-Type PbTe

The exploration of n-type PbTe as thermoelectric materials always falls behind its p-type counterpart, mainly due to their quite different electronic band structure. In this work, elemental Sb and Cu₂Te are introduced into an n-type base material (PbTe)₈₁-Sb₂Te₃. The introduction of extra Sb can effectively tune the concentration of electrons; meanwhile, Sb precipitates can also scatter low-energy electrons (negatively contribute to the Seebeck coefficient) thus enhance the overall Seebeck coefficient. The added Cu₂Te is found to always co-precipitate with Sb, forming an interesting Sb/CuTe core/shell structure; moreover, the interface between core/shell precipitates and PbTe matrix simultaneously shows coherent lattice and strong strain contrast, beneficial for electron transport but adverse to phonon transport. Eventually, a peak figure of merit ZT_max  ≈  1.6 @ 823K and simultaneously an average ZT  ≈  1.0 (323–823 K) are realized in the (PbTe)₈₁Sb₂Te₃-0.6Sb-2Cu₂Te sample, representing the state of the art for n-type PbTe-based thermoelectric materials. Moreover, for the first time the three existing forms of Cu atoms in Cu₂Te alloyed PbTe are unambiguously clarified with aberration-corrected scanning transmission electron microscopy (C_s-STEM).     

Influence of Doping on Structural and Thermoelectric Properties of AgSbSe<Subscript>2</Subscript>

A series of samples with nominal compositions of AgSb_1−x Sn _x Se₂ (with x = 0.0, 0.1, 0.2, and 0.3) and AgSbSe_2−y Te _y (with y = 0.0, 0.25, 0.5, 0.75, and 1.0) were prepared. The crystal structure of both single crystals and polycrystalline samples was analyzed using x-ray and neutron diffractometry. The electrical conductivity, thermal conductivity, and Seebeck coefficient were measured within the temperature range from 300 K to 700 K. In contrast to intrinsic AgSbSe₂, samples doped with Sn and Te exhibit apparent semiconducting properties (E _g = 0.3 eV to 0.5 eV), lower electrical conductivity, and higher values of the Seebeck coefficient for a small amount of Sn (x = 0.1). Further doping leads to decrease of the thermoelectric power and increase of the electrical conductivity. In order to explain electron transport behavior observed in pure and doped AgSbSe₂, electronic structure calculations were performed by the Korringa–Kohn–Rostoker method with coherent potential approximation (KKR–CPA).     

PbTe/Te superlattice structures with enhanced thermoelectric figures of merit

The thermoelectric properties of PbTe/Te superlattice structures grown by molecular beam epitaxy have been investigated. The in-plane Seebeck coefficient, Hall coefficient, and electrical resistivity have been measured at 300K. The data show that a significant enhancement of the in-plane Seebeck coefficient, thermoelectric power factor and figure of merit has been achieved.     

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.