Effect of Composition on Thermoelectric Properties of Polycrystalline CrSi2

Ingots with compositions CrSi_2?x (with 0 < x < 0.1) were synthesized by vacuum arc melting followed by uniaxial hot pressing for densification. This paper reports the temperature and composition dependence of the electrical resistivity, Seebeck coefficient, and thermal conductivity of CrSi_2?x samples in the temperature range of 300 K to 800 K. The silicon-deficient samples exhibited substantial reductions in resistivity and Seebeck coefficient over the measured temperature range due to the formation of metallic secondary CrSi phase embedded in the CrSi₂ matrix phase. The thermal conductivity was seen to exhibit a U-shaped curve with respect to x, exhibiting a minimum value at the composition of x = 0.04. However, the limit of the homogeneity range of CrSi₂ suppresses any further decrease of the lattice thermal conductivity. As a consequence, the maximum figure of merit of ZT = 0.1 is obtained at 650 K for CrSi_1.98.     

Effect of Heat Treatment on the Thermoelectric Properties of Bismuth–Antimony–Telluride Prepared by Mechanical Deformation and Mechanical Alloying

In this work, p-type 20%Bi₂Te₃–80%Sb₂Te₃ bulk thermoelectric (TE) materials were prepared by mechanical deformation (MD) of pre-melted ingot and by mechanical alloying (MA) of elemental Bi, Sb, and Te granules followed by cold-pressing. The dependence on annealing time of changes of microstructure and TE properties of the prepared samples, including Seebeck coefficient, electrical resistivity, thermal conductivity, and figure-of-merit, was investigated. For both samples, saturation of the Seebeck coefficient and electrical resistivity were observed after annealing for 1 h at 380°C. It is suggested that energy stored in samples prepared by both MA and MD facilitated their recrystallization within short annealing times. The 20%Bi₂Te₃–80%Sb₂Te₃ sample prepared by MA followed by heat treatment had higher a Seebeck coefficient and electrical resistivity than specimens fabricated by MD. Maximum figures-of-merit of 3.00 × 10^?3/K and 2.85 × 10^?3/K were achieved for samples prepared by MA and MD, respectively.     

Ball Mill Synthesis of Bulk Quaternary Cu<Subscript>2</Subscript>ZnSnSe<Subscript>4</Subscript> and Thermoelectric Studies

In this work, quaternary chalcogenide Cu₂ZnSnSe₄ (CZTSe) was synthesized using a mechanochemical ball milling process and its thermoelectric properties were studied by electrical resistivity, Seebeck coefficient, and thermal conductivity measurements. The synthesis process comprises three steps viz., wet ball milling of the elemental precursors, vacuum annealing, and densification by hot pressing. The purpose of this is to evaluate the feasibility of introducing wet milling in place of vacuum melting in solid state synthesis for the reaction of starting elements. We report the structural characterization and thermoelectric studies conducted on samples that were milled at 300 rpm and 500 rpm. X-ray diffraction (XRD) analysis showed the existence of multiple phases in the as-milled samples, indicating the requirement for heat treatment. Therefore, the ball milled powders were cold pressed and vacuum annealed to eliminate the secondary phases. Annealed samples were hot pressed and made into dense pellets for further investigations. In addition to XRD, energy dispersive spectroscopy (EDS) studies were performed on hot pressed samples to study the composition. XRD and EDS studies confirm CZTSe phase formation along with ZnSe secondary phase. Electrical resistivity and Seebeck coefficient measurements were done on the hot pressed samples in the temperature range 340–670 K to understand the thermoelectric behaviour. Thermal conductivity was calculated from the specific heat capacity and thermal diffusivity values. The thermoelectric figure of merit zT values for samples milled at 300 rpm and 500 rpm are ～0.15 and ～0.16, respectively, at 630 K, which is in good agreement with the values reported for solid state synthesized compounds.     

Synthesis and Measurement of the Thermoelectric Properties of Multiphase Composites: ZnSb Matrix with Zn4Sb3, Zn3P2, and Cu5Zn8

We synthesized a series of samples with composition around 52 at.% zinc (Zn), 44 at.% antimony (Sb), 4 at.% phosphorus (P), and up to 3 at.% copper (Cu) by melting the elements and subsequent annealing. This resulted in dense and almost crack-free samples. X-ray powder diffraction (XRD) and scanning electron microscopy (SEM) revealed composites with a majority phase of ZnSb containing varying amounts of Zn₃P₂ and Cu₅Zn₈, in addition to Zn₄Sb₃ in some of the samples. We measured the Seebeck coefficient, electrical conductivity, and thermal conductivity as a function of temperature. The thermoelectric performance tended to improve with increasing Cu content. At Cu content of 2 at.%, a reduced resistivity allows for the highest dimensionless figure of merit, with a maximum zT value of 0.18 at around 573 K.     

Thermoelectric Properties of CdTe1−x Cl x Material Prepared by Spark Plasma Sintering Method

CdTe compound is a prospective thermoelectric material due to its high Seebeck coefficient and low thermal conductivity. In the present study, we optimized its carrier concentration by substituting Cl on the Te site in order to improve the electrical conductivity and decrease the lattice thermal conductivity. The polycrystalline CdTe_1?x Cl _x (x = 0.005, 0.01, 0.03, 0.05) samples were fabricated by solid state reaction followed with spark plasma sintering, and the relative densities of the sintered samples were higher than 98%. Thermoelectric properties, including Seebeck coefficient (α), electrical conductivity (σ). and thermal conductivity (κ), were measured in the temperature range of 300–700 K. The increase of Cl content (x) caused an increase of σ, and the maximum ZT value of 0.2 was obtained at about 630 K for the CdTe_0.97Cl_0.03 sample.     

Enhanced Thermoelectric Properties of (PbTe)0.88(PbS)0.12 Composites by Sb Doping

The effects of Sb doping on (PbTe)_0.88(PbS)_0.12 composites prepared by melting, ball milling, and spark plasma sintering were investigated. The x-ray diffraction results indicate that all samples Sb _x Pb_1?x Te_0.88S_0.12 with x = 0, 0.002, 0.004, 0.006 and 0.008 are composites containing PbTe with NaCl-type structure as the major phase and PbS with NaCl-type structure as the minor phase. The electrical resistivity is reduced with increasing Sb doping, from 1.95 × 10^?5 Ωm for Sb content x = 0 to 5.55 × 10^?6 Ωm for x = 0.008 at 298 K, showing that Sb is an efficient electron donor. However, the absolute Seebeck coefficient decreases, from 196 μV/K for x = 0 to 57.0 μV/K for x = 0.008 at 298 K, and the thermal conductivity increases, from 0.989 W/m K for x = 0 to 1.64 W/m K for x = 0.008, with Sb doping. The power factor and figure of merit ZT can be enhanced by proper Sb doping. The maximum dimensionless figure of merit ZT of 1.20 was obtained in the sample Sb_0.004Pb_0.996Te_0.88S_0.12 at 773 K.     

Effects of In Substitution for Ga on the Thermoelectric Properties of Type-VIII Clathrate Ba8Ga16Sn30 Single Crystals

We have prepared single crystals of type-VIII clathrate Ba₈Ga_15.9?x In _x Sn_30.1 for x ≤ 0.60 by the Sn-flux method. As x is increased from 0 to 0.60, the lattice parameter increases by 0.2%, which is consistent with the larger covalent diameter for In than for Ga. The Seebeck coefficient α, electrical resistivity ρ, and thermal conductivity κ were measured in the temperature range from 300 K to 600 K. For all samples, α is negative, indicating the dominant charge carriers are electrons. With increasing x from 0 to 0.20, ρ and \(\left| \alpha \right|\) decrease by 50% and 30%, respectively. As a result, the lattice thermal conductivity at 300 K decreases from 0.58 W/Km to 0.41 W/Km, which is ascribed to enhancement of rattling of the guest atoms. It is found that the maximum of the dimensionless figure of merit ZT reaches 1.05 at 540 K for x = 0.20.     

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.     

Possible Enhancement of Thermoelectric Properties by Use of a Magnetic Semiconductor: Carrier-Doped Chalcopyrite Cu1−x Fe1+x S2

We focus on the chalcopyrite CuFeS₂ to utilize the interaction between carriers and magnetic moments of Fe as a possible source to achieve high power factor. Polycrystalline samples of Cu_1?x Fe_1+x S₂ were synthesized, and their thermoelectric properties are reported. Electrical resistivity decreased by two orders of magnitude with increasing x, while the Seebeck coefficient showed large values of ?200 μV/K at room temperature. Thermal conductivity also decreased with the increase of x. As a result, the power factor and the figure of merit, zT, of the carrier-doped samples are about 10 times larger than those of CuFeS₂. These observations suggest that magnetic semiconductors can make good thermoelectric materials.     

On the Thermoelectric Properties of Zintl Compounds Mg3Bi2−x Pn x (Pn = P and Sb)

A series of Zintl compounds Mg₃Bi_2-x Pn _x (Pn = P and Sb) have been synthesized by the solid-state reaction method. While Sb can be substituted to a level as high as x = 1.0, P can be substituted only up to x = 0.5. The thermoelectric potential of these compounds has been evaluated by measuring resistivity (ρ), Seebeck (α) and Hall coefficients, and thermal conductivity between 80 K and 850 K. The measured resistivity and Seebeck coefficient values are consistent with those expected for small-bandgap semiconductors. Hall measurements suggest that the carriers are p type with concentration (p) increasing from ~10¹⁹ cm^?3 to ~10²⁰ cm^?3 as the Bi content is increased. The Hall mobility decreases with increasing temperature (T) and reaches a more or less similar value (~45 cm²/V s) for all substituted compositions at room temperature. Due to mass defect scattering, the lattice thermal conductivity (κ _L) is decreased to a minimum of ~1.2 W/m K in Mg₃BiSb. The power factor (α ²/ρ) is found to be rather low and falls in the range 0.38 mW/m K² to 0.66 mW/m K². As expected, at a high temperature of 825 K, the total thermal conductivity (κ) of Mg₃BiSb reaches an impressive value of ~1.0 W/m K. The highest dimensionless figure of merit (ZT) is realized for Mg₃BiSb and is ~0.4 at 825 K.     

Low Thermal Conductivity and High Thermoelectric Performance in In<Subscript>4</Subscript>Se<Subscript>3−<Emphasis Type="Italic">x</Emphasis></Subscript> with Phase-Separated Indium Inclusions

We report the thermoelectric properties of undoped hot-pressed In₄Se_3?x (x = 0.05). Stoichiometric imbalance due to selenium deficiency in In₄Se₃ was found to create a secondary phase of elemental indium in the host material. Heat treatment drove grain growth and increased the indium solubility in In₄Se₃. Indium-rich domains at grain surfaces/boundaries in untreated samples were found to redistribute inside the grains and their junctions after heat treatment. Due to enhanced phonon scattering by secondary phase of indium, very low values of thermal conductivity were observed for all samples, leading to a maximum thermoelectric figure of merit (zT) of 1.13 at 723 K along the hot-pressing direction for the heat-treated sample.     

Enhancement in Thermoelectric Properties of TiS<Subscript>2</Subscript> by Sn Addition

A series of Sn added TiS₂ (TiS₂:Sn _x ; x = 0, 0.05, 0.075 and 0.1) were prepared by solid state synthesis with subsequent annealing. The Sn atoms interacted with sulfur atoms in TiS₂ and formed a trace amount of misfit layer (SnS)_1+m(TiS_2?δ)_n compound with sulfur deficiency. A significant reduction in electrical resistivity with moderate decrease in the Seebeck coefficient was observed in Sn added TiS₂. Hence, a maximum power factor of 1.71 mW/m-K² at 373 K was obtained in TiS₂:Sn_0.05. In addition, the thermal conductivity was decreased with Sn addition and reached a minimum value of 2.11 W/m-K at 623 K in TiS₂:Sn_0.075, due to the impurity phase (misfit phase) and defects (excess Ti) scattering. The zT values increased from 0.08 in pristine TiS₂ to an optimized value of 0.46 K at 623 K in TiS₂:Sn_0.05.     

Enhanced Thermoelectric Properties of Hole-Doped Bi2−x Ba x Sr2Co2O y Ceramics

The influence of Ba doping on the thermoelectric properties of Bi_2?x Ba _x Sr₂ Co₂O _y (x = 0.00, 0.025, 0.05, 0.075, 0.10, 0.125, and 0.15) samples prepared by the solid-state reaction method was investigated from 333 K to 973 K. For the samples with x ≤ 0.075, the electrical resistivity decreased with increase of the Ba doping amount due to p-type doping and they exhibited metallic electrical conductivity behavior, whereas the samples with x ≥ 0.10 exhibited semiconductor-like electrical conductivity behavior. The Seebeck coefficients of all the samples decreased with increase of the Ba doping amount. The thermal conductivity first decreased for x ≤ 0.075, then increased with higher Ba doping amounts. As an overall result, the dimensionless figure of merit (ZT) of Bi_1.925Ba_0.075Sr₂Co₂O _y reached the maximum value of 0.245 at 973 K, being 41% higher than that of the undoped sample.     

Effects of Al/Sb Double Doping on the Thermoelectric Properties of Mg2Si0.75Sn0.25

Al/Sb double-doped Mg₂Si_0.75Sn_0.25 materials were prepared by liquid–solid reaction synthesis and the hot-pressing technique. The effects of Al/Sb double doping on the thermoelectric properties were investigated at temperatures between room temperature and 900 K, and the resistivity and Hall coefficient were investigated at 80 K to 900 K. Al/Sb double-doped samples were found to be n-type semiconductors in the investigated temperature range. The absolute Seebeck coefficient (α), resistivity (ρ), and thermal conductivity (κ) for Al/Sb double-doped samples at room temperature were in the ranges of 152.5 μV K^?1 to 109.2 μV K^?1, 2.92 × 10^?5 Ω m to 1.29 × 10^?5 Ω m, and 2.50 W K^?1 m^?1 to 2.86 W K^?1 m^?1, respectively. The absolute values of α increased with increasing temperature up to a maximum, and decreased thereafter. This could be attributed to mixed carrier conduction in the intrinsic region. κ decreased linearly with increasing temperature to a minimum near the intrinsic region, then increased rapidly because of bipolar components. The highest ZT value measured was 0.94 at 850 K for Mg_1.9975Al_0.0025Si_0.75Sn_0.2425Sb_0.0075. Sb doping was effective for enhancement of ZT, because of a remarkable increase in the carrier concentration. However, Al doping was almost ineffective for enhancing ZT.     

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.     

Effect of Fe Substitution on Thermoelectric Properties of Fe x In4−x Se3 Compounds

Starting from elemental powder mixtures of Fe _x In_4?x Se₃ (x = 0, 0.05, 0.1, 0.15), polycrystalline In₄Se₃-based compounds with homogeneous microstructures were prepared by mechanical alloying (MA) and hot pressing (HP). With the increase of x from 0 to 0.15, the electrical resistivity and the absolute value of the Seebeck coefficient increased, while the thermal conductivity first decreased and then increased. The maximal dimensionless figure of merit ZT of 0.44 was obtained for the Fe _x In_4?x Se₃ (x = 0.05) sample at 723 K.     

High Thermoelectric Performance in PbTe Due to Large Nanoscale Ag2Te Precipitates and La Doping

Thermoelectrics are being rapidly developed for waste heat recovery applications, particularly in automobiles, to reduce carbon emissions. PbTe‐based materials with small (<20 nm) nanoscale features have been previously shown to have high thermoelectric figure‐of‐merit, zT, largely arising from low lattice thermal conductivity particularly at low temperatures. Separating the various phonon scattering mechanisms and the electronic contribution to the thermal conductivity is a serious challenge to understanding, and further optimizing, these nanocomposites. Here we show that relatively large nanometer‐scale (50–200 nm) Ag₂Te precipitates in PbTe can be controlled according to the equilibrium phase diagram and these materials show intrinsic semiconductor behavior with high electrical resistivity, enabling direct measurement of the phonon thermal conductivity. This study provides direct evidence that even large nanometer‐scale microstructures reduce thermal conductivity below that of a macro‐scale composite of saturated alloys with Kapitza‐type interfacial thermal resistance at the same overall composition. Carrier concentration control is achieved with lanthanum doping, enabling independent control of the electronic properties and microstructure. These materials exhibit lattice thermal conductivity which approaches the theoretical minimum above ～650 K, even lower than that found with small nanoparticles. Optimally La‐doped n‐type PbTe‐Ag₂Te nanocomposites exhibit zT > 1.5 at 775 K.     

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.     

Effects of Ge Dopant on Thermoelectric Properties of Barium and Indium Double-Filled p-Type Skutterudites

A series of Ge-doped and (Ba,In) double-filled p-type skutterudite materials with nominal composition Ba_0.3In_0.2FeCo₃Sb_12?x Ge _x (x = 0 to 0.4, Δx = 0.1) have been prepared by melting, quenching, annealing, and spark plasma sintering methods. The effects of Ge dopant on the phase composition, microstructure, and thermoelectric properties of these materials were investigated in this work. A single-phase skutterudite material was obtained in the samples with 0 < x ≤ 0.2, and trace Fe₃Ge₂ was detected in the samples with x ≥ 0.3. The electrical conductivity increased and Seebeck coefficient decreased with increasing x in the range of 0 to 0.2, while the inverse behaviors of electrical conductivity and Seebeck coefficient were observed in the samples with x ≥ 0.3. The variations of electrical conductivity and Seebeck coefficient are attributed to the significant increase in the carrier concentration in the x range of 0 to 0.2 and the intensive impact of Fe₃Ge₂ when x ≥ 0.3. The lattice thermal conductivity of all the Ge-doped samples was considerably reduced as compared with the undoped Ba_0.3In_0.2FeCo₃Sb₁₂ sample, and the lowest value of lattice thermal conductivity of the Ba_0.3In_0.2FeCo₃Sb_11.8Ge_0.2 sample reached 1.0 W m^?1 K^?1 at 700 K. The highest ZT value of 0.54 was obtained at 800 K for the Ba_0.3In_0.2FeCo₃Sb_11.7Ge_0.3 sample, increased by 10% as compared with that of Ba_0.3In_0.2FeCo₃Sb₁₂.     

Thermoelectric and Magnetic Properties of Pt-Substituted $${BaFe_{4-{x}}Pt_{{x}}Sb_{12}}$$ Compounds

\({BaFe_{4-{x}}Pt_{{x}}Sb_{12}}\) (x = 0, 0.1, 0.2) compounds were prepared by melting and annealing, followed by a spark plasma sintering method. Low-temperature thermoelectric and magnetic properties were investigated based on Seebeck coefficient, electrical and thermal conductivity and magnetization measurements. The structural properties of \({BaFe_{4-{x}}Pt_{{x}}Sb_{12}}\) (x = 0, 0.1, 0.2) compounds were ascertained by powder x-ray diffraction analysis, confirming that all samples have a main phase of a skutterudite structure with the space group Im\({\mathrm {\bar{3}}}\). The lattice parameters obtained, 9.202(5), 9.199(5) and 9.202(1) Å for x = 0, 0.1 and 0.2, respectively, were found consistent with literature. The Seebeck coefficient sign shows that holes are dominant carriers in all compounds. The local maximum Seebeck coefficient was observed around 50 K which may be a trace of paramagnon-drag effect of charge carriers. Thermal conductivity and electrical resistivity measurements were carried out between 4.2 and 300 K. Temperature dependence of electrical resistivity reflects that all samples show semi-metallic behavior in our temperature range of 4.2–300 K. Samples for x = 0.1 and x = 0.2 show Kondo-like behavior. In magnetization measurement, we observe that there are two successive magnetic transitions in Pt-substituted compounds; however, there is only one (transition from a paramagnetic state to long-range magnetic ordering) in Pt-free compounds. In Pt-substituted compounds, the first transition appears at \( T _{ {\rm c}}\) = 48 K. In addition, the second transition is observed at \( T _{ {\rm irr}}\) = 30 K where an intermediate state is observed before the magnetic ordering transforms to an irreversible ferromagnetic state. We concluded that Pt substitution on the Fe side effectual on the thermoelectric and magnetic properties of \({BaFe_{4-{x}}Pt_{{x}}Sb_{12}}\) (x = 0, 0.1, 0.2) compounds.