Microstructures and Thermoelectric Properties of an Annealed Ti<Subscript>0.5</Subscript>(Hf<Subscript>0.5</Subscript>Zr<Subscript>0.5</Subscript>)<Subscript>0.5</Subscript>NiSn<Subscript>0.998</Subscript>Sb<Subscript>0.002</Subscript> Ribbon

The thermoelectric half-Heusler compound Ti_0.5(Hf_0.5Zr_0.5)_0.5NiSn_0.998Sb_0.002 was fabricated by spin-casting and subsequent annealing. ZT at room temperature increased with annealing time through an increase in absolute Seebeck coefficients despite a decrease in electrical conductivity. ZT reached 0.10 after annealing at 1050 K for 48 h. In powder x-ray diffraction analysis, each half-Heusler peak was accompanied by a bump at the high-angle side, corresponding to a minor Ti-rich half-Heusler phase. The quantity and Ti composition of the minor phase increased with annealing time, although those of the major half-Heusler phase were almost constant. In transmission electron microscopic analysis, granular domains, several nanometers in size, with atomic ordering or disordering were observed. Thermoelectric properties were␣improved by annealing through the growth of heterogeneous microstructures of the Ti-rich and Ti-poor half-Heusler grains and of the granular domains.     

Thermoelectric Properties of Tix(HfyZr1?y)1?xNiSn0.998Sb0.002 Half-Heusler Ribbons

Ribbons of Ti _x (Hf _y Zr_1−y )_1−x NiSn_1−z Sb _z (x = 0.1 to 1, y = 0.1 to 0.9, z = 0, 0.002, 0.004) were prepared by spin casting and annealed for 1 h at T _a = 1000 K, 1050 K, 1073 K, and 1100 K. The crystal phase of the ribbons was investigated by x-ray diffraction analysis and transmission electron microscopy. All the ribbons consisted of a phase with a half-Heusler structure. The Seebeck coefficient, electrical conductivity, thermal conductivity, power factor, and figure of merit ZT at room temperature were clarified experimentally as a function of x, y, z, and T _a. Despite the large thermal conductivity, the power factor and figure of merit were remarkably large at x = 0.5, y = 0.5, z = 0.002, and T _a = 1073 K, because the Seebeck coefficient and electrical conductivity were large.     

Large Closed-Circuit Seebeck Current in Quaternary (Ti,Zr)NiSn Heusler Alloys

In the (Ti _x ,Zr _y )Ni _w Sn _z quaternary system with a composition near (x + y):w:z = 1:1:1 the existence of the half-Heusler (HH) phase has been confirmed, where Ti and Zr occupy one of the three lattice positions substitutionally. The goal of this study is to characterize the thermoelectric (TE) properties of such materials. TE properties were measured at large temperature differences up to ΔT = 800 K, exhibiting Seebeck voltages of about ±50 mV corresponding to Seebeck coefficients above 0.07 mV/K, with the highest value measured for the (Ti_0.4Zr_0.6)Ni_0.9Sn_1.1 composition. Fe and Mn doping could not improve these values further. Measurements under closed-circuit conditions showed very high currents of 0.4 mA for specimens at this particular composition. According to the composition, interfaces between full-Heusler and HH phases are responsible for an electron pull-out phenomenon due to the electric field at their interfaces. First-principle calculations of the electronic band structure confirm this explanation for why (TiZr)NiSn and CrNiSn are p-type TEs whereas NbNiSn is an n-type TE. These considerations will be useful in the search for other such systems.     

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.     

Improved Thermoelectric Properties of (GeTe)90(AgySb2?yTe3?y)10 by Tuning the Ag-to-Sb Ratio

(GeTe)₉₀(Ag _y Sb_2−y Te_3−y )₁₀ (y = 0.6, 0.7, 0.8, 1.0) compounds were prepared by combining melting and hot pressing, and the thermoelectric properties were studied over the temperature range of 300 K to 770 K. Powder x-ray diffraction results revealed that all the samples were the rhombohedral phase with space group R3m. The electrical conductivity of samples decreased with temperature, while the Seebeck coefficient increased. The thermal conductivity of all the samples was very low, especially for those with the lower y values. High ZT values above 1.6 were obtained for the samples with y = 0.6, 0.7, and 0.8.     

Effects of Ir Substitution and Processing Conditions on Thermoelectric Performance of p-Type Zr0.5Hf0.5Co1?xIrxSb0.99Sn0.01 Half-Heusler Alloys

A series of samples with the composition Zr_0.5Hf_0.5Co_1−x Ir _x Sb_0.99Sn_0.01 (x = 0.0 to 0.7) were synthesized by high-temperature solid-state reaction at 1173 K. High-density pellets of the powders were obtained using hot press (HP) and spark plasma sintering (SPS) techniques. The thermoelectric properties of the pellets were measured from 300 K to 750 K. Independently of the pressing conditions, all Ir-containing samples (x > 0) showed p-type semiconducting behavior. At 300 K, the electrical conductivity and thermopower of Zr_0.5Hf_0.5Co_1−x Ir _x Sb_0.99Sn_0.01 materials surprisingly increased with increasing Ir concentration. The largest electrical conductivity and thermopower values of 150 S/cm and 140 μV/K, respectively, were observed at 300 K for x = 0.7. The thermal conductivity of the synthesized materials decreased with increasing Ir content, went through a minimum value (x = 0.3), and increased thereafter with further addition of Ir. Pellets fabricated by SPS showed smaller thermal conductivity than pellets of the same composition obtained from uniaxial hot pressing. A thermal conductivity value of ∼2.0 W/m K was observed at 300 K for an SPS pellet with the com- position Zr_0.5Hf_0.5Co_0.5Ir_0.5Sb_0.99Sn_0.01. The thermal conductivity of Zr_0.5Hf_0.5- Co_1−x Ir _x Sb_0.99Sn_0.01 decreased with rising temperature, and the smallest value of ∼1.5 W/m K was observed at 750 K for the SPS specimen with x = 0.5.     

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.     

Thermoelectric Properties of Zintl Compound YbZn<Subscript>2</Subscript>Sb<Subscript>2</Subscript> with Mn Substitution in Anionic Framework

The thermoelectric properties of the Zintl compound YbZn₂Sb₂ with isoelectronic substitution of Zn by Mn in the anionic (Zn₂Sb₂)²⁻ framework have been studied. The p-type YbZn_2−x Mn _x Sb₂ (0.0 ≤ x ≤ 0.4) samples were prepared via melting followed by annealing and hot-pressing. Thermoelectric property measurement showed that the Mn substitution effectively lowered the thermal conductivity for all the samples, while it significantly increased the Seebeck coefficient for x < 0.2. As a result, a dimensionless figure of merit ZT of approximately 0.61 to 0.65 was attained at 726 K for x = 0.05 to 0.15, compared with the ZT of ~0.48 in the unsubstituted YbZn₂Sb₂.     

Thermoelectric Properties of Co<Subscript>4</Subscript>Sb<Subscript>12</Subscript> Skutterudite Materials with Partial In Filling and Excess In Additions

The properties of Co₄Sb₁₂ with various In additions were studied. X-ray diffraction revealed the presence of the pure δ-phase of In_0.16Co₄Sb₁₂, whereas impurity phases (γ-CoSb₂ and InSb) appeared for x = 0.25, 0.40, 0.80, and 1.20. The homogeneity and morphology of the samples were observed by Seebeck microprobe and scanning electron microscopy, respectively. All the quenched ingots from which the studied samples were cut were inhomogeneous in the axial direction. The temperature dependence of the Seebeck coefficient (S), electrical conductivity (σ), and thermal conductivity (κ) was measured from room temperature up to 673 K. The Seebeck coefficient of all In-added Co₄Sb₁₂ materials was negative. When the filler concentration increases, the Seebeck coefficient decreases. The samples with In additions above the filling limit (x = 0.22) show an even lower Seebeck coefficient due to the formation of secondary phases: InSb and CoSb₂. The temperature variation of the electrical conductivity is semiconductor-like. The thermal conductivity of all the samples decreases with temperature. The central region of the In_0.4Co₄Sb₁₂ ingot shows the lowest thermal conductivity, probably due to the combined effect of (a) rattling due to maximum filling and (b) the presence of a small amount of fine-dispersed secondary phases at the grain boundaries. Thus, regardless of the non-single-phase morphology, a promising ZT (S ² σT/κ) value of 0.96 at 673 K has been obtained with an In addition above the filling limit.     

Thermoelectric Properties of Triple-Filled BaxYbyInzCo4Sb12 Skutterudites

Indium-filled skutterudites are promising power generation thermoelectric materials due to the presence of an InSb nanostructure that lowers the thermal conductivity. In this work, we have investigated thermoelectric properties of triple-filled Ba _x Yb _y In _z Co₄Sb₁₂ (0 ≤ x, y, z ≤ 0.14 actual) compounds by measuring their Seebeck coefficient, electrical conductivity, thermal conductivity, and Hall coefficient. All samples were prepared by a melting–annealing–spark plasma sintering method, and their structure was characterized by x-ray diffraction and transmission electron microscopy (TEM). TEM results show the development of an InSb nanostructure with a grain size of 30 nm to 500 nm. The nanostructure is present in all samples containing In and is also detected by specific heat measurements. The Seebeck and Hall coefficients indicate that the compounds are n-type semiconductors. Electrical conductivity increases with increasing Ba content. Thermal conductivity is strongly suppressed upon the presence of In in the skutterudite structure, likely due to enhanced boundary scattering of phonons on the nanometer-scale InSb inclusions. The highest thermoelectric figure of merit is achieved with Ba_0.09Yb_0.07In_0.06Co₄Sb_11.97, reaching ZT = 1.25 at 800 K.     

Natural Microstructure and Thermoelectric Performance of (GeTe)80(AgySb2?yTe3?y)20

Thermoelectric (TE) materials (GeTe)₈₀(Ag _y Sb_2−y Te_3−y )₂₀ (y = 0.6, 0.8, 1.0, 1.2, and 1.4) were prepared, and their TE properties and microstructure studied in this work. Due to their relatively low thermal conductivity and proper carrier concentration, high ZT values were obtained for all samples except for y = 1.4. Using transmission electron microscopy, twins, antiphase domains, and low-angle grain boundaries were observed throughout the sample with y = 1.2. Nanoscale regions with double atomic spacing were detected. These regions and the matrix were coherent without obvious mismatch. The relationship between high ZT values and microstructure is discussed.     

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).     

High-Temperature Thermoelectric Properties of Co4Sb12-Based Skutterudites with Multiple Filler Atoms: Ce0.1InxYbyCo4Sb12

Void-filling in the CoSb₃ skutterudite lattice with different kinds of heavy elements has proven to be an effective mechanism to enhance thermoelectric performance due primarily to a reduction in lattice thermal conductivity. Specifically, our findings on the series In _x Yb _y Co₄Sb₁₂ [0 ≤ (x, y) ≤ 0.2] have further motivated an attempt to form triple-filled skutterudites Ce_0.1In _x Yb _y Co₄Sb₁₂ with In and Yb concentrations [0 ≤ (x, y) ≤ 0.2] and with the Ce concentration held constant (Ce_0.1). All of these samples have been prepared via a simplified melting–annealing–sintering procedure and were first characterized by means of x-ray powder diffraction and scanning electron microscopy, followed by measurements of the Hall coefficient, electrical and thermal conductivities, and Seebeck coefficient. Our aim is to further elucidate the roles of the three elements (Ce, In, and Yb) in these materials. Compared with the addition of just In or Yb, we found that simultaneous addition of both In and Yb reduced the lattice thermal conductivity without significantly degrading the power factor. Further addition of the third element (Ce), along with In and Yb, also produced a similar result. However, we noticed that some of the In and Yb were also observed in the form of secondary phases (InSb and Yb₂O₃), not entering entirely as filler atoms. As a result of our investigation, several compositions achieved increased sustainability and enhanced thermoelectric performance, with maximum ZT values of about 1.3 to 1.4 obtained at around 800 K.     

Thermoelectric Properties of Melt-Spun Zn x Sb3 Ribbons

Melt-spun ribbons composed of Zn _x Sb₃ (3.4????x????4.3) were fabricated through a single-wheel melt-spinning process at wheel velocities of 0.6?m?s^?1 to 4.2?m?s^?1 and annealed for 2?h at 673?K. The structures were investigated using x-ray diffraction. The dimensionless figure of merit ZT, Seebeck coefficient, and electrical conductivity were measured to estimate the power factor and thermal conductivity. ??-Zn₄Sb₃ in the as-spun ribbons coexisted with ZnSb or Zn at 0.6?m?s^?1, while it coexisted with ??-Zn₃Sb₂ in x????3.8 at 4.2?m?s^?1, where ??-Zn₃Sb₂ disappeared in the annealed ribbons. The Seebeck coefficient in the as-spun and annealed ribbons tended to decrease slightly with increasing x at all the wheel velocities. At 0.6?m?s^?1, the ZT and power factor of as-spun and annealed ribbons increased with increasing x at x?<?4.0 because of increase in the electrical conductivity. At 4.2?m?s^?1, ZT was smaller than that at 0.6?m?s^?1 because the electrical conductivity was small in the as-spun ribbons and the thermal conductivity was large in the annealed ribbons.     

Crystal Structure and High-Temperature Thermoelectric Properties of the Mo<Subscript>3−<Emphasis Type="Italic">x</Emphasis></Subscript>Ru<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Sb<Subscript>7</Subscript> Compounds

Zintl phases are currently receiving great attention for their thermoelectric potential typified by the discovery of a high ZT value in Yb₁₄MnSb₁₁-based compounds. Herein, we report on the crystallographic characterization via neutron and x-ray diffraction experiments, and on the thermoelectric properties measured in the 300 K to 1000 K temperature range, of Mo₃Sb₇ and its isostructural compounds Mo_3−x Ru _x Sb₇. Even though Mo₃Sb₇ displays rather high ZT values given its metallic character, the partial substitution of Mo by Ru substantially improves its thermoelectric properties, resulting in a ZT value of ∼0.45 at 1000 K for x = 0.8.     

Effects of Microstructural Evolution on the Thermoelectric Properties of Spark-Plasma-Sintered Ti0.3Zr0.35Hf0.35NiSn Half-Heusler Compound

The MNiSn (M = Ti, Zr, Hf) half-Heusler semiconducting compounds are widely investigated due to their good potential for thermoelectric (TE) power generation applications. In the current work, the evolution of the transport and structural properties of the Ti_0.3Zr_0.35Hf_0.35NiSn compound upon various thermal treatments was studied. The nominal composition was arc melted, ball milled, and spark plasma sintered (SPS). Following SPS, large Hf-rich domains were found by scanning electron microscopy (SEM) and energy-dispersive x-ray spectroscopy (EDS). Subsequently, the samples were subjected to homogenization treatments at 1163 K for 480 h and 610 h under argon atmosphere. Following these thermal treatments, the relative amount of the Hf-rich domains was reduced and they became smaller in size, with increasing thermal treatment duration. Nevertheless, no uniphased structure was reached. The dissolution of the Hf-rich domains in the half-Heusler matrix resulted in increase of both the Seebeck coefficient and electrical resistivity values and a decrease of the carrier concentration, attributed to elimination of these metallic domains. Resulting from the high atomic disorder caused by substitution at the M site, low thermal conductivity values of ~3.8 W m^?1 K^?1 were obtained leading to high ZT values of up to 0.82 following SPS.     

Thermoelectric Properties of Directionally Solidified Half-Heusler (M 0.5a ,M 0.5b )NiSn (Ma, Mb?=?Hf, Zr, Ti) Alloys

To evaluate the effect of the substitution of the M-site atoms Ti, Zr, and Hf on thermoelectric properties, nearly single-phase (M_0.5^a,M_0.5^b)NiSn alloys (M^a, M^b = Hf, Zr, Ti) were fabricated by directional solidification. The lattice thermal conductivity can be most effectively reduced in the (Ti_0.5,Hf_0.5)NiSn alloy, probably due to the solid-solution effect, since the difference in atomic size and atomic mass are maximized between Ti and Hf. Moreover, we have found the phase separation between Ti-rich and Ti-poor half-Heusler phases in (Ti_0.5,Hf_0.5)NiSn and (Ti_0.5,Zr_0.5)NiSn alloys through observation of microstructure, chemical concentration measurement, and x-ray diffractometry.     

Thermoelectric Properties of NdGd<Subscript>1+<Emphasis Type="Italic">x</Emphasis></Subscript>S<Subscript>3</Subscript> Prepared by CS<Subscript>2</Subscript> Sulfurization

Ternary rare-earth sulfides NdGd_1+x S₃, where 0 ≤ x ≤ 0.08, were prepared by sulfurizing Ln₂O₃ (Ln = Nd, Gd) with CS₂ gas, followed by reaction sintering. The sintered samples have full density and homogeneous compositions. The Seebeck coefficient, electrical resistivity, and thermal conductivity were measured over the temperature range of 300 K to 950 K. All the sintered samples exhibit a negative Seebeck coefficient. The magnitude of the Seebeck coefficient and the electrical resistivity decrease systematically with increasing Gd content. The thermal conductivity of all the sintered samples is less than 1.9 W K⁻¹ m⁻¹. The highest figure of merit ZT of 0.51 was found in NdGd_1.02S₃ at 950 K.     

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.     

Low-Temperature Transport Properties of InxFeyCo4?ySb12

Interesting results for cobalt triantimonide partially filled with indium have encouraged us to explore skutterudites filled with higher indium fractions. For pure In _x Co₄Sb₁₂, the fraction of voids filled is limited to about x = 0.25. To enable the insertion of more indium atoms, charge compensation is necessary. In this work, we studied the skutterudite compound In _x Fe _y Co_4−y Sb₁₂ partially filled with indium, where iron substitution for cobalt was employed for charge compensation. Polycrystalline samples were prepared by direct reaction of constituents. Structural and chemical characterization were accomplished by x-ray diffraction and energy-dispersive x-ray spectroscopy. Electrical resistivity, thermoelectric power, and thermal conductivity were measured between 2 K and 350 K. The influence of indium and iron on the charge-carrier transport properties and thermal conductivity in In _x Fe _y Co_4−y Sb₁₂ compounds is presented and discussed.