Effects of doping on the high-temperature thermoelectric properties of IrSb3 skutterudite compounds

The IrSb₃-based skutterudite compounds have a potential for thermoelectric applications because of high Hall mobility, Seebeck coefficient, and relatively low thermal conductivity. In the present study, polycrystalline p- and n-type IrSb₃ compounds are prepared by powder metallurgy techniques. The effect of doping on thermoelectric properties has been investigated in binary and ternary IrSb₃ compounds using Ru, Ge, Pd, or Pt as a dopant. It is shown that the electrical properties depend strongly not only on the kinds of doping impurities but also their levels. Our theoretical analysis suggests that the effective mass is significantly affected by doping impurities and the levels.     

Thermoelectric Properties of Co<Subscript>4</Subscript>Sn<Subscript>6</Subscript>Se<Subscript>6</Subscript> Ternary Skutterudites

A ternary ordered variant of the skutterudite structure, the Co₄Sn₆Se₆ compound, was prepared. Polycrystalline samples were prepared by a modified ceramic method. The electrical conductivity, the Seebeck coefficient and the thermal conductivity were measured over a temperature range of 300–800 K. The undoped Co₄Sn₆Se₆ compound was of p-type electrical conductivity and had a band gap E _g of approximately 0.6 eV. The influence of transition metal (Ni and Ru) doping on the thermoelectric properties was studied. While the thermal conductivity was significantly lowered both for the undoped Co₄Sn₆Se₆ compound and for the doped compounds, as compared with the Co₄Sb₁₂ binary skutterudite, the calculated ZT values were improved only slightly.     

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.     

Solid-State Synthesis of Te-Doped Mg<Subscript>2</Subscript>Si

Te-doped Mg₂Si (Mg₂Si:Te _m , m = 0, 0.01, 0.02, 0.03, 0.05) alloys were synthesized by a solid-state reaction and mechanical alloying. The electronic transport properties (Hall coefficient, carrier concentration, and mobility) and thermoelectric properties (Seebeck coefficient, electrical conductivity, thermal conductivity, and figure of merit) were examined. Mg₂Si was synthesized successfully by a solid-state reaction at 673 K for 6 h, and Te-doped Mg₂Si powders were obtained by mechanical alloying for 24 h. The alloys were fully consolidated by hot-pressing at 1073 K for 1 h. All the Mg₂Si:Te _m samples showed n-type conduction, indicating that the electrical conduction is due mainly to electrons. The electrical conductivity increased and the absolute value of the Seebeck coefficient decreased with increasing Te content, because Te doping increased the electron concentration considerably from 10¹⁶ cm⁻³ to 10¹⁸ cm⁻³. The thermal conductivity did not change significantly on Te doping, due to the much larger contribution of lattice thermal conductivity over the electronic thermal conductivity. Thermal conduction in Te-doped Mg₂Si was due primarily to lattice vibrations (phonons). The thermoelectric figure of merit of intrinsic Mg₂Si was improved by Te doping.     

Thermoelectric Properties of Skutterudites Co4−x Ni x Sb11.9−y Te y Se0.1

CoSb₃-based skutterudites with substitution of Ni atoms for Co, and substitution of Te and Se atoms for Sb were successfully prepared by solid-state reaction and spark plasma sintering. According to x-ray diffraction analysis the major phase of all the samples had a CoSb₃-type structure, although back-scattered electron images showed that small amounts of impurity phases were present in all the samples. The temperature-dependent transport properties were characterized over the temperature range 300–800 K for all the samples. It was found that appropriate substitution with Ni, Te, and Se effectively improved the power factor and reduced the thermal conductivity. As a result, Ni, Te, and Se-tri-doped CoSb₃ materials with enhanced thermoelectric figures of merit, ZT, were obtained. The highest ZT was greater than 1.1 at high temperature.     

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 Magnesium Silicide Deposited by Use of an Atmospheric Plasma Thermal Spray

The thermoelectric properties of magnesium silicide (Mg₂Si) samples prepared by use of an atmospheric plasma spray (APS) were compared with those of samples prepared from the same feedstock powder by use of the conventional hot-pressing method. The characterization performed included measurement of thermal conductivity, electrical conductivity, Seebeck coefficient, and figure of merit, ZT. X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive x-ray spectroscopy (EDX) were used to assess how phase and microstructure affected the thermoelectric properties of the samples. Hall effect measurements furnished carrier concentration, and measurement of Hall mobility provided further insight into electrical conductivity and Seebeck coefficient. Low temperature and high velocity APS using an internal-powder distribution system achieved a phase of composition similar to that of the feedstock powder. Thermal spraying was demonstrated in this work to be an effective means of reducing the thermal conductivity of Mg₂Si; this may be because of pores and cracks in the sprayed sample. Vacuum-annealed APS samples were found to have very high Seebeck coefficients. To further improve the figure of merit, carrier concentration must be adjusted and carrier mobility must be enhanced.     

Effect of In Impurity on Thermoelectric Properties of Ba and In Double-Filled n-Type Skutterudite Materials

A series of (Ba,In) double-filled n-type skutterudite materials with nominal composition Ba_0.4In _m Co₄Sb₁₂ (m?=?0 to 0.4, ??m?=?0.1) has been prepared by melt quenching, annealing, and spark plasma sintering (SPS). The presence of In impurity and its effect on the thermoelectric properties of the filled skutterudite materials have been precisely investigated in this work. All samples consisted of skutterudite phase, while traces of In-containing impurity were detected in samples with m????0.3. The electrical conductivity and thermal conductivity decreased, and the absolute value of the Seebeck coefficient increased with increasing m in the range 0 to 0.2; however, the inverse behavior of the electrical conductivity, thermal conductivity, and Seebeck coefficient was observed in the samples with m????0.3. The thermoelectric properties of Ba_0.4In _m Co₄Sb₁₂ in the m range of 0 to 0.2 were changed because of carrier concentration degradation and strong lattice scattering induced by the In filler, while they were intensively affected by the In-containing impurity for m????0.3. Compared with the Ba single-filled skutterudite material, the power factors of all (Ba,In) double-filled skutterudite materials significantly increased and the lattice thermal conductivity dramatically decreased. As a result, two large ZT values for the samples with m?=?0.2 and 0.4 reached 1.19 and 1.25 at 800?K, which is an enhancement of 52% and 60%, respectively.     

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

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

Thermoelectric Properties of Nb-Doped Ordered Mesoporous TiO<Subscript>2</Subscript>

Mesoporous materials have pores with diameters between 2 nm and 50 nm, the presence of which generally decreases the thermal conductivity of the material. By incorporating mesoporous structures into thermoelectric materials, the thermoelectric properties of these materials can be improved. Although TiO₂ is an ordinary insulator, reduced TiO₂ shows better electrical conductivity and is therefore a potential thermoelectric material. Furthermore, the addition of a dopant to TiO₂ can improve its electrical conductivity. We hypothesized that, by doping ordered mesoporous TiO₂ films with niobium, we would be able to minimize the thermal conductivity and maximize the electrical conductivity. To investigate the effects of Nb doping and a mesoporous structure on the thermoelectric characteristics of TiO₂ films, Nb-doped mesoporous films were investigated using x-ray diffraction, ellipsometry, four-point probe measurements, and thermal conductivity analysis. We found that Nb doping of ordered mesoporous TiO₂ films improved their thermoelectric properties.     

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.     

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).     

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.     

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.     

Solid-State Synthesis and Thermoelectric Properties of Al-Doped Mg2Si

The electronic transport and thermoelectric properties of Al-doped Mg₂Si (Mg₂Si:Al _m , m?=?0, 0.005, 0.01, 0.02, 0.03) compounds prepared by solid-state synthesis were examined. Mg₂Si was synthesized by solid-state reaction (SSR) at 773?K for 6?h, and Al-doped Mg₂Si powders were obtained by mechanical alloying (MA) for 24?h. Mg₂Si:Al _m were fully consolidated by hot pressing (HP) at 1073?K for 1?h, and all samples showed n-type conduction, indicating that the electrical conduction is due mainly to electrons. The electrical conductivity increased significantly with increasing Al doping content, and the absolute value of the Seebeck coefficient decreased due to the significant increase in electron concentration from 10¹⁶ cm^?3 to 10¹⁹ cm^?3 by Al doping. The thermal conductivity was increased slightly by Al doping, but was not changed significantly by the Al doping content due to the much larger contribution of lattice thermal conductivity over electronic thermal conductivity. Mg₂Si:Al_0.02 showed a maximum thermoelectric figure of merit of 0.47 at 823?K.     

Charge‐Compensated Compound Defects in Ga‐containing Thermoelectric Skutterudites

Heavy doping changes an intrinsic semiconductor into a metallic conductor by the introduction of impurity states. However, Ga impurities in thermoelectric skutterudite CoSb₃ with lattice voids provides an example to the contrary. Because of dual‐site occupancy of the single Ga impurity charge‐compensated compound defects are formed. By combining first‐principle calculations and experiments, we show that Ga atoms occupy both the void and Sb sites in CoSb₃ and couple with each other. The donated electrons from the void‐filling Ga (Ga_VF) saturate the dangling bonds from the Sb‐substitutional Ga (Ga_Sb). The stabilization of Ga impurity as a compound defect extends the region of skutterudite phase stability toward Ga_0.15Co₄Sb_11.95 whereas the solid–solution region in other directions of the ternary phase diagram is much smaller. A proposed ternary phase diagram for Ga‐Co‐Sb is given. This compensated defect complex leads to a nearly intrinsic semiconductor with heavy Ga doping in CoSb₃ and a much reduced lattice thermal conductivity (κ_L) which can also be attributed to the effective scattering of both the low‐ and high‐frequency lattice phonons by the dual‐site occupant Ga impurities. Such a system maintains a low carrier concentration and therefore high thermopower, and the thermoelectric figure of merit quickly increases to 0.7 at a Ga doping content as low as 0.1 per Co₄Sb₁₂ and low carrier concentrations on the order of 10¹⁹ cm^?3.     

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.     

The Impact of Nanostructuring on the Thermal Conductivity of Thermoelectric CoSb3

The high concentration of grain boundaries provided by nanostructuring is expected to lower the thermal conductivity of thermoelectric materials, which favors an increase in their thermoelectric figure‐of‐merit, ZT. A novel chemical alloying method has been used for the synthesis of nanoengineered‐skutterudite CoSb₃. The CoSb₃ powders were annealed for different durations to obtain a set of samples with different particle sizes. The samples were then compacted into pellets by uniaxial pressing under various conditions and used for the thermoelectric characterization. The transport properties were investigated by measuring the Seebeck coefficient and the electrical and thermal conductivities in the temperature range 300 K to 650 K. A substantial reduction in the thermal conductivity of CoSb₃ was observed with decreasing grain size in the nanometer region. For an average grain size of 140 nm, the thermal conductivity was reduced by almost an order of magnitude compared to that of a single crystalline or highly annealed polycrystalline material. The highest ZT value obtained was 0.17 at 611 K for a sample with an average grain size of 220 nm. The observed decrease in the thermal conductivity with decreasing grain size is quantified using a model that combines the macroscopic effective medium approaches with the concept of the Kapitza resistance. The compacted samples exhibit Kapitza resistances typical of semiconductors and comparable to those of Si–Ge alloys.     

Lower Thermal Conductivity and Higher Thermoelectric Performance of Fe-Substituted and Ce, Yb Double-Filled p-Type Skutterudites

Substituting Fe on Co sites is an effective way to produce p-type skutterudite compounds as well as to reduce the thermal conductivity of skutterudites. In this work, we investigated thermoelectric properties of Fe-substituted and Ce + Yb double-filled Ce _x Yb _y Fe _z Co_4?z Sb₁₂ (x = y = 0.5, z = 2.0 to 3.25 nominal) skutterudite compounds by studying the Seebeck coefficient, electrical conductivity, thermal conductivity, and Hall coefficient over a broad range of temperatures. All samples were prepared by using the traditional method of melting–annealing and spark plasma sintering. The signs of the Hall coefficient and Seebeck coefficient indicate that all samples are p-type conductors. Electrical conductivity increases with increasing Fe content. The temperature dependence of electrical conductivity indicates that a transition from the extrinsic to the intrinsic regime of conduction depends on the amount of Fe substituted for Co. The temperature dependence of mobility reflects the dominance of acoustic phonon scattering at temperatures above ambient. Except for Ce_0.5Yb_0.5Fe_3.25Co_0.75Sb₁₂, the thermal conductivity increases with increasing Fe content, reaching the maximum value of 2.23 W/m K at room temperature for Ce_0.5Yb_0.5Fe₃CoSb₁₂. A high power factor (27 μW/K² cm) combined with a rather low thermal conductivity for Ce_0.5Yb_0.5Fe_3.25Co_0.75Sb₁₂ (nominal) lead to a dimensionless figure of merit ZT = 1.0 at 750 K for this compound, one of the highest ZT values achieved in p-type skutterudite compounds prepared by the traditional method of melting–annealing and spark plasma sintering.     

Effect of Synthesis and Sintering Conditions on the Thermoelectric Properties of n-Doped Mg2Si

Magnesium silicide (Mg₂Si)-based alloys are promising candidates for thermoelectric (TE) energy conversion in the middle–high temperature range. The detrimental effect of the presence of MgO on the TE properties of Mg₂Si based materials is widely known. For this reason, the conditions used for synthesis and sintering were optimized to limit oxygen contamination. The effect of Bi doping on the TE performance of dense Mg₂Si materials was also investigated. Synthesis was performed by ball milling in an inert atmosphere starting from commercial Mg₂Si powder and Bi powder. The samples were consolidated, by spark plasma sintering, to a density >95%. The morphology, and the composition and crystal structure of samples were characterized by field-emission scanning electronic microscopy and x-ray diffraction, respectively. Moreover, determination of Seebeck coefficients and measurement of electrical and thermal conductivity were performed for all the samples. Mg₂Si with 0.1 mol% Bi doping had a ZT value of 0.81, indicative of the potential of this method for fabrication of n-type bulk material with good TE performance.