Effects of Second Phase Yb5Sb3 on the Thermoelectric Properties of YbAl3

The compound YbAl₃ exhibits a very high power factor but also rather a large thermal conductivity, leading to a low figure of merit. The second phase Yb₅Sb₃ was introduced in the YbAl₃ matrix to reduce its thermal conductivity. The composites (YbAl₃)_1?x (Yb₅Sb₃) _x with x = 0, 0.01, 0.05, 0.10, and 0.20 were synthesized by high frequency induction melting, annealing treatment, and spark plasma sintering. The thermoelectric properties of the composites were evaluated. The composites are of n-type conduction. The pure YbAl₃ obtained in this work shows a high power factor of 11,500 μW m^?1 K^?2 but also a high thermal conductivity of 19.6 W m^?1 K^?1. However, the existence of Yb₅Sb₃ compound in the YbAl₃ matrix enhances the electrical resistivity and the absolute Seebeck coefficient of the composite, but significantly reduces its thermal conductivity in the temperature range considered, thereby enhancing the figure of merit. The highest ZT value of 0.23 may be obtained in the sample (YbAl₃)_0.95(Yb₅Sb₃)_0.05 at room temperature, which is apparently higher than that of pure YbAl₃.     

Thermoelectric Properties of Polycrystalline SrZn2Sb2 Prepared by Spark Plasma Sintering

Compact polycrystalline samples of SrZn₂Sb₂ [space group $ P\overline{3} m1 $ , a = 4.503(1) Å, c = 7.721(1) Å] were prepared by spark plasma sintering. Thermoelectric performance, Hall effect, and magnetic properties were investigated in the temperature range from 2 K to 650 K. The thermoelectric figure of merit ZT was found to increase with temperature up to ZT = 0.15 at 650 K. At this temperature the material showed a high Seebeck coefficient of +230 μV K^?1, low thermal conductivity of 1.3 W m^?1 K^?1, but rather low electrical conductivity of 54 S cm^?1, together with a complex temperature behavior. SrZn₂Sb₂ is a diamagnetic p-type conductor with a carrier concentration of 5 × 10¹⁸ cm^?3 at 300 K. The electronic structure was calculated within the density-functional theory (DFT), revealing a low density of states (DOS) of 0.43 states eV^?1 cell^?1 at the Fermi level.     

Effect of Cooling Conditions on the Microstructure and Thermoelectric Properties of Zn/Si-Codoped InSb

InSb is a good candidate thermoelectric (TE) material owing to its high carrier mobility and narrow band gap around 0.18 eV. However, a high figure of merit (ZT) value has not been achieved with InSb because of its high lattice thermal conductivity (κ _lat). To reduce the κ _lat of InSb, we prepared a ZnIn₁₈SiSb₂₀ alloy by Zn/Si codoping into the In lattice sites of InSb. Polycrystalline samples of ZnIn₁₈SiSb₂₀ were prepared by a solid-state reaction method combined with hot pressing. To investigate the microstructures and TE properties resulting from different cooling conditions, samples were prepared by water quenching or slow cooling after an annealing process. The different cooling conditions led to different ZnIn₁₈SiSb₂₀ microstructures and TE properties. The electrical transport properties showed that both samples exhibited metal-like behavior and p-type conduction. The thermal conductivity values of the quenched and slow-cooled samples at room temperature were 8.7 W m^?1 K^?1 and 11.7 W m^?1 K^?1, respectively. A maximum ZT value of 0.23 was obtained at 723 K for the quenched ZnIn₁₈SiSb₂₀ sample.     

Development of a Thermal Conductivity Measurement System Using the 3ω Method and Application to Thermoelectric Particles

For this study, we developed a thermal conductivity, κ, measurement system using 3ω method. We checked the system accuracy by measuring κ for a glass substrate (1737; Corning). Conventional evaporated aluminum wire and ink-jet printed silver wire were used as sensor wires. The system realized a κ measurement of glass within 10 % error. We estimated κ of aggregated p-type (Bi_1?x Sb _x )₂Te₃ particles using a two heat flow model. The estimated thermal conductivity of the sample κ _sample are 0.06–0.27 WK^?1 m^?1, which is smaller than the bulk value.     

Effect of Sintering Temperature on Microstructure, Electrical Properties, and Thermal Expansion of Perovskite-Type La0.8Ca0.2CrO3 Complex Oxides Synthesized by a Combustion Method

Perovskite-type La_0.8Ca_0.2CrO₃ complex oxides were synthesized by a combustion method. Microstructural evolution, electrical properties, and thermal expansion behavior of the ceramics were investigated in the sintering temperature range of 1250°C to 1450°C. It was found that the electrical conductivity (σ _e) remarkably improved with increasing sintering temperature from 1250°C to 1400°C, ascribed to the development of microstructural densification, whereas it declined slightly above 1400°C due to generation of excessive liquid. The specimen sintered at 1400°C had a maximum conductivity of 31.6 S cm^?1 at 800°C, and lowest activation energy of 0.148 eV. The improvement of the thermal expansion coefficient (TEC) with increasing sintering temperature was monotonic as a result of the microstructural densification of the materials. The TEC of La_0.8Ca_0.2CrO₃ sintered at 1400°C was about 10.5 × 10^?6 K^?1, being consistent with other components as high-temperature conductors. With respect to microstructure, electrical properties, and thermal expansion, the preferable sintering temperature was ascertained to be about 1400°C, which is much lower than for the traditional solid-state reaction method.     

Crystal Structure and Physical Properties of Skutterudites SrPd4Sn x Sb12−x

A Pd-based skutterudite phase SrPd₄Sn _x Sb_12?x in which the 8c sites of the structure are occupied solely by Pd atoms and with a homogeneity range of 4.3(2) ≤ x ≤ 5.8(2) (wavelength dispersive x-ray spectroscopy) has been synthesized by solid-state reaction then spark-plasma sintering (SPS). It crystallizes as the filled-skutterudite structure type, electronically compensated by substitution of Sn for Sb at framework (24g) positions. The unit cell decreases substantially with increasing nominal and detected Sn content. Magnetization, specific heat, Hall effect, electrical resistivity, thermopower, and thermal conductivity were measured for the SPS-treated samples. SrPd₄Sn _x Sb_12?x is a diamagnetic material. Depending on composition it occurs in the metallic or semiconducting states. Hall effect data show that the type and concentration of most of the carriers depend on the Sn/Sb atomic ratio. The thermal conductivity of SrPd₄Sn _x Sb_12?x is approximately 3.0–5.0 W K^?1 m^?1 at 300 K. The Seebeck coefficient is negative throughout the temperature range covered, reaching approximately ?20 μV K^?1 at 300 K.     

Crystallographic, Thermoelectric, and Mechanical Properties of Polycrystalline Ba8Al x Si46−x Clathrates

The Al content dependence of crystallographic, thermoelectric, and mechanical properties is reported for polycrystalline Ba₈Al _x Si_46?x (nominal x = 15 to 17) clathrates prepared by combining arc melting and spark plasma sintering methods. The elastic constants and the coefficient of thermal expansion (CTE), which are also important properties for designing thermoelectric devices, are presented. Powder x-ray diffraction, scanning electron microscopy, and energy-dispersive x-ray spectroscopy (EDX) indicate that the type I clathrate is the major phase of the samples but impurity phases (mainly BaAl₂Si₂, Si, and Al) are included in the samples with high Al contents. The actual Al content x determined by EDX ranges from approximately 14 to 15. The absolute value of the Seebeck coefficient increases and the electrical conductivity decreases as the Al content increases. The changes in Seebeck coefficient and electrical conductivity are explained in terms of the dependence of the carrier concentration on the Al content. The elastic constants and the CTE of the samples depend weakly on the Al content. Some of the properties are compared with reported data of single crystals of Ba₈Al₁₆Ge₃₀, Ba₈Ga₁₆Ge₃₀, Sr₈Ga₁₆Ge₃₀, silicon, and germanium as standard references. The effective mass, Hall carrier mobility, and lattice thermal conductivity, which govern the transport properties, are determined to be ~ 2.4m ₀, ~ 7 cm² V^?1 s^?1, and ~ 1.3 W m^?1 K^?1, respectively, for actual Al content x of about 14.77. The thermoelectric figure of merit ZT is estimated to be about 0.35 at 900 K for actual Al content x of about 14.77.     

Electrical Conductivity of V2O5–TeO2–Sb Glasses at Low Temperatures

Semiconducting glasses of the type 40TeO₂–(60 ? x) V₂O₅–xSb were prepared by rapid melt quenching and their dc electrical conductivity was measured in the temperature range 180–296 K. For these glassy samples, the dc electrical conductivity ranged from 2.26 × 10^?7  S cm^?1 to 1.11 × 10^?5 S cm^?1 at 296 K, indicating the conductivity is enhanced by increasing the V₂O₅ content. These experimental results could be explained on the basis of different mechanisms (based on polaron-hopping theory) in the different temperature regions. At temperatures above Θ _D/2 (where Θ _D is the Debye temperature), the non-adiabatic small polaron hopping (NASPH) model is consistent with the data, whereas at temperatures below Θ _D/2, a T ^?1/4 dependence of the conductivity indicative of the variable range hopping (VRH) mechanism is dominant. For all these glasses crossover from SPH to VRH conduction was observed at a characteristic temperature T _R ≤ Θ _D/2. In this study, the hopping carrier density and carrier mobility were determined at different temperatures. N (E _F), the density of states at (or near) the Fermi level, was also determined from the Mott variables; the results were dependent on V₂O₅ content.     

Scattering of phonons by a spatially correlated system of Fe atoms and the low-temperature anomaly of thermal conductivity in HgSe:Fe crystals

The thermal conductivity κ of HgSe:Fe samples with various content N _Fe of Fe impurity was studied in the temperature range of 8–60 K. It was found that the dependence of the thermal conductivity κ on N _Fe is unconventional at low temperatures. For T<12 K, the value of κ first decreases with an increase in the Fe concentration up to N _Fe=5×10¹⁸ cm^?3 and then increases and attains a maximum for N _Fe=(1–2)×10¹⁹ cm^?3. A further increase in Fe concentration brings about a steady decrease in thermal conductivity. The electron-and phonon-related thermal conductivity of HgSe:Fe crystals with consideration of the effects caused by the ordering of trivalent Fe ions was analyzed. It is shown that both the electron-and phonon-related contributions to thermal conductivity at low temperatures are increasing functions of Fe concentration in the range of 5×10¹⁸<N _Fe<(1–2)×10¹⁹ cm^?3. However, the electronic contribution is too small to account for the experimental increase in thermal conductivity. An analysis of the lattice contribution to thermal conductivity showed that an anomalous increase in thermal conductivity is caused by a reduction in the Rayleigh scattering of phonons by a system of Fe ions with mixed valence and is related to the spatial ordering of Fe³⁺ ions.     

Reducing Lattice Thermal Conductivity of the Thermoelectric Compound AgSbTe2 (P4/mmm) by Lanthanum Substitution: Computational and Experimental Approaches

In this study we performed lattice dynamics first-principles calculations for the promising thermoelectric (TE) compound AgSbTe₂, and estimated the stability of its three polymorphs over a wide temperature range from 0 to 600 K. We calculated the vibrational density of states of the AgSbTe₂ (P4/mmm) phase. The results suggested that formation of substitutional defects at Ag-sublattice sites impedes lattice vibrations, thereby reducing lattice thermal conductivity. We focused on calculations based on the Debye approximation for the compound La_0.125Ag_0.875SbTe₂, and predicted reduction of the average sound velocity from 1684 to 1563 m s^?1 as a result of La doping. This is manifested as a ca. 14% reduction in thermal conductivity. To confirm the results from computation we produced two Ag–Sb–Te-based alloys, a ternary alloy without La addition and a quaternary alloy containing La. We measured the thermal conductivity of both alloys by use of the laser flash analysis method, and, as a result of La alloying, observed a reduction in thermal conductivity from 0.92 to 0.71 W m^?1 K^?1 at 573 K, as calculated from first principles.     

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.     

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.     

Paradoxical Enhancement of the Power Factor of Polycrystalline Silicon as a Result of the Formation of Nanovoids

Hole-containing silicon has been regarded as a viable candidate thermoelectric material because of its low thermal conductivity. However, because voids are efficient scattering centers not just for phonons but also for charge carriers, achievable power factors (PFs) are normally too low for its most common form, i.e. porous silicon, to be of practical interest. In this communication we report that high PFs can, indeed, be achieved with nanoporous structures obtained from highly doped silicon. High PFs, up to a huge 22 mW K^?2 m^?1 (more than six times higher than values for the bulk material), were observed for heavily boron-doped nanocrystalline silicon films in which nanovoids (NVs) were generated by He⁺ ion implantation. In contrast with single-crystalline silicon in which He⁺ implantation leads to large voids, in polycrystalline films implantation followed by annealing at 1000°C results in homogeneous distribution of NVs with final diameters of approximately 2 nm and densities of the order of 10¹⁹ cm^?3 with average spacing of 10 nm. Study of its morphology revealed silicon nanograins 50 nm in diameter coated with 5-nm precipitates of SiB _x . We recently reported that PFs up to 15 mW K^?2 m^?1 could be achieved for silicon–boron nanocomposites (without NVs) because of a simultaneous increase of electrical conductivity and Seebeck coefficient. In that case, the high Seebeck coefficient was achieved as a result of potential barriers on the grain boundaries, and high electrical conductivity was achieved as a result of extremely high levels of doping. The additional increase in the PF observed in the presence of NVs (which also include SiB _x precipitates) might have several possible explanations; these are currently under investigation. Experimental results are reported which might clarify the reason for this paradoxical effect of NVs on silicon PF.     

Low Thermal Conductivity in High-Z Thermoelectric Materials with Controlled Nanodispersions

We report wet chemical synthesis of a hierarchical nanocomposite thermoelectric material, (Bi,Sb)₂Te₃ + 2 vol.% Sb₂O₃, which exhibits a very high ZT value of 1.5 at 333 K. The key to such a high ZT value is to design the interfacial density (ID) of the nanodispersion and the mean diameter of the matrix (d) in the nanocomposite. To this end, (Bi,Sb)₂Te₃ with Sb₂O₃ nanodispersion was developed using in situ precipitation during solvothermal treatment. Nanocomposite structure was observed in sintered specimens. By evaluation of thermoelectric properties, it was confirmed that phonon scattering on the surface of Sb₂O₃ dispersion and κ _ph correspondingly decreased with ID. The formation of a well-controlled Sb₂O₃ dispersion (mean diameter of dispersion: D = 1.5 nm, ID = 0.06 nm^?1) and fine grains (d = 38 nm) led to an extremely low lattice thermal conductivity of 0.28 W m^?1 K^?1, while reducing the electrical conductivity moderately according to the conventional mixture rule.     

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 Properties of Polyaniline Films with Different Doping Concentrations of (±)-10-Camphorsulfonic Acid

The temperature dependence of the thermoelectric properties was investigated for polyaniline (PANI) films doped with different concentrations of (±)-10-camphorsulfonic acid (CSA) with molar ratio x of CSA to two phenyl-nitrogen units of x = 1 to 0.2. All PANI-CSA films exhibit p-type conduction. The temperature dependence of the electrical conductivity of the films with low CSA concentrations is consistent with a transport mechanism of variable-range hopping. On the other hand, the Seebeck coefficient above room temperature shows a linear increase with temperature, attributed to the metallic nature of PANI-CSA. As the CSA concentration decreases, the absolute value of the Seebeck coefficient increases while the electrical conductivity extremely decreases, probably due to the changes not only in the carrier concentration but also in the degree of structural disorder. The power factor increases monotonically with increasing CSA concentration toward x = 1 (the maximum limit). The thermal conductivity value of CSA-PANI film with x = 1 is as low as about 0.20 W m^?1 K^?1 in the through-plane direction and about 0.67 W m^?1 K^?1 in the in-plane direction. The thermoelectric figure of merit ZT in the in-plane direction is estimated to be approximately 1 × 10^?3 for x = 1.     

Fabrication of Titanium Oxide-Based Composites by Reactive SPS Sintering and Their Thermoelectric Properties

Titanium oxide-based composites containing (1) Nb, (2) Nb and Sr, and (3) Sr and La were fabricated by a combination of wet processing and reactive spark plasma sintering in which the metal oxide components were reduced by reaction with titanium nitride. If only TiO₂ was used as the starting material, several Magneli-type phases of oxygen-deficient titanium oxides were obtained. When mixed with Nb ions with Ti:Nb = 0.9:0.1, microsegregation of Nb ions was observed (case 1). If Sr was added, a perovskite, SrTiO₃ (STO) phase occurred (case 2), which contained La ions in the case of La addition (case 3). The sintered compacts consisted largely of grains of about 1 μm in size. In the case of Ti-Nb combination (case 1), a unique stripe pattern also appeared inside the grains. The electrical conductivity increased monotonically with increasing temperature in the case of the pure Magneli phases and the Nb-containing composite, whereas bow-shaped temperature dependences with a maximum were observed in the case of the composites containing STO phases. The Seebeck coefficients were commonly negative, and the absolute values increased with temperature. The thermal conductivity was between 2 W m^?1 K^?1 and 4 W m^?1 K^?1 in the temperature range from room temperature to 800°C. A maximum ZT of 0.34 was achieved at 800°C (case 2).     

Low-Temperature Physical and Thermoelectric Properties of Ba8Ni5Ge41

Resistivity, Hall resistivity, thermopower, thermal conductivity, and magnetization are reported for polycrystalline Ba₈Ni₅Ge₄₁. Ba₈Ni₅Ge₄₁ is diamagnetic with susceptibility χ _dia = (?2.4 to ?2.82) × 10^?7 emu/g. Semiconductor-like behavior was observed for the resistivity. The thermopower shows positive values for a wide temperature range. The Hall resistivity indicates the dominance of electrons, suggesting the existence of multiband conductance. At room temperature, the thermal conductivity is 1.78(5) W/K m. The highest ZT of Ba₈Ni₅Ge₄₁ is 0.0016 at about 278 K.     

Effects of Ni, Pd, and Pt Substitutions on Thermoelectric Properties of CoSi Alloys

Ni-, Pd-, and Pt-substituted CoSi samples have been prepared by an arc melting and annealing procedure. The x-ray diffraction and scanning electron microscopy results show that Ni and Pd are effective n-type dopants for CoSi, while Pt is immiscible with CoSi and forms an impurity phase with a possible chemical formula of PtCoSi₂. The thermoelectric properties were measured from 80 K to 300 K. For Ni- and Pd-doped samples, the electrical resistivity and Seebeck coefficient decrease simultaneously due to the increasing carrier concentration. For Pt-substituted samples, the electrical resistivity also decreases. However, this reduction is thought to be not due to an increase in carriers but rather to originate from the effect of the Pt-rich impurity phase at the grain boundaries. The Seebeck coefficient is not affected by 1% Pt substitution; however, further increase of the Pt level also causes a decrease in the Seebeck coefficient. The room-temperature power factor is 63 μW K^?2 cm^?1 for pure CoSi and 73 μW K^?2 cm^?1 for the Co_0.99Pt_0.01Si sample. Although the thermal conductivity is reduced for both n-type-doped and Pt-substituted samples around 80 K, the room-temperature values are still close to that of pure CoSi. As a result, ZT of 0.13 is obtained at room temperature for Co_0.99Pt_0.01Si, an 18% increase compared with CoSi.     

Thermoelectric Properties of Al-Doped ZnO Thin Films

We have prepared 2 % Al-doped ZnO (AZO) thin films on SrTiO₃ substrates by a pulsed laser deposition technique at various deposition temperatures (T _dep = 300–600 °C). The thermoelectric properties of AZO thin films were studied in a low temperature range (300–600 K). Thin film deposited at 300 °C is fully c-axis-oriented and presents electrical conductivity 310 S/cm with Seebeck coefficient ?65 μV/K and power factor 0.13 × 10^?3 Wm^?1 K^?2 at 300 K. The performance of thin films increases with temperature. For instance, the power factor is enhanced up to 0.55 × 10^?3 Wm^?1 K^?2 at 600 K, surpassing the best AZO film previously reported in the literature.