Round-robin measurements of two candidate materials for a Seebeck coefficient Standard Reference Material™

A Standard Reference Material (SRM^™) for the Seebeck coefficient is critical for inter-laboratory data comparison and for instrument calibration. To develop this SRM^™, we have conducted an international round-robin measurement survey of two candidate materials—undoped Bi₂Te₃ and constantan (55% Cu and 45% Ni alloy). Measurements were performed in two rounds by twelve laboratories involved in active thermoelectric research using a number of commercial and custom-built measurement systems and techniques. We report the results of these measurements and the statistical analysis performed. Based on this extensive study, we have selected Bi₂Te₃ as the prototype standard material.     

Influence of negative pressure on thermoelectric properties of Sb2Te3

We investigated the influence of negative pressure on the electrical conductivity, the Seebeck coefficient, and the power factor of Sb₂Te₃. We performed first-principles calculations with the linearized-augmented plane-wave method considering negative hydrostatic pressure in the range from zero to −2 GPa and doping for electrons and holes up to 10²⁰ cm⁻³. Our results predict a significant increase of the Seebeck coefficient and the power factor under negative pressure for certain doping concentrations.     

Modified texture and high temperature transport properties of doubly substituted BaxAgyCa2.8Co4O9 thermoelectric oxide

Doubly substituted polycrystalline compound bulk samples of Ba_xAg_yCa_2.8Co₄O₉ were prepared via citrate acid sol-gel method followed by spark plasma sintering. The phase composition, orientation, texture and high temperature electrical properties were systematically investigated. The results showed that the orientation and the texture could be modified by altering ratio of Ba to Ag. The resistivity and the Seebeck coefficient of substituted samples were decreased by decreasing Ba/Ag ratio except for that of Ba_0.1Ag_0.1Ca_2.8Co₄O₉ sample with lowest electrical resistivity (7.2 mΩ cm at 973 K), moderately high Seebeck coefficient (172 μV/K at 973 K) and improved power factor (0.42 mW/mK² at 973 K).     

Development of a high-throughput thermoelectric screening tool for combinatorial thin film libraries

We have developed a high-throughput thermoelectric screening tool for the study of combinatorial thin films. This tool consists of a probe to measure resistance and Seebeck coefficient on an automated translation stage. A thin film library of the (Ca_1−x−ySr_xLa_y)₃Co₄O₉ ternary system has been fabricated on a Si (1 0 0) substrate, using combinatorial pulsed laser deposition by the natural-composition-spread method. We have demonstrated successful mapping of the resistance and Seebeck coefficient of this film library. The mapping indicates that the substitution of La for Ca results in an increase of both resistance and Seebeck coefficient, and that of Sr results in a decrease of resistance. The screening tool allows us to measure 1080 data points in 6 h.     

Transport and magnetic properties of cobalt doped CeNiAl4

Electrical resistivity and thermoelectric power (TEP) have been measured in polycrystalline sample of CeNi_0.75Co_0.25Al₄. The magnetization measurements have been performed in oriented powder with a-axis of the crystallites parallel to the external magnetic field. All the data have been compared with its parent compound CeNiAl₄. In the range 120-300 K, the Seebeck coefficient is significantly higher for alloy than for the parent material and exhibits a peak at ∼150 K. R(T)/R(300) follows a logarithmic temperature dependence for all samples above 100 K, and rapidly decreases as the temperature is lowered. The decrement is much faster in the cobalt doped samples than in the parent compound, suggesting stronger electronic correlations in the former. Inverse magnetic susceptibility in oriented powder follows a Curie-Weiss law above 100 K and shows p_eff=2.7 slightly higher than that of the free Ce³⁺ ion value of 2.5.     

Combinatorial synthesis and high throughput evaluation of thermoelectric power factor in Mg-Si-Ge ternary compounds

Discrete phase libraries of thermoelectric compounds, Mg_xSi_yGe_1−y, were fabricated by a combinatorial pulsed laser deposition followed by annealing as a thin film form on an integrated ceramic substrate. In the substrate are embedded four probe electrical contacts to each sample, lead wires and pads to be accessed by needle probes. Resistivity and Seebeck coefficient were evaluated electrically, while temperature difference was locally given to each sample by a local heater also embedded in the substrate. The sample temperature (300-673 K) was controlled by a heating stage and temperature difference at the two contact points for each sample was evaluated by an infrared camera. The dependences of polarity and absolute values of Seebeck coefficient on the composition agree well with the data in literature.     

Magnetic and transport properties of UPd2Sb

A new compound UPd₂Sb was prepared and studied by means of X-ray diffraction, magnetization, electrical resistivity, magnetoresistivity, thermoelectric power and specific heat measurements. The phase crystallizes with a cubic structure of the MnCu₂Al-type (s.g. ). It orders antiferromagnetically at T_N=55 K and exhibits a modified Curie-Weiss behaviour with reduced effective magnetic moment at higher temperatures. The electrical resistivity behaves in a manner characteristic of systems with strong electronic correlations, showing Kondo effect in the paramagnetic region and Kondo-like response to the applied magnetic field. The Seebeck coefficient exhibits a behaviour expected for scattering of conduction electrons on a narrow quasiparticle band near the Fermi energy. The low-temperature electronic specific heat in UPd₂Sb is moderately enhanced being about 81 mJ/mol K².     

High-temperature electronic transport properties of La1−xCaxMnO3+δ (0.0?x?1.0)

La_1−xCa_xMnO_3+δ (0.0?x?1.0) samples were prepared and their resistivity and Seebeck coefficients were measured in the high-temperature range. Ca doping changes the ratio of Mn³⁺/Mn⁴⁺ and influences the electronic transport behavior markedly. With the increase of Ca concentration, the samples change from a p-type semiconductor to an n-type one and Seebeck coefficient becomes increasingly negative. Low doping (x=0.2) and high doping (x=0.8) induces the drop of the resistivity compared with undoped LaMnO_3+δ and CaMnO_3+δ samples due to the rise of carrier concentration. However, the resistivity of moderate-doped samples (x=0.4, 0.6) is larger than low- and high-doped samples because dopant scattering decreases carrier mobility.     

Power factor enhancement in Pr-substituted alloys prepared by high-pressure sintering

Bi₈₅Sb_15−xPr_x (x=0,1,2,3) alloys with partial substitution of Pr for Sb were synthesized by mechanical alloying followed by high-pressure sintering. The crystal structure was characterized by X-ray diffraction. The electrical conductivity and Seebeck coefficient were measured in the temperature range of 80–300 K. The results show that the electrical conductivity and Seebeck coefficient of Pr-substituted samples are both larger than those of the reference sample, Bi₈₅Sb₁₅, in the whole measurement temperature range. The power factor of Bi₈₅Sb₁₃Pr₂ reaches a maximum value of 3.83×10⁻³ W K⁻² m⁻¹ at 235 K, which is about four times larger than that of the reference sample, Bi₈₅Sb₁₅, at the same temperature.     

Hall mobility of amorphous Ge2Sb2Te5

The electrical conductivity, Seebeck coefficient, and Hall coefficient of three-micron-thick films of amorphous Ge₂Sb₂Te₅ have been measured as functions of temperature from room temperature down to as low as 200 K. The electrical conductivity manifests an Arrhenius behavior. The Seebeck coefficient is p-type with behavior indicative of multi-band transport. The Hall mobility is n-type and low (near 0.07 cm²/V s at room temperature).     

Thermoelectric power of Ce-based intermediate valent systems

The thermoelectric power was measured in the temperature range 6-300 K for a few Ce-based compounds known as intermediate valent systems, i.e. Ce₂Ni₂In, Ce₂Rh₂In, Ce₂Ni₂Ga and CeNi₅Sn, in order to scan these ternaries for possible low-temperature thermoelectric applications. The experimental data were analyzed in terms of phenomenological models and compared to those reported in the literature for similar materials. The results corroborated unstable character of the Ce valence in the ternaries studied. However, the magnitude of the Seebeck coefficient, though being considerably enhanced, is for all of them much lower than those known for the best performers in the field of strongly correlated thermoelectrics: CePd₃ and YbAl₃.     

Magnetic and transport properties of YbRhIn5 and YbIrIn5 single crystals

Single crystals of YbRhIn₅ and YbIrIn₅ have been grown by flux method. The crystals were characterized by means of X-ray diffraction, magnetic and electrical transport measurements. Both compounds were found to be weak diamagnets with metallic character of the electrical conductivity and the Seebeck coefficient.     

Effect of Zn substitution for Co on the transport properties of Y BaCo4O7

Electrical resistivity and Seebeck coefficients of Y BaCo_4−xZn_xO₇ (x=0.0,0.5,1.0,2.0) were investigated in the temperature range 350-1000 K. It was found that the electrical resistivity and activation energy increase with increasing Zn concentration, while Seebeck coefficients do not increase but decrease when electrical resistivity increases. We explained the increase of electrical resistivity and the drop of Seebeck coefficients for Zn-substituted samples by the decrease of carrier mobility, rather than of carrier concentration. The effect of oxygen absorption and desorption on the electrical resistivity and Seebeck coefficients was also investigated. An abrupt change of transport properties happens at about 650 K for x=0.0 and 0.5 samples measured in oxygen. For x=1.0 and 2.0 samples, however, such change disappears and the transport behavior in oxygen is almost same as that in nitrogen due to the significant suppression of oxygen diffusion caused by the higher Zn concentration in these samples.     

Thermoelectric properties of Bi0.9Sb0.1 prepared by high pressure

The Bi_0.9Sb_0.1 powders were prepared by mechanical alloying and then pressed under 6 GPa at different pressing temperatures. X-ray diffraction spectra showed that the single phase was formed. The nanostructure of grain was observed by bright-field imaging. Electrical conductivity, Seebeck coefficient, and thermal conductivity had been investigated in the temperature range of 80-300 K. The absolute Seebeck coefficient value of 120.3 μV/K was measured at 130 K. The figure-of-merit reached a maximum value of 0.90×10⁻³ K⁻¹ at 140 K.     

Influence of Thomson effect on the resultant local Seebeck coefficient in thermoelectric composite materials

The resultant local Seebeck coefficient α _R (=α _S−α _T) at the interface of a thermoelement has not yet been measured, although it is an important factor governing the thermoelectric efficiency, where α _S is the local Seebeck coefficient and α _T is the one caused by the Thomson effect. It is shown in this paper that α _S, α _T, and α _R of the p- and n-type Cu/Bi–Te/Cu composites are obtained analytically and experimentally on the assumption that the local temperature of the composite on which the temperature difference ΔT is imposed varies linearly with changes in position along the composite. They were indeed estimated as a function of position from the local experimental data of R,ΔI,ΔT, and V generated by applying an additional current of ±I to the composite, where R is the electrical resistance and ΔI is a current generated by the composite. As a result, it was found that the absolute values of α _S at the hot interface of the p- and n-type composites are approximately 1.5 and 1.4 times higher than their lowest values in the middle region of the composite, respectively, while those of α _T are less than 8% of α _S all over the composite and are so small that the relation α _R≈α _S can be held. We thus succeeded in measuring α _R at the interfaces of the composite.     

Thermoelectric properties of the Bi2−xYxRu2O7 (x=0-2) pyrochlores

Electrical conductivity and Seebeck coefficient for the Bi_2−xY_xRu₂O₇ pyrochlores with x=0.0,0.5,1.0,1.5,2.0 were measured in the temperature range of 473-1073 K in air. With increasing Bi content, the temperature dependence of the electrical conductivity changed from semiconducting to metallic. The signs of the Seebeck coefficient were positive in the measured temperature range for all the samples, indicating that the major carriers were holes. The temperature dependence of the Seebeck coefficient for the Y₂Ru₂O₇ indicated the thermal activation-type behavior of the holes, while that for the Bi_2−xY_xRu₂O₇ with x=0.0-1.5 indicated the itinerant behavior of the holes. The change in the conduction behavior from semiconductor to metal with increasing Bi content is consistent with the increase in the overlap between the Ru4d t_2g and O2p orbitals, but the mixing of Bi6s, 6p states at E_F may not be ruled out. The thermoelectric power factors for the Bi_2−xY_xRu₂O₇ with x=1.5 and 2.0 were lower than 10⁻⁵ W m⁻¹ K⁻² and those with x=0.0,0.5,1.0 were around 1-3×10⁻⁵ W m⁻¹ K⁻².     

Low temperature thermoelectric properties of Pb- or Sn-doped Bi-Sb alloys

Pb- or Sn-doped Bi₈₈Sb₁₂ alloys were prepared by direct melting, quenching, and annealing. The Bi-Sb alloy phase was predominant in all samples. Pb or Sn atoms were distributed almost uniformly in Bi₈₈Sb_12, while some segregation was confirmed at the grain boundaries when Pb or Sn was involved heavily. The thermoelectric properties of these doped materials were investigated by measuring the Hall coefficient, electrical resistivity, and Seebeck coefficient between 20 K and 300 K. The Hall and Seebeck coefficients of Pb- or Sn-doped samples were positive at low temperatures, indicating that the doping element acted as an acceptor. Temperatures resulting in positive Hall and Seebeck coefficients further increased with increasing doping amount and with respect to the annealing process. As a result, a large power factor of 1.2 W/mK² could be obtained in the 3-at% Sn-doped sample at 220 K, with a large positive Seebeck coefficient.     

Effect of high electric field on the dc conduction of TeO2-V2O5-MoO3 amorphous bulk material

Effect of high electric field on the dc conductivity of TeO₂-V₂O₅-MoO₃ amorphous bulk samples with different molar ratio of each component was investigated with gap-type electrode arrangement. At low electric fields, the current-voltage (I–V) characteristics has a linear shape, while at high electric fields (>10³ V/cm), bulk samples show nonlinear behavior (nonohmic conduction) and current-voltage characteristics shows increasing deviation from Ohm’s law with increasing current density. High-field effect of Pool-Frenkel type was observed at electrical fields about 10³−10⁴ V/cm. In addition, positive deviation from Pool-Frenkel effect was observed when a field higher than about 10⁴ V/cm was applied.     

Low-temperature thermoelectric properties of Bi85Sb15−xNbx alloys prepared by high-press sintering

The nanocrystalline materials with the general formula Bi₈₅Sb_15−xNb_x (x=0, 0.5, 1, 2, 3) were prepared by mechanical alloying and subsequent high-pressure sintering. Their transport properties involving electrical conductivity, Seebeck coefficient and thermal conductivity have been investigated in the temperature range of 80-300 K. The absolute value of Seebeck coefficient of Bi₈₅Sb₁₃Nb₂ reaches a maximum of 161 μV/K at 105 K, which is 69% larger than that of Bi₈₅Sb₁₅ at the same temperature. The power factor and figure-of-merit are 4.45×10⁻³ WK⁻²m⁻¹ at 220 K and 1.79×10⁻³ K⁻¹ at 196 K, respectively. These results suggest that thermoelectric properties of Bi₈₅Sb₁₅ based material can be improved by Nb doping.     

The effect of annealing process on the physical properties of La1−xNaxMnOy

The effect of Na doping and annealing time on the structure, electrical properties, magnetoresistance and thermopower properties has been investigated in perovskite La_1−xNa_xMnO_y (x=0.025, 0.075 and 0.1) systems. La_1−xNa_xMnO_y crystallizes in a single-phase rhombohedral structure. It is observed a simultaneous occurrence of the ferromagnetic to paramagnetic state and metallic to insulating state. In the meanwhile, a large negative magnetoresistance with low applied magnetic field is observed. In addition, ρ(T) curves for Na-doped samples exhibit another broad transition T_ms2 below T_ms. Such double peak behavior in the ρ(T) curve interpreted by the electronic inhomogeneity in the samples. The sign of S changes from positive to negative depending on composition. The values of Seebeck coefficient are small (in the microvolt range).