Polycrystalline ceramics with nominal composition of Ca3-xYxCo4O9+δ (0≤x≤0.10) were grown using the citrate-complex method. Thermoelectric properties were studied using Seebeck coefficient S(T) and electrical resistivity ρ(T) measurements. These transport properties were studied in the temperature range between 100 and 290K. For low doping levels in Y substituted samples (x≤0.06) the magnitude of S(T) and ρ(T) decreases with yttrium content. The temperature behavior of S(T) and ρ(T) was interpreted in terms of the small-polaron hopping mechanism. From S(T) and ρ(T) data it was possible to calculate the thermoelectric power factor PF, which reaches maximum values close to 23 μW/K2-cm. These values become these compounds promissory thermoelectric compounds for use in low temperature thermoelectric applications.

A study of the impact of surface preparation and post-deposition annealing on contact resistivity for sputtered Ni and Co contacts to thin film Bi2Te3 is presented. The contact resistance values obtained using the transfer length method (TLM) for Ni is compared to Co as a potential contact metal to Bi2Te3. Post-deposition annealing at 100°C on samples that were sputter cleaned reduces the contact resistivity to < 10-7 Ω-cm2 for both Ni and Co contacts to Bi2Te3. Co provided similar contact resistance values as Ni, but had better adhesion and less diffusion into the thermoelectric (TE) material, making it a suitable candidate for contact metallization to Bi2Te3 based devices.

The synthesis and properties characterization of several PbS1-xTexx = 0-0.16 samples are presented. Notably it is shown how a local minimum occurs in the thermal diffusivity for the PbS1-xTex samples at x ≈ 0.03. The thermoelectric properties of doped PbS1-xTex with x = 0.03 are reported and the properties are compared to the pure PbS and PbTe end members. The electronic contribution to the total thermal conductivity is analyzed for PbS1-xTexx = 0.03 and it is shown how the lattice thermal conductivity is significantly lowered compared to single crystalline PbS.

Heat dissipation in Silicon-On-Insulator (SOI) based microdevices is hindered in the silicon device layer by the low thermal conductivity of the neighboring oxide and reduced in-plane thermal conductivity in very thin layers. This work shows that the in-plane thermal conductivity of a 260 nm thick device layers in SOI substrates can be characterized by measuring the temperature distributions induced by AC joule heating through microfabricated heaters by a scanning thermoreflectance technique. These data were fitted to numerical solutions of the heat conduction equation calculated using COMSOL® Multiphysics modeling software, suggesting the in-plane thermal conductivity of the device layer is reduced to 90±10 W/(m.K), which is consistent with phonon boundary scattering theory predictions.

The thermoelectric (Pb1-mSnmTe)1-x(PbS)x where m = 0.05 and x = 0.08 has been shown to produce PbS nanostructures that effectively scatter phonons, enhancing ZT. As Sn substitution is increased, a new phase of PbSnS2 precipitates. We find that incorporation of PbSnS2 in PbTe results in a significant reduction in lattice thermal conductivity around 0.6 W/mK at room temperature. We present preliminary characterization and thermoelectric properties.

Although AgSbTe2 exhibits excellent thermoelectric properties, the single phase is unstable and second phases such as Ag2Te and Sb2Te3 are easy to precipitate. In the present study, we tried to stabilize the AgSbTe2 phase by adding a small amount of another phase. Here we chose Pb0.16Ge0.84Te as the adding phase because the crystal structure and the lattice parameter were completely the same as those of AgSbTe2. The samples of (Ag0.5Sb0.5Te1-x(Pb0.16Ge0.84Te)x (x = 0, 0.01, 0.02, 0.05, and 0.1) were prepared and the phase stability and the thermoelectric properties were examined. The AgSbTe2 phase was stabilized in the samples of x = 0.01 and 0.02. All the samples exhibited large thermoelectric figure of merit.

We demonstrate the shape- and size-controlled synthesis of colloidal ∼10 nm bismuth telluride nanoparticles stabilized by organic ligands in solution. Post-synthetic ligand exchange with oleic acid allows for a quick and simple ligand removal by consecutive washing with basic ammonia solution. Mild spark plasma sintering yields a macroscopic nanostructured bulk solid with nanograins unaltered in size and shape. We present the full thermoelectric characterization with an emphasis on the thermal properties of this material. It will be shown that thus prepared nanostructured bulk solids possess significantly altered physical properties typical for materials with high surface-to-volume-ratios. These alterations have the potential to lead to improved thermoelectric performances benefiting from their phonon-glass electron-crystal behavior.

We investigated the impact of doping group III elements (Al, Ga, In and Tl) on the electronic structure of PbTe by first principles calculations. The impurity-induced defect level changes with respect to the charge state of the impurity. We find that among the four elements, Tl is the best candidate for the enhancement of thermoelectric efficiency, consistent with the experimental data.

The influence of incorporating nanoparticulate additions into Ca3Co4O9 (CCO) thin films prepared by pulsed laser deposition using composite targets of CCO and CCO + 3wt% BaZrO3 (BZO) on Si and LaAlO3 substrates is investigated. X-ray data and high-resolution scanning electron microscopy reveal preferred c-axis orientation of the films deposited on Si substrates with the formation of nanoparticles between ∼ 10 – 50 nm. Preliminary thermoelectric behavior shows an enhancement of the power factor α2/ρ at room temperature. The microstructure and thermoelectric behavior of the CCO films are compared to the BZO-doped films.

The paper presents the results of studies related to the technology for obtaining glass-insulated bifilar microwires (BMWs) of a thermoelectric material based on Bi2Te3 with one wire exhibiting the n-type and the other p-type conduction as well as the study of their mechanical properties by the strain method and the microscopic analysis of the morphology of structural defects with a view to preparing microthermocouples on their basis.

Preliminary studies showed that BMWs are more flexible than single microwires of the same material. The rupture strength of BMWs per unit cross section of a sample (together with the glass) ranges within 18-6 kg/mm2 with respect to diameters of 90-120 μm.

Microthermocouples with a signal value on the order of 2-12 mV in a temperature range of 23-50°C have been developed. The preparation of thermoelectric microthermocouples of BMWs significantly reduces the number of process operations in the course of their production and considerably increases their resistance to impacts and vibrations. Microthermocouples based on glass-insulated BMWs have smaller sizes and weight; they can be used for measuring temperatures in chemically aggressive media.

Samples with a composition ZrNiSn were synthesized by a combination of mechanical alloying (MA) and consolidation by either Spark Plasma Sintering (SPS) or hot pressing (HP). Appropriate stoichiometric ratios of the starting materials were milled under an inert atmosphere in a high energy ball mill for 6 hours, achieving a half-Heusler phase. X-Ray diffraction patterns of as milled powders and consolidated samples were compared and analyzed for phase purity. Thermal conductivity, electrical conductivity and Seebeck coefficient were measured as a function of temperature in the range 300 K to 800 K and compared with measurements reported for high temperature solid state reaction synthesis of this compound. HP samples, compared to SPS samples, demonstrate increased grain growth due to longer heating times. Reduced grain size achieved by MA and SPS causes increased phonon scattering due to the increased number of grain boundaries, which lowers the thermal conductivity without doping the base system with addition phonon scattering centers.

We report the effect of adding NiO nanoparticles on the transport properties of the half-Heusler alloys Zr0.5Hf0.5Ni1-xPdxSn0.99Sb0.01 (x=0, and 0.2). The half-Heusler matrix materials are prepared by traditional powder metallurgy methods. The resulting bulk matrix is mixed with different volume fractions of nanometer-sized NiO particles, previously synthesized by solution-phase chemical methods. The resulting mixture is densified under uniaxial pressure to form a composite. The resulting material is found to contain both half-Heusler and full-Heusler phases. The corresponding compounds have higher thermal conductivity and electron mobility.

Thermoelectric (TE) effects as a coupling between heat and charge transfer can be described on a classical level in the framework of the Onsager theory. Under isotropic and steady state conditions the conservation equations can be combined to obtain a thermal energy balance containing the temperature distribution as target function. Besides the temperature the balance equation contains material properties represented by the Seebeck coefficient S, the electrical and thermal conductivities σ and κ, respectively. For the sake of simplicity, a 1D scheme has been chosen for the analytical and numerical treatment. Performance investigations are often done within the framework of the Constant Properties Model (CPM) or based on temperature dependent material properties. In the 1D steady state, there is an alternative approach available based on spatial material profiles. Following the approach by Müller and co-workers, the temperature profile T(x) is calculated numerically within a model-free setup directly from the 1D thermal energy balance, e.g., based on continuous monotonous gradient functions for all material profiles, and independent and free variability of the material parameters S(x), σ(x), and κ(x) is assumed initially. Doing so, the optimum electrical current density can be determined from the maximum of the global performance parameter (power output P or efficiency η). We present analytical results for the performance optimization calculating P and η with linear material profiles for S(x), a constant electrical and thermal conductivity, fixed TE element length L and fixed boundary temperatures.

Studies on microstructures in thermoelectric compounds in the pseudobinary PbTe-Sb2Te3 system are overviewed and strategies to control the microstructure of thermoelectric compounds are discussed on the basis of the phase diagram and phase transformation theories. The morophology of solidification from the melt results in dendrite or lamellar structure depending on composition. The size-scales of the microstructures obtained by solidification can be controlled from the order of micrometers to tens of micrometers by controlling cooling rates (dendrites) or solidification velocity (lamellae). Lamellar and Widmansttäten structures are obtained by eutectoid (Pb2Sb6Te11 → PbTe + Sb2Te3) and precipitation (PbTe (Sb2Te3) → PbTe + Sb2Te3) reactions, respectively. These solid-state transformations show features with nanometer size-scales. For the eutectoid reaction the size-scale depends on annealing temperature and time. For precipitation, the size-scale depends on composition as well as cooling rate or annealing temperature. Such behavior can be understood in terms of phase transformation theories.

A series of LaCo1-xRhxO3 (x=0-1) samples and La1-ySryCo1-xRhxO3 (y = 0.05, 0.15 and x = 0.1-0.3) samples were prepared to study the effect of Rh substituion for Co in the four component system and Sr substitution for La in the five component system on the crystal structure and thermoelectric performance of the LaCoO3. At Rh substitution for Co of x=0.2 greater, the crystal structure shifts from rhombohederal (LaCoO3) to orthorhombic (LaRhO3). Thermoelectric evaluation revealed that Rh doped samples (0.3 <x <1) show large positive seebeck coefficients indicating a P-type conduction in the temperature range of the tests (273 to 775K). Rh substitution for Co decreases thermal conductivity, increases Seebeck coefficient and consequently increases the theroelectric figure of merit ZT. Sr substitution for La increases thermal and electrical conductivity and consquenently negligiblely decreases the seebeck coefficient. A thermoelectric figure-of-merit (ZT) around 0.075 has been achieved for LaCo0.5Rh0.5O3 at 775 K, and is expected to be above 0.1 at 1000 K. Sr substitution improved the TE properties throughout the lower temperature range with a ZT =0.045 observed for La0.95Sr0.05Co0.9Rh0.1O3 at 425 K and ZT = 0.05 for La0.85Sr0.15Co0.5Rh0.5O3 at 775 K. These findings provide new insight into thermoelectric perovskite oxides containing rhodium and strontium.

We report room temperature ZT calculations for silicon and indium antimonide nanowires of varying radii. Interestingly, some systems deviate significantly from the anticipated trend of ZT vs. radius. The InSb results are particularly remarkable due to the non-monotonic relationship seen between n-type ZT and wire radius; where typically we expect to see only a decrease with increasing radius, for InSb ZT increases between 20 and 100 nm wire radii. This is thought to be due to the high level of degeneracy of subbands for larger nanowire radii. These results indicate that the monotonic relationship between ZT and wire radius observed under strong confinement conditions cannot be assumed, but must be tested on a case-by-case basis for each materials system.

The formation of nanostructures within the matrix of half-Heusler thermoelectric materials can be produced by spinodal decomposition of off-stoichiometric compositions. CoSb is insoluble at high temperatures in Zr0.5Hf0.5Co1-yIrySb1-zSnz half-Heusler phases. This phase can be solubilized into the half-Heusler matrix by the use of high energy ball milling at room temperature as the synthetic method of choice. The metastable half-Heusler material decomposes in-situ while hot-pressing the powder sample into a compact pellet. Despite the fact that the thermal conductivity of the inclusion material, CoSb, is very large, (>35W/m•K), we observed reduction in the lattice thermal conductivity of the composite material. Furthermore, the electrical resistivity of the specimen was also reduced due to the metallic nature of the CoSb inclusion phase. Addition of a large fraction of the metallic inclusion leads to a percolation network of the metallic phase, thus reducing the Seebeck coefficient of the composites. Electron microscopy is carried out in order to examine boundaries between the two. Changes in the thermoelectric properties of Zr0.5Hf0.5Co1-yIrySb1-zSnz half-Heusler matrix with increasing mass percent of CoSb inclusion will be discussed.

We report synthesis of the sodium cobalt oxide γ-NaxCoO2 submicron tubules using the citric acid-based sol-gel route with the assistance of commercial porous anodized aluminium oxide (AAO) membrane with a nominal pore size of 200nm as supporting templates. The γ-NaxCoO2 submicron tubules can be obtained at 500°C using a rapid-heat-up procedure and held for 30 min. The submicron tubules have a diameter of 200-250 nm. The products are investigated using various techniques including powder x-ray diffraction, field emission scanning electron microscope and transmission electron microscope. The atomic ratio of Na/Co of theγ-NaxCoO2 submicron tubules is determined using energy dispersive x-ray spectra. The atomic ratio of Na/Co tends to be less than 0.5 due to the tendency of Na+ de-intercalating from its parent structure during the tubules collecting process.

The utilization of thermal fluctuations or Johnson/Nyquist noise as a spectroscopic technique to experimentally measure transport properties is applied to Pb and Cu metal films. Through cross-correlation and autocorrelation functions obtained from power spectral density measurements, multiple transport coefficients are obtained through the Green-Kubo formalism. Supported rigorously by the underlying fluctuation-dissipation theory, this new experimental technique provides a direct measurement of absolute thermoelectric coefficients in addition to the electrical resistivity, electronic contribution to thermal conductivity, Lorentz number and various diffusion coefficients. This work reports the validation results of the experiment accomplished through the use of materials with thermoelectric properties widely accepted by the thermoelectric community, Pb and Cu. Further validation of the data was accomplished by comparing resistivity results to standard collinear four-probe resistivity measurements. Thermal fluctuation data for Pb at 300 K resulted in 5.9% and 2.02% agreement with the published Seebeck and four-probe resistivity data respectively. The Cu thermal fluctuation measurements at 300 K showed agreement within 3.76% and 6.14% for the published Seebeck and four-probe data respectively thus lending further credibility to the experimental method and underlying theory.

The performance of the thermoelectric devices and materials is shown by a dimensionless figure of merit, ZT = S2σT/K, where S is the Seebeck coefficient, σ is the electrical conductivity, T is the absolute temperature and K is the thermal conductivity. ZT can be increased by increasing S, increasing σ or decreasing K. We have prepared 100 alternating nanolayered films of SiO2/SiO2+CoSb3 using the ion beam assisted deposition (IBAD). The 5 MeV Si ions bombardments have been performed using the AAMU Pelletron ion beam accelerator to make quantum clusters in the nanolayered superlattice films at the three different fluences to decrease the cross plane thermal conductivity, increase the cross plane Seebeck coefficient and cross plane electrical conductivity. We have characterized 100 alternating nanolayered films of SiO2/SiO2+CoSb3 before and after Si ion bombardments as we measured the cross-plane Seebeck coefficient, the cross-plane electrical conductivity, and the cross-plane thermal conductivity for three different fluences.