We report on the thermoelectric properties of the filled skutterudite Ce0.9Fe3CoSb12 prepared via non-equilibrium synthesis method. Melt-spun ribbons were directly converting into single phase polycrystalline pellets under pressure. For comparison, pellets with the same composition were also prepared using the conventional solid-state reaction followed by long term annealing. It was found that the non-equilibrium synthesized samples have higher power factors and lower thermal conductivity, leading to substantially higher figure of merit.

Composites containing mainly-half-Heusler MNiSn (HH) and full-Heusler MNi2Sn (FH) were prepared by solid state reaction of a mixture of polycrystalline bulk HH alloy with various concentrations of Ni up to 10 wt.%. Electrical conductivities, thermal conductivities and thermopowers of spark plasma sintered specimens of the as synthesized composite materials were measured in the temperature range from 300 K to 750 K. The conduction type of the composite changes from semiconductor to semimetal for Ni concentrations up to 2 wt.% and from semimetal to metal for higher Ni concentrations above 5 wt.%. A strong reduction in lattice thermal conductivity was observed for the composite containing 10 wt. % Ni inclusions.

The performance of the thermoelectric materials and devices 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 multi-nano layer of SiO2/SiO2+Cu superlattice films using the ion beam assisted deposition (IBAD). The 5 MeV Si ions bombardments have been performed at the different fluences using the AAMU Pelletron ion beam accelerator to make quantum clusters in the multi-layer superlattice thin films to decrease the cross plane thermal conductivity increase the cross plane Seebeck coefficient and cross plane electrical conductivity. To characterize the thermoelectric thin films before and after Si ion bombardments we have measured the cross-plane Seebeck coefficient, the cross-plane electrical conductivity, and the cross-plane thermal conductivity for different fluences.

Recently nanostructured bulk silicon and silicon-germanium have achieved large increases in the thermoelectric figure of merit (ZT). The ZT enhancement is attributed to a significant reduction in the lattice thermal conductivity while maintaining relatively high carrier mobility. Silicon-based thermoelectric devices are attractive due to their low-toxicity, thermal stability, low density, relative abundance and low cost of production. Although significant enhancements in ZT have been achieved using the nanostructuring route, additional decoupling of the thermal and electric transport terms is still necessary in order for silicon-based materials to be viable for thermoelectric applications such as waste heat recovery or radioisotope thermoelectric generators. It is theorized that additional increases in ZT could be achieved by forming composites with nanostructured inert inclusions to further scatter the heat-carrying phonons. Here we present the impact of insulating and conductive nanoparticle composites on ZT. The nanostructured composites are formed via ball milling and high pressure sintering of the nanoparticles. The thermoelectric properties and microstructure of the silicon-based composites are discussed.

Thermoelectric calcium cobalt oxide (Ca1.24Co1.62O3.86) with high Seebeck coefficient was prepared by self-propagating high temperature synthesis (SHS) followed by a short post treatment process. Synthesized samples were analyzed by XRD for their phase purity for samples prepared from different reactants mixtures. A final element model of SHS of calcium cobalt oxide was developed to study the temperature history and reaction rate change during the synthesis. This model can be used to predict reaction temperatures for various initial conditions.

This study shows for the first time, the correlation between the microstructural properties (chemical composition and its homogeneity) and the thermoelectric properties for p-type Bi0.5Sb1.5Te3 electroplated films (10-15 μm thickness). High microstructural quality of Bi0.5Sb1.5Te3 electroplated films (a close to stoichiometry chemical composition with its high homogeneity elements distribution) was achieved by using an additive in the plating solution (sodium ligninsulfonate) as a surfactant agent. A fine-grained microstructure of 280 nm to 1μm has been observed for these materials, which half that of the plated films without a surfactant. The thermoelectric properties of electrodeposited Bi0.5Sb1.5Te3 films obtained without microstructural optimisation, show modest Seebeck coefficient values of 20-120 μm/K, electrodeposited film with an optimised microstructure exhibits very high values of Seebeck coefficient of 220-300 μm/K.

Zr0.5Hf0.5Ni0.8Pd0.2Sn0.99Sb0.01 composites with various concentrations of WO3 inclusions were synthesized by mechanical alloying using high energy shaker mill. High density hot pressed pellets of the synthesized materials were characterized using powder X-ray diffraction and transmission electron microscopy and their thermoelectric properties were investigated in the temperature range from 300 to 750 K. The electrical conductivity of the composites at 300 K decreases from 2500 S/cm for 0 wt.% WO3 alloy to 2200 S/cm for the composite with 2 wt.% WO3 inclusion. The electrical conductivity of composites containing 5 wt.% and 10 wt.% WO3 inclusions showed sharp increases with increasing WO3 content. The electrical conductivity of the composites monotonically decreases with rising temperature. All samples showed n-type semiconducting behavior and the thermopower values decrease with increasing WO3 content. The lattice thermal conductivity of the composites increases with increasing WO3 content. However, these values are about 30% lower than that of Zr0.5Hf0.5Ni0.8Pd0.2Sn0.99Sb0.01 alloy prepared by high temperature solid-state techniques. The synthesized composites showed lower figure of merit than the half-Heusler matrix due to large reduction in the thermopower values with increasing WO3 content.

With the advent of nanotechnology, the field of thermoelectric (TE) materials has been re-invigorated with many recent advances towards materials with high thermoelectric efficiency (dimensionless figure of merit, ZT). The realization of such materials opens up new avenues to the creation of devices that can be used in freon-less refrigeration, micro-electronic cooling, or for harnessing lost heat energy from sources such as car engines. In our own research work, we have successfully synthesized thermoelectric nanoscale materials composed of bismuth, antimony, and tellurium. By using a wet chemical thermal reduction procedure, we were able to create bismuth, antimony, and tellurium composite particles. What's more, by employing different molecular encapsulating agents in the synthesis, we were able to control the resulting shapes of the nanomaterials, resulting in both one and two dimensional bismuth, antimony, and tellurium nanoparticles. The one dimensional nanowires exhibit a micron scale length and ∼20-50nm diameter, while the two dimensional nanodiscs exhibit a diameter of ∼100nm and a thickness of ∼25nm. The unique morphology of these materials make them ideal candidates for processing into functional thermoelectric devices. This paper focuses on our recent study of the synthesis of bismuth, antimony, and tellurium composite nanomaterials of a nanowire and nanodisc morphology, which was directed by the capping agents used in the synthesis. Part of our preliminary study includes analysis of the thermoelectric efficiency of the materials. The resulting nanomaterials are characterized using techniques such as HR-TEM, XPS, XRD, and SEM the results of which provide insight into the design and synthesis of nanoscale materials with enhanced thermoelectric properties.

Indentation tests were performed to assess the influence of compositional changes on the mechanical properties of several half-Heusler compounds with the general composition Zr0.5Hf0.5Co1-x Ir x Sb0.99Sn0.01 (x=0.0,0.1,0.3,0.5,0.7). These samples were synthesized by high temperature solid-state reactions and were consolidated by hot-pressing. Indentation measurements were obtained using both microhardness testing (Vickers) and depth-sensing nanoindentation. These measurements were used to determine the microhardness and the elastic modulus of each half-Heusler compound. The Vickers hardness values were found to range between 876 and 964. A slight increase in hardness was observed with the addition of iridium. The elastic stiffness values ranged from 229 GPa to 246 GPa. Here, a slight decrease in stiffness was observed with the addition of iridium.

AgSbTe2 is the critical component in both LAST-m and TAGS-x system, which are two state-of-the-art mid-temperature thermoelectric bulk nanocomposites. By adjusting the Ag2Te/Sb2Te3 ratio, Sb2Te3 and Ag2Te precipitated samples were obtained with x = 0.68 to 0.74 and x = 0.84 to 0.90 (x as in (Ag2Te)x/2(Sb2Te3)1-x/2), respectively. The single phased AgSbTe2 was obtained with the x value of 0.78 and 0.81, which is consistent of the previous results on the phase diagram of (Ag2Te)x(Sb2Te3)1-x system. Comparing the effect of the two different precipitates, Ag2Te are much effective for the improvements of thermoelectric properties in AgSbTe2 nanocomposites. Utilizing the high-resolution transmission electron microscopy, Ag2Te was observed as nanodots and nano-lamellae embedded in the AgSbTe2 matrix, which can be related to the energy filtering effect for the increase of Seebeck coefficient. The relationship among the composition, microstructure and thermoelectric properties was systematically studied. It can be noticed that the thermoelectric properties of AgSbTe2 system are very sensitive to the composition, especially at low temperature. The maximum figure of merit ZT value of 1.53 was obtained at 500 K for Ag0.84Sb1.16Te2.16 with 40% increase comparing with the single phased sample.

High energy density and power density are two important considerations in the design of a portable power source. High efficiency of energy conversion is one of the important factors in achieving high energy density. We report on the design, fabrication and characterization of a high efficiency and power density thermoelectric generator. Segmented thermoelectric elements with a high temperature-weighted average zT are used in the fabrication of the generator to achieve high energy conversion efficiency. A comprehensive model of the generator has been developed that includes temperature dependent thermoelectric properties for the segmented thermoelectric element design, and system level thermal and electrical losses. These models are used to guide the design of a high efficiency thermoelectric generator. A 14W size portable thermoelectric generator was built and its performance for converting thermal energy into electrical energy was characterized and compared to the model predictions. The magnitude of individual loss mechanisms and their effect on overall system efficiency are presented. The evolution of the device design and critical design parameters that have been incorporated or modified to minimize performance losses and improved device robustness are discussed. Important future design optimizations that can further reduce losses for improved performance were identified.

The dramatic reduction in the thermal conductivity of rough silicon nanowires is due to phonon localization in the wire resulting from multiple scattering of phonons from the rough walls. We report the dependence of thermal conductivity of the nanowires as a function of the surface roughness and the diameter of the wire by modeling the nanowire as a waveguide. In addition, we estimate the impact of boundary condition, dimensionality and cross section of rough wire on the thermal conductivity. This theoretical model gives insights for tailoring thermal conductivity and enhancing the ZT of silicon to 1 for its use in thermoelectrics

Yb14MnSb11 is a very promising thermoelectric material for high temperature applications. This compound is a member of a large family of Zintl phases with a “14-1-11” A14MPn11 stoichiometry (Pn = P, As, Sb, Bi; A = Ca, Ba, La, Sr, Yb, Eu; M = Mn, Al, Cd, Ga, In, Nb, Zn). Yb14MnSb11 exhibits low lattice thermal conductivity values and a p-type semimetallic behavior with values of the non-dimensional figure of merit zT peaking at 1.4 above 1200 K. There is significant interest in investigating how substitutions on any of the atomic sites impact the charge carrier concentration and mobility, band gap and lattice thermal conductivity. Recent reports have studied substitutions on the Yb and Mn sites with the goal of reducing hole carrier concentration and improving carrier mobility values.

High energy ball milling has been shown to be a convenient method of synthesis to prepare Yb14MnSb11 and it has been used here to explore the solid solution systems derived from this compound by substituting Sb with Bi. High energy ball milling is a non-equilibrium process and not all of the 14-1-11 compounds are easily formed with this method. Characterization of the synthesized compositions was done by X-ray diffraction, electron microprobe, and high temperature measurements of the electrical and thermal transport properties up to 1275 K. The experimental results on undoped and doped solid solution samples are compared to that of pure Yb14MnSb11 samples prepared by the same high energy ball milling technique.

Bismuth antimony telluride (BiSbTe) nanowires were electrodeposited at constant potentials into polycarbonate templates from a tartaric-nitric acid baths having different electrolyte compositions. Composition analysis of the nanowires showed that Sb deposits at higher potentials compared to BiTe. Maximum seebeck coefficients of -337.7 μV/K and 227.2 μV/K were obtained for n-type and p-type nanowires samples Bi4.6Te5.4 and Bi4.3Sb5 respectively. Nonmonotonic resistance behavior was observed for all the nanowires.

PbTe-based materials are promising for efficient heat energy to electricity conversion. We present studies of the thermoelectric properties of the PbTe-SrTe system. X-ray diffraction patterns reveal that all the samples crystallize in the rock salt structure without noticeable secondary phase. Na2Te doping of the PbTe-SrTe materials resulting in a positive sign Hall coefficient indicating p-type conduction. Lattice thermal conductivity is significantly decreased with the insertion of SrTe in PbTe lattice. The ZT ∼ 1.3 of these materials is derived from their very low thermal conductivities and reasonably high power factor at 800 K.

We have prepared a variety of filled skutterudites through non-equilibrium synthesis by converting melt-spun ribbons into single phase polycrystalline bulk under pressure. In general, better thermoelectric properties are found in these samples. In this work, we performed microstructure characterization of non-equilibrium synthesized p-type filled skutterudite CeFe4Sb12 by X-ray diffraction, scanning electron microscopy and transmission electron microscopy in order to understand the structural origin of the improved thermoelectric properties. It is found that the non-equilibrium synthesized samples have smaller grain size and cleaner grain boundaries when compared to the samples prepared by the conventional solid-state reaction plus long term annealing. While smaller grain size can help reduce the lattice thermal conductivity, cleaner grain boundaries ensure higher carrier mobility and subsequently, higher electrical conductivity at the application temperatures.

Design of semiconducting nanomaterials with an indirect electronic bandgap is currently one of the major areas of research to obtain a high thermoelectric yield by lowering their lattice thermal conductivity. Intensive investigations on superlattices were performed to achieve this goal. However, like one-dimensional nanowires, they decrease heat transport in only one propagation direction of the phonons. Moreover, they often lead to dislocations since they are composed of layered materials with a lattice mismatch. Design of superlattices with a thermoelectric figure of merit ZT higher than unity is therefore hazardous. Self-assembly of epitaxial layers on silicon has been used for bottom-up synthesis of three-dimensional (3D) Ge quantum-dot (QD) arrays in Si for quantum-device and solar-energy applications. Using the atomic-scale 3D phononic crystal model, it is predicted that high-density 3D arrays of self-assembled Ge QDs in Si can as well show an extreme reduction of the thermal transport. 3D supercrystals of Ge QDs in Si present a thermal conductivity that can be as tiny as that of air. These extremely low values of the thermal conductivity are computed for a number of Ge filling ratios and size parameters of the 3D Si-Ge supercrystal. Owing to incoherent phonon scattering with predominant near-field effects, the same conclusion holds for supercrystals with moderate QD disordering. As a result, design of highly-efficient CMOS-compatible thermoelectric devices with ZT possibly much higher than unity might be possible. In this theoretical study, simultaneous evolution of both temperature and average distance between the Ge QDs is analyzed for a non-variable Ge filling ratio to obtain thermal-conductivity values as low as that of air (+/- 0.025 W/m/K).

We have prepared 100 periodic nano-layers of SiO2/AgSiO2 with Au layer deposited on both sides as metal contacts. The deposited multi-layer films have a periodic structure consisting of alternating layers where each layer is 3.3 nm thick. The purpose of this research is to tailor the figure of merit of the thermoelectric materials generated from the nanolayers of nanocrystals of Ag with SiO2 as host and as buffer layer using a combination of co-deposition and MeV ions bombardment taking advantage of energy deposited in the MeV ion track to nucleate nanoclusters. The electrical and thermal properties of the nanolayered structures were studied before and after 5 MeV Si ions bombardment at various fluences to form nanocrystals. In addition to thermoelectric properties, some optical properties of the SiO2/SiO2+Ag multi-layer superlattice films have been studied.

In this work, we have studied the possibility to use a microwire of BiSn to design an anisotropic thermoelectric generator. The glass-coated microwire of pure and Sn-doped bismuth was obtained by the Ulitovsky method; it was a cylindrical single-crystal with orientation (1011) along the wire axis; the C3 axis was deflected at an angle of 70° to the microwire axis. It is found that doping of bismuth wires with tin increases the thermopower anisotropy in comparison with Bi by a factor of 2 – 3 in the temperature range of 200 – 300 K. According to the preliminary results, for a Bi microwire with a diameter of 10 μm with a glass coating of 35 μm, the transverse thermopower is ∼ 150 μV/(K*cm); for BiSn, 300 μV/(K*cm).The design of an anisotropic thermogenerator based on BiSn microwire is proposed. The miniature thermogenerator will be efficient for power supply of devices with low useful current.

In addition to the considerable thermopower anisotropy of BiSn wires in a glass coating, they exhibit stable thermoelectric properties, high mechanical strength and flexibility, which allows designing thermoelectric devices of various configurations on their basis.

We report the effects of HfO2 nanoparticles as inclusion to the Zr0.5Hf0.5Ni0.8Pd0.2Sn0.99Sb0.01 half-Heusler matrix on the thermoelectric properties. X-ray powder diffraction and transmission electron microscopy were employed for the phase identification and microstructure characterization of the composites. The transport properties are mainly discussed with regards to the microstructure details.