In this article we report a facile, highly energy-efficient synthesis route for the fabrication of nanostructured bulk thermoelectric copper selenide (Cu 2 Se). Using microwave-assisted thermolysis, nanopowders of Cu 2 Se were produced starting from commonly available precursor 2 materials. Optimized compaction parameters were achieved through an investigation of different factors in the compaction process to achieve enhanced thermoelectric properties. The high ZT value of 2 obtained at 900 K for optimized SPS-compacted Cu 2 Se nanopowders exceeds the state of the art Cu 2 Se by 25% at the same temperature. The results demonstrate the prominent improvement in ZT attributed both to the low thermal conductivity, as low as 0.38 W/m-K at 900 K, and the enhancement in the power factor of nanostructured Cu 2 Se.

Low temperature thermoelectric (TE) materials are in demand for more efficient cooling and power generation applications. Iron antimonide (FeSb2) draws great attention over the past few years because of its enhanced power factor values. Polycrystalline bulk FeSb2 nanopowder was prepared via a low-temperature molten salts approach followed by subsequent thermal treatment in synthetic air and hydrogen gas for calcination and reduction reactions, respectively. Structural analysis confirms the desired final phase with submicrometer grain size and high compaction density after consolidation using spark plasma sintering (SPS). TE transport properties revealed that the material is n-type below 150 K and p-type above this temperature; this suggests antimony vacancies in FeSb2. The electrical conductivity increased significantly, and the highest conductivity achieved was 6000 S/cm at 100 K. The maximum figure-of-merit, ZT, of 0.04 is achieved at 500 K, which is about 6 times higher than the earlier reported state-of-the art ZT value for the same material.

A novel synthesis route for the fabrication of p-type nanostructured skutterudite, FexCo1-xSb3 in large quantity is reported. This scalable synthesis route provides nano-engineered material with less impact on the environment compared to conventional synthesis procedures. Several Fe substituted compositions have been synthesized to confirm the feasibility of the process. The process consists of a nano-sized precursor fabrication of iron and cobalt oxalate, and antimony oxides by chemical co-precipitation. Further thermochemical processes result in the formation of iron substituted skutterudites. The nanopowders are compacted by Spark Plasma Sintering (SPS) technique in order to maintain nanostructure. Detailed physicochemical as well as thermoelectric transport properties are evaluated. Results reveal strongly reduced thermal conductivity values compared to conventionally prepared counterparts, due to nanostructuring. P-type characteristic was observed from the Seebeck measurements while electrical conductivity is high and shows metallic behavior. The highest TE figure of merit of 0.25 at 800 K has been achieved, which is strongly enhanced with respect to the mother compound CoSb 3 . This suggests the promise of the utilized method of fabrication and processing for TE applications with improved performance.

In this work, a novel CMOS compatible process for Si-based materials has been presented to form SiGe nanowires (NWs) on SiGe On Insulator (SGOI) wafers with unprecedented thermoelectric (TE) power factor (PF). The TE properties of SiGe NWs were characterized in a back-gate configuration and a physical model was applied to explain the experimental data. The carrier transport in NWs was modified by biasing voltage to the gate at different temperatures. The PF of SiGe NWs was enhanced by a factor of >2 in comparison with bulk SiGe over the temperature range of 273 K to 450 K. This enhancement is mainly attributed to the energy filtering of carriers in SiGe NWs, which were introduced by imperfections and defects created during condensation process to form SiGe layer or in NWs during the processing of NWs.

Latest nanotechnology concepts applied in thermoelectric (TE) research have opened many new avenues to improve the ZT value. Low dimensional structures can improve the ZT value as compared to bulk materials by substantial reduction in the lattice thermal conductivity, κL. However, the materials were not feasible for the industrial scale production of macroscopic devices because of complicated and costly manufacturing processes involved. Bulk nanostructured (NS) TEs are normally fabricated using a bulk process rather than a nano-fabrication process, which has the important advantage of producing in large quantities and in a form that is compatible with commercially available TE devices.We developed fabrication strategies for bulk nanostructured skutterudite materials based on FexCo1-xSb3. The process is based on precipitation of a precursor material with the desired metal atom composition, which is then exposed to thermochemical processing of calcination followed by reduction. The resultant material thus formed maintains nanostructured particles which are then compacted using Spark Plasma Sintering (SPS) by utilizing previously optimized process parameters. Microstructure, crystallinity, phase composition, thermal stability and temperature dependent transport property evaluation has been performed for compacted NS FexCo1-xSb3. Evaluation results are presented in detail, suggesting the feasibility of devised strategy for bulk quantities of doped TE nanopowder fabrication.

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Skutterudites are known to be efficient thermoelectric (TE) materials in the temperature range from 600 K to 900 K. Dimensionless figure of merit (ZT) for filled skutterudite TE materials have been reported as ca. 1 at 800 K. Novel nano- engineering approaches and filling of the skutterudites crystal can further improve the transport properties and ultimately the ZT. Although classified among the promising TE materials, research on their large-scale production via bottom up synthetic routes is rather limited. In this work, large quantity of cobalt antimonide (CoSb3) based skutterudites nanopowder (NP) was fabricated through a room temperature co-precipitation precursor method. Dried precipitates were process by thermo-chemical treatment steps including calcination (in air) and reduction (i n hydrogen). CoSb3 NPs were then mixed with silver (Ag) nanoparticles at different weight percentages (1%, 5% and 10% by wt) to form nanocomposites. Skutterudite NP was then consolidated by Spark Plasma Sintering (SPS) technique to produce highly dense compacts while maintaining the nanostructure. Temperature dependent TE characteristics of SPSd CoSb3 and Ag containing nanocomposite samples were evaluated for transport properties, including thermal conductivity, electrical conductivity and Seebeck coefficient over the temperature range of 300 - 900 K. Physicochemical, structural and microstructural evaluation results are presented in detail

Depending on their application temperature thermoelectric (TE) materials are classified in three main categories; as low (up to 250°C), intermediate (up to 550°C) and high (above 600°C) temperature. Currently, Skutterudites (CoSb3) based materials have shown promising results in the intermediate temperature range (300-500°C). This family of material is highly suitable for automotive, marine transportation and industrial power generation applications to recover the waste heat from the exhaust and generate electricity. Conventional TE modules need p- and n-type semiconductor materials and for the skutterudite family, iron (Fe) has proven to be among the best candidates for the substitution of cobalt sites. Additionally, rare earths are introduced as rattlers in the crystal cages of the skutterudite to decrease the thermal conductivity, thus improving the figure of merit ZT of the TE material. For practical application for device fabrication, stability of these materials is of great importance. Compositional stability is being addressed as the material decomposes above certain temperature. Temperature dependent x-ray diffraction study was performed on Fe substituted, Yb-filled skutterudites, using Beam Line I711 at MAX LAB, to observe the crystal structure as a function of temperature. Diffraction patterns were collected from room temperature up to 500°C by utilizing Huber furnace. The results show success in filling process showing almost 80% reduction of the thermal conductivity from bulk. Additionally the thermal expansion coefficient value was within the average value for skutterudites which proves practical application of this powder for industrial applications.