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.

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.

Current fossil fuel based energy sources have a huge shortcoming when one discusses their efficiency. The conversion efficiency of fossil fuel-based technologies is less than 40% in best cases. Therefore, until the renewable energy section is mature enough to handle all the energy demand one has to research and develop the technologies available to harvest the energy from the waste heat generated in fossil fuel-based supply sources. One of these emerging technologies is the use of thermoelectric (TE) devices to achieve this goal, which are solid-state devices capable of directly interconverting between heat and electrical energy. In the past decade there has been a significant scientific and financial investment within the field to enhance their properties and result in time/energy efficient fabrication processes of TE materials and devices for a more sustainable environment.

In this thesis with use of chemical synthesis routes for nanostructured bulk thermoelectric materials iron antimonide (FeSb₂), skutterudites (based on general formula of R_zM_xCo_1-xSb_3-yN_y) and copper selenide (Cu₂Se) are developed. These materials are promising candidates for use in thermoelectric generators (TEG) or for sensing applications. Using chemical synthesis routes such as chemical co-precipitation, salt melting in marginal solvents and thermolysis, fabrication of these TE materials with good performance can be performed with high degree of reproducibility, in a much shorter time, and easily scalable manner for industrial processes. The TE figure of merit ZT of these materials is comparable to, or better than their conventional method counterparts to ensure the applicability of these processes in industrial scale.

Finally, through thorough investigation, optimized consolidation parameters were generated for compaction of each family of materials using Spark Plasma Sintering technique (SPS). As each family of TE nanomaterial investigated in this thesis had little to no prior consolidation literature available, specific parameters had to be studied and generated. The aim of studies on compaction parameters were to focus on preservation of the nanostructured features of the powder while reaching a high compaction density to have positive effects on the materials TE figure of merit.

Dagens fossilbränslebaserade energikällor har en enorm brist gällande effektivitet. Effektiviteten av fossilbränslebaserade teknologiers omvandling är mindre än 40 % i bästa fall. Därför tills förnybar energi är mogen nog att hantera alla energibehov, måste man forska och utveckla teknik för att skörda energi från spillvärme i fossilbränslebaserade försörjningskällor. En av dessa nya tekniker är tillämpning av termoelektriska (TE) material för att uppnå målet. Nämnde material är Soldi-State materialer som kan transformera mellan värme och elektrisk energi. Under det senaste decenniet har det pågått en stor vetenskaplig och ekonomisk investering inom området för att förbättra termoelektriska materials egenskaper. Dessutom ville man ta fram tid/energieffektiva TE material och komponenter för en mer hållbar miljö.

I denna avhandling utvecklades och producerades termoelektriska material såsom järn antimonid (FeSb₂), skutterudit (baserat på allmänna formeln R_zM_xCo_1-xSb_3-YN_Y) och koppar selenid (Cu₂Se) med hjälp av kemiska syntesmetoder. Genom att Använda kemiska syntesmetoder som kemisk samutfällning, salt smältning i marginella lösningsmedel och termolys, kan material med hög grad av reproducerbarhet och ställbar för industriella processer tillverkas.   Termoelektrisk omvandling effektivitet hos uppnådde material är betydligt högre än resultat av andra studier. I och med detta kan man säga att materialet kan användas inom industri.

Slutligen, genom en grundlig undersökning optimerades packningsparametrar som genererades för packning av varje materialgrupp med hjälp av Spark Plasma Sintring teknik (SPS). Eftersom ingen relevant studie finns för varje grupp av termoelektriska nanomaterial som undersökts i denna avhandling, studerades och genererades dessa specifika parametrar. Syftet med studien är att fokusera på bevarande av nanostrukturerade egenskaperna hos pulvret och att samtidigt nå en hög packningstäthet för att ha positiva effekter på materialens termoelektriska omvandlingseffektivitet.

In this article an alternative high yield route for the synthesis of CoSb3-based unfilled skutterudites is presented. Using low-melting temperature salts of the constituents, melting and mixing them homogeneously in a hydrophobic liquid with postprocessing of the powders we achieve a more intimately mixed alloy compared to the conventional melting and metallurgical processes. The proposed method consists of a fast and low-temperature processing step followed by a thermochemical post-processing step, compared to the conventional methods of fabricating skutterudites, which require high temperatures and long processing times. Several structural characterization techniques were used to assess the mechanism of synthesis, verify the purity of the material as well as the reproducibility of the process. Detailed analysis and results are presented in support of the proposed process. Additionally, compaction of the powders with SPS technique provided a safe route to maintaining the nanopowder size and achieving low thermal conductivity (3 W/mK). The proposed method can easily be scaled up and adopted by the industry.

A facile and high yield synthesis route was developed for the fabrication of bulk nanostructured copper selenide (Cu2Se) with high thermoelectric efficiency. Starting from readily available precursor materials and by means of rapid and energy-efficient microwave-assisted thermolysis, nanopowders of Cu2Se were synthesized. Powder samples and compacted pellets have been characterized in detail for their structural, microstructural and transport properties. alpha to beta phase transition of Cu2Se was confirmed using temperature dependent X-ray powder diffraction and differential scanning calorimetry analyses. Scanning electron microscopy analysis reveals the presence of secondary globular nanostructures in the order of 200 nm consisting of <50 nm primary particles. High resolution transmission electron microscopy analysis confirmed the highly crystalline nature of the primary particles with irregular truncated morphology. Through a detailed investigation of different parameters in the compaction process, such as applied load, heating rate, and cooling profiles, pellets with preserved nanostructured grains were obtained. An applied load during the controlled cooling profile was demonstrated to have a big impact on the final thermoelectric efficiency of the consolidated pellets. A very high thermoelectric figure of merit (ZT) above 2 was obtained at 900 K for SPS-compacted Cu2Se nanopowders in the absence of the applied load during the controlled cooling step. The obtained ZT exceeds the state of the art in the temperature ranges above phase transition, approaching up to 25% improvement at 900 K. The results demonstrate the prominent improvement in ZT attributed both to the low thermal conductivity, as low as 0.38 W m(-1) K-1 at 900 K, and the enhancement in the power factor of nanostructured Cu2Se. The proposed synthesis scheme as well as the consolidation could lead to reliable production of large scale thermoelectric nanopowders for niche applications.

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 CoSb3. This suggests the promise of the utilized method of fabrication and processing for TE applications with improved performance.

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.

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 Fe xCo1-xSb3. Evaluation results are presented in detail, suggesting the feasibility of devised strategy for bulk quantities of doped TE nanopowder fabrication.

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 coprecipitation precursor method. Dried precipitates were process by thermo-chemical treatment steps including calcination (in air) and reduction (in hydrogen). CoSb3 NPs were then mixed with silver (Ag) nanopanicles 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 SPS'd 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.

In this article we report a highly efficient synthesis route for fabrication of nanostructured bulk thermoelectric (TE) copper selenide (Cu₂Se) nanopowders. Using Microwave (MW) assisted synthesis and through bottom-up synthesis approach, copper selenide nanopowders were fabricated. The nanopowders then underwent an optimized SPS compaction generated with the aim of high compaction density as well as the overall thermoelectric figure of merit ZT. The structural and thermoelectric transport property evaluation was performed and a ZT of 2.1 at 900 K was achieved. The high ZT value was attributed to the dramatically reduced thermal conductivity which reached values of as low as 0.38 W/mK. Detailed process, structural evaluation and TE transport property measurements of the prepared samples are presented.IntroductionThermoelectric