Ionic liquids (ILs) are able to activate elements that are insoluble in common solvents. Here, the synthesis of binary antimony compounds directly from elements was explored. The 12 elements Ti-Cu, Al, Ga, In, and Te, known to form binary compounds with Sb, were reacted with Sb in [P₆₆₆₁₄]Cl under inert conditions in a closed glass flask with vigorous stirring for 16 h at 200 °C. This was immediately successful in four cases and resulted in the formation of NiSb, InSb, Cu₂Sb and Sb₂Te3. The applied reaction temperature is several hundred degrees below the temperatures required for solvent-free conversions. Compared to reactions based on diffusion in the solid state, reaction times are much shorter. The IL is not consumed and can be recycled. Since the reaction with Cu showed almost complete conversion, the influences of reaction time, temperature and medium were further investigated. Among the tested imidazolium ILs ([BMIm]Cl, [BMIm][OAc], [BDMIm]Cl) and phosphonium ILs ([P₆₆₆₁₄]X, X=Cl⁻, [DCA]⁻, [OAc]⁻, [NTf₂]⁻), those with chloride anion yielded the best results. In a diffusion experiment, Cu₂Sb formed on the copper, which indicates that antimony forms mobile species in these ILs. Supplemental crystal structure data of (As₃S₄)[AlCl₄], which was ionothermally synthesized from As and S, are reported.

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 RzMxCo1-xSb3-yNy) 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 RzMxCo1-xSb3-YNY) 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. / <p>QC 20160503</p> / NEXTEC / SCALTEG

A high resolution photoconductivity investigation of two 13 -3 photon magneto-absorption (TPMA) in n-InSb (n - 9 x 10 cm ) has been performed. This is the first time that two-photon absorption in a semiconductor has been studied with cw lasers only. With a stable cw CC>2 laser and a highly sensitive sampling and magnetic field modulation technique, a minimum of 4 2 transitions in the TPMA photoconductivity spectra can be observed. Most of these transitions are a result of the usual spherical approximation TPMA selections rules (An =0, ±2; As = 0 for e ⊥ B and Δn = 0; Δs = 0 for e || B) . However, some transitions, in particular several near the TPMA band edge, are not explained by these rules. The TPMA spectra have been found to depend upon crystallographic orientation. This has not been previously observed. The temperature variation of the fundamental energy gap Eg between 2 and 100° K is also obtained from TPMA experiments.

No description available.

The increasing price of oil, global warming and rapid industrial growth has drawn much attention to renewable energy technologies over the last few decades. The total energy consumption is estimated to increase 1.4% per year globally. About 90% of this energy supply is generated through fossil fuel combustion with a typical efficiency of 30-40%. The remaining 60-70% of the energy is lost to the environment via automotive exhaust or industrial processes. It is highly desired to retrieve wasted heat to improve the overall efficiency of the energy conversion. Developing thermoelectric materials and devices is a potential solution to utilize waste heat as an energy source. Skutterudites are known to be promising thermoelectric materials in the temperature range 600K to 900K. Novel nanoengineering approaches and filling of skutterudites structure can further improve the transport properties of the material. In this work, Cobalt Antimonide (Co4Sb12) based skutterudites were fabricated via mechanical milling and alloying. Rear earth material Ytterbium and Cerium are used as fillers to substitute the cages in the crystal lattice of these materials. Base material is synthesized via thermochemical reduction of the precursors under hydrogen. Further processing of the material is performed with ball milling and Spark Plasma Sintering (SPS). Ball milling parameters were optimized for nanostructuring of Co4Sb12. Grain size was significantly reduced after SPS compaction. Finally, Thermoelectric transport properties of the material is evaluated over the temperature range 300K to 900K for five different composition of the skutterudites materials. Significant reduction in materials thermal conductivity was achieved through nanostructuring.

No description available.

Many studies and experiments have been conducted over the years to find solutions to the electricity problem. This issue is not just related to how fossil fuels are dispensed. Also, the environmental concerns associated with using fossil fuels have become a severe issue, which is a major cause of environmental pollution and ozone layer damage. As such, the need for energy becomes one of the essential goals. Therefore, research has begun to revolve around thermoelectrics, which is a straightforward approach for generating energy, by converting heat directly into electricity. Cobalt antimonide (CoSb3) belongs to a broad family of materials with the skutterudite structure, which have been recently identified as potential new thermoelectric materials with high performance. The CoSb3 is one of the numerous promising thermoelectric materials in the intermediate temperature range. The binary CoSb3 is a narrow bandgap semiconductor with a relatively flat band structure and excellent electrical performance. The thermoelectric performance efficiency of binary CoSb3 is measured by its figure of merit. The figure of merit is important for thermoelectric materials and is primarily governed by the Seebeck coefficient because it exhibits a square dependence. The Seebeck coefficient of the CoSb3 can be affected by many factors that can either increase or decrease it. Strain is an important aspect for the transport properties, including the Seebeck coefficient. The goal of this thesis project is to study the effect of point defects and strain on the Seebeck coefficient of skutterudite CoSb3. The binary CoSb3 skutterudite was explored through density functional theory (DFT) to calculate the ground-state properties, in particular the Seebeck coefficient. Two different CoSb3 structures were considered, an ideal one (without any defects) and the other was termed real (containing defects). In both cases, the Seebeck coefficient and its response were studied while strain was applied by changing the volume of the structure. The non-equilibrium Green's function was used within a DFT simulation to get a transmission distribution, where it was essential for calculating the Seebeck coefficient. Moreover, oxygen molecules were placed over the (001) surface of 2 × 2 × 1 CoSb3 supercell to establish if oxidation leads to point defect formation. These simulations were carried out by DFT-based molecular dynamics. It is found that the strain affects the Seebeck coefficient in the ideal structure. At compression, the absolute value of the Seebeck coefficient increases.  By contrast, the Seebeck coefficient changed its sign from negative to positive and increased to 894 μVK−1at tension, which was unexpected. The electron density distribution map was explored to explain the behavior of the Seebeck coefficient at equilibrium, compression, and tension. It can be seen that the electron distribution between Co and Sb is increased at compression, implying an increased orbital overlap (covalent interaction). By contrast, the tension reduces the electron distribution between Sb and Co. The real structure induced by oxidation exhibits Sb vacancies. The See-beck coefficient is affected differently than that of the ideal structure. At equilibrium, the Seebeck coefficient increases to 151 μVK−1. The electron density distribution between Sb and Co is enhanced in the real structure compared to the ideal one. The most drastic change is found at tension, where the Seebeck coefficient reaches−270 μVK−1. It may be speculated that this occurs due to O which increases the orbital overlap. The strategy introduced in this work, an interplay of defects and strain effects, may be beneficial for other thermoelectric materials.

A TPV-system consists of a hot surface emitting heat radiation on a solar cell with a narrow bandgap.  A unit consisting of a boiler and a TPV-system has been constructed for testing of the performance of TPV cells. The emitter is heated by a fuel consisting of RME-oil. The radiation is collected and concentrated through two reflecting cones formed like a Faberge-egg, with an edge-type optical filter between the cones. The Faberge-egg is treated with electro-polishing in order to obtain a high reflectance of radiation. The edge filter transmits radiation of short wavelengths towards the solar cells and reflects long wavelengths back to the emitter. This increase the temperature of the emitter to prevent the TPV-cells to be overheated. The construction made was working as expected and can be used for further experiments. The performance of the TPV-cells were however very poor because of a low emitter temperature. The main problem was to obtain a good heat transport from the flame to the emitter. It is required that the emitter temperature is considerably increased for justifying a continued work on TPV-systems in combination with boilers.

Systems that exhibit the extraordinary magnetoresistance (EMR) effect and other more disordered semiconductor-metal hybrid structures have been investigated numerically with the use of the finite element method (FEM). Initially, modelling focused on circular geometry EMR devices where a single metallic droplet is embedded concentrically into a larger semiconducting disk. The dependence of the magnetoresistance of such systems on the transverse magnetic field (0 5T) and filling factor (1/16 15/16) are reported and generally show a very good agreement with existing experimental data. The influence of the geometry of the conducting region of these EMR systems was then investigated. The EMR effect was found to be highly sensitive to the shape of the conducting region with a multi-branched geometry producing a four order of magnitude enhancement of the magnetoresistance over a circular geometry device of the same filling factor. Conformal mapping has previously been shown to transform a circular EMR device into an equivalent linear geometry. Such a linear EMR device has been modelled with the EMR mechanism clearly observed. The magnetoresistive response of a circular EMR device upon changes to: the mobility of the semiconducting region; the ratio of metal to semiconductor conductivity; and the introduction of a finite resistance at the semiconductor-metal interface, have also been investigated. In order for a large EMR effect to be observed the system requires: the semiconductor mobility to be large; the conductivity of the metal to be greater than two orders of magnitude larger than that of the semiconductor; and a very low interface resistance. This modelling procedure has been extended to include inhomogeneous semiconductor-metal hybrids with a more complex and disordered structure. Two models are presented, both based upon the random distribution of a small proportion of metal inside a semiconducting material. The resultant magnetoresistance in each case is found to have a quasi-linear dependence on magnetic field, similar to that observed in the silver chalcogenides.

Le développement des systèmes de conversion photovoltaïques ces trente dernières années a permis des améliorations considérables en terme de coût et de performances. A ce jour, les meilleurs rendements de conversion photovoltaïques sont obtenus avec des systèmes à oncentration solaire utilisant des cellules multi-jonctions (MJ) à base de matériaux semi-conducteurs III-V. Dans ce domaine, le meilleur rendement atteint à ce jour est de 46,0 % sous une concentration de 508 soleils avec une cellule à 4 jonctions issu du partenariat Soitec/Fraunhofer ISE/CEA. Cette cellule MJ est composée d’une cellule tandem accordée sur GaAs assemblée par collage moléculaire à une autre cellule tandem accordée sur InP. Bien que le rendement atteint soit élevé, les performances de la cellule sont limitées sous fortes concentrations à cause de ce collage moléculaire. Dans le domaine des fortes concentrations, le record est actuellement détenu par la société américaine Solar Junction avec un rendement de 44,0 % mesuré sur une cellule triple jonction monolithique en GaInP/GaAs/GaInNAs de 0,3 cm² pour un taux de concentration de 942 soleils (irradiance directe de 942 kW/m²). Une seconde cellule a atteint un rendement performant à une irradiance directe supérieure à 1 MW/m², il s’agit d’une cellule tandem en GaInP/GaAs de l’IES-UPM qui a atteint 32,6 % sous une concentration de 1026 soleils.Dans le contexte précédent, les travaux présentés dans ce manuscrit visent à l’évaluation d’une nouvelle filière dans le domaine du CPV à base de semi-conducteurs III-V : la filière antimoniure (III-Sb). Les cellules que nous avons étudiées dans le cadre de cette thèse sont à base de GaSb et de l’alliage AlxGa1-xAsySb1-y, fabriquées de façon monolithique par MBE (Molecular Beam Epitaxy) sur substrat GaSb. Ce type de cellules, du fait de la très bonne complémentarité des gaps des matériaux, constitue une alternative crédible et originale aux cellules existantes pour une utilisation sous flux solaire fortement concentré.Le travail à réaliser dans le cadre de cette thèse porte sur :- La caractérisation électrique et optique des alliages quaternaires utilisés.- La conception et le design des cellules.- La réalisation et la mise au point de toutes les étapes technologiques nécessaires à la conception des cellules (photolithographie UV, gravure, métallisation, …).- La caractérisation électrique et optique des cellules fabriquées (I(V), TLM, réponse spectrale, …).- La caractérisation des cellules sous flux solaire (fortement) concentré.Ce travail a été cofinancé par l’Université de Montpellier et le LabEx SOLSTICE. / The development of photovoltaic conversion systems these past thirty years led to considerable improvements in terms of cost and performances. The best conversion efficiencies are currently obtained with solar concentration systems associated with multi-junction solar cells (MJSC) made of III-V materials. In this field, the record efficiency is of 46.0% under a 508-sun solar concentration with a 4-junction cell from Soitec/Fraunhofer ISE/CEA. This MJSC is composed of a tandem cell lattice-matched to GaAs wafer bonded to another tandem cell lattice-matched to InP. Although it reached high conversion efficiency, its performances are limited under solar concentration because of the wafer bonding. In the field of high solar concentrations, the record is held by Solar Junction with a monolithic triple junction GaInP/GaAs/GaInNAs cell of 0.3 cm² that reached an efficiency of 44.0% under 942 suns (direct irradiance of 942 kW/m²). Another high solar concentration efficiency record worth mentioning is held by IES-UPM with a tandem solar cell (GaInP/GaAs) that reached an efficiency of 32.6% under a concentration of 1026 suns.In this context, the work presented in this manuscript aims to evaluate the potential of a new family of III-V materials for high solar concentration applications: antimonide-based materials (III-Sb). The studied cells in this thesis are made out of GaSb and the quaternary AlxGa1-xAsySb1-y, monolithically grown by MBE (Molecular Beam Epitaxy) on a GaSb substrate. These materials, thanks to the large range of available band-gaps, represent an original and well-founded alternative to existing solar cells for high solar concentration applications.The work achieved in this thesis covers:- The electrical and optical characterization of the quaternary materials used.- The conception and designing of the cells.- The production and tuning of every technological steps in order to fabricate our solar cells (UV photolithography, etching, metal deposition,…).- The electrical and optical characterization of our fabricated solar cells (I(V), TLM, spectral response,…).- The characterization under (high) solar concentration of our cells.This work was cofounded by the University of Montpellier and the LabEx SOLSTICE.