L'augmentation des émissions de CO2 entraîne un réchauffement de la planète préjudiciable aux équilibres écologiques terrestres. Dans ce contexte, le stockage de CO2 dans des formations géologiques terrestres et sous-marines se pose comme un moyen intéressant de limiter les conséquences de ces émissions. Cependant cette solution nécessite une surveillance continue afin de détecter d'éventuelles fuites au niveau d'une zone de stockage. Les travaux de thèse présentés concernent le développement d'un capteur optique en fibre de chalcogénures pour la détection de CO2 gazeux fonctionnant dans le moyen infrarouge. Cette détection est basée sur un phénomène de luminescence, jouant le rôle de source déportée et partiellement absorbée en présence de CO2. Le développement de ces fibres optiques a demandé un important travail en sciences des matériaux et en caractérisation spectroscopique. Un prototype a été fabriqué et utilisé avec succès sur le terrain lors de campagnes de mesure menées in-situ. / The increase of CO2 emissions causes global warming harmful to ecological balances in earth. In this context, CO2 storage in geological formations is an interesting way to limit the consequences of these emissions. However, this solution requires continuous monitoring to detect possible leaks at storage area. The presented work involves the development of an optical fiber sensor based on chalcogenide glasses for the CO2 gas detection operating in the infrared. This detection is based on a luminescent phenomenon, acts as a remote source and partly absorbed in the presence of CO2. The development of these fiber optic asked important work in materials science and spectroscopic characterization. A prototype was manufactured and successfully used in the field during measurement campaigns in situ.

L’objectif principal de ce travail est de développer des optiques moulées transparentes du visible à l’infrarouge thermique 8-12μm pour des applications de vision multi-spectrales. La recherche de compositions de verres utilisables pour ces applications a été faite parmi les verres de chalcogénures (connus pour leurs grandes transparences dans l’infrarouge), plus précisément dans les systèmes GeS2-Ga2S3-CsCl et GeSe2-Ga2Se3-CsI. Ces deux systèmes présentent des transparences étendues dans le visible avec l’ajout d’halogénures d’alcalin.En privilégiant une transparence dans le domaine visible, le système à base de soufre a été plus précisément étudié avec la sélection de deux compositions 75GeS2-15Ga2S3-10CsCl et 65GeS2-20Ga2S3-15CsCl. Les transmissions optiques, les indices de réfraction, les dispersions chromatiques et les variations d’indices en fonction de la température pour ces compositions ont été mesurés. Les propriétés thermiques, la mise en forme des verres ainsi que les propriétés mécaniques ont été présentées pour compléter la caractérisation de ces matériaux. Ces compositions possèdent de bonnes stabilités contre la cristallisation et des transparences étendues de 0,5μm à 11,5μm. Ces résultats nous permettent d’envisager la production d’optiques couvrant une large bande spectrale et de proposer une alternative au matériau ZnS pour les systèmes optiques. Cependant, les dispersions chromatiques de ces deux verres possèdent des comportements très similaires. Une étude de ce paramètre important pour corriger les aberrations chromatiques a été faite pour permettre de déterminer une composition avec une dispersion différente.Pour ces verres, l’addition de chlorure de césium engendre une légère dégradation des propriétés optiques due à la réaction du verre avec l’humidité environnante. Pour protéger ces verres contre la corrosion de l’atmosphère, une couche protectrice de ZnS a été appliquée par pulvérisation cathodique. De plus, un traitement antireflet a été appliqué par Thales Angénieux pour optimiser la transmission de ces verres dans les bandes spectrales spécifiées. Ce revêtement antireflet agit également comme un revêtement de protection. Ces travaux sur des verres à base de GeS2-Ga2S3 pour des applications optiques, nous ont également conduits à étudier ces verres contenant des ions de sodium pour la conduction ionique avec l’ajout d’halogénure de sodium (NaI et NaCl). La conductivité ionique de ces verres a été mesurée et comparée à la conductivité des verres contenant du lithium. Il a été démontré que le système GeS2-Ga2S3-NaI peut conduire à des verres avec une conductivité ionique de 10-6 S.cm-1 à température ambiante. / The objective of our study is to develop moldable optics operating simultaneously from the visible up to the thermal infrared region (8-12μm) for multispectral applications. The research of a suitable composition for optical applications has been done among chalcogenide glasses (well known for their extended transmission in the infrared domain), more precisely in the GeS2-Ga2S3-CsCl and GeSe2-Ga2Se3-CsI glass-forming systems. These two systems present extended transparency in the visible region due to alkali halide addition.In order to have enough transparency in the visible region, the sulfide based system has been more precisely studied with the selection of two compositions: 75GeS2-15Ga2S3-10CsCl and 65GeS2-20Ga2S3-15CsCl. Their optical transmissions, the refractive indices, the chromatic dispersions and the indices as function of temperature are studied. The thermal properties, molding ability and mechanical properties have been also studied in addition to the above-mentioned optical properties. These two compositions shows good stability against crystallization and extended transparency from 0,5 to 11,5 μm. It makes possible to consider the production of optics which cover a large spectral band, leading to an alternative to the ZnS for multispectral optical system. However, the chromatic dispersion of these two glasses is similar. A study of this important parameter as function of the glass composition has been performed in order to find a new composition with significantly different chromatic dispersion.For all these glasses, the addition of cesium chloride causes a slight degradation of optical properties due to its sensitivity to moisture. In order to protect these glasses against the atmospheric aggression, an efficient protective coatings of zinc sulfide has been applied by sputtering. An antireflective coating has been developed by Thales Angénieux to enhance the transmission in different specific wavelength ranges. The Antireflection coating acts also as a protective coating.This work on glasses in the GeS2- Ga2S3 system for optical applications, has also led us to study these glasses containing sodium ions for ionic conduction. The ionic conductivity has been measured and compared to that of glasses containing lithium ion. It has been demonstrated that the GeS2-Ga2S3-NaI can lead to glasses with an ionic conductivity of 10-6 S.cm-1 at room temperature.

The work described herein deals with the synthesis and characterization of lead chalcogenide thin films and nanocrystals. The first part of thesis describes the properties of semiconductors followed by an analysis on the chemical vapour deposition and nanoparticulate formation. In the next part of thesis, single-source precursors of type thioselenophosphinato, selenoureato, dithiocarbamato and dithiocarbanato complexes of lead have been synthesised and characterised. As-synthesised compounds have been utilised for the fabrication of lead sulfide and lead selenide thin films by aerosol-assisted chemical vapour deposition as well as nanocrystals by colloidal injection method. Lead sulfide thin films were also deposited by liquid-liquid interface from lead dithiocarbanato at room temperature. The as grown thin films of lead sulfide and lead selenide have been characterised by XRD, SEM and energy dispersive x-ray (EDX) analysis. In the second part of the thesis, preparation of lead sulfide and lead selenide nanocrystals in olive oil at low growth temperatures (50-60°C) is described and have shown that by controlling experimental conditions, well-defined particles with tunable emission in mid and far-infrared region can be synthesised. Furthermore, compositionally-tuned PbSxSe1-x nanocrystals has also been prepared by adding controlled amount of sulur and selenium ingredients into lead oxide. Homogenous distribution of sulfur and selenium within alloyed nanocrystals is confirmed by transmission electron microscope studies. Moreover, attempts have been made to prepare quaternary (PbTe/Se/S) nanocrystals of lead chalcogenides and depth (1.9-5.8 nm) profile analysis by x-ray photoelectron spectroscopy confirmed the formation of core/shell/shell type structure i.e. PbTe/S/Se.

Le domaine des couches minces optiques a vu les fonctions de filtrage se complexifier et les techniques de dépôt se perfectionner. Cependant, certains filtres requièrent des performances ultimes notamment en termes d’uniformité et de centrage de leur réponse spectrale. Atteindre ces spécificités requiert un contrôle précis de l'épaisseur optique des couches de l’empilement. Pour se faire, l’utilisation d’un matériau dont l’indice de réfraction peut être modifié localement après dépôt est une solution. Le candidat retenu est un verre de chalcogénures : l’AMTIR-1, un verre commercial, dont l’indice de réfraction décroit sous l’action d’un champ électrique lumineux. Des couches minces de ce matériau ont été déposées par évaporation par canon à électrons et leurs propriétés optiques ont été caractérisées par mesures spectrophotométriques. Des variations d’indice photo-induites de ~4.10-2 ont été enregistrées à λ = 1 μm. Ces variations d’indice ont ensuite été exploitées pour concevoir des composants à base de couches minces optiques spatialement structurés. En particulier, des composants optiques diffractifs binaires ont été enregistrés dans le volume d’une monocouche épaisse de chalcogénure par exposition structurée. Un accord quasi parfait entre théorie et expérience a ainsi été obtenu. L’insertion de ces couches photosensibles à base de chalcogénures dans des filtres optiques interférentiels multicouches a également été investiguée. Une démonstration du contrôle local de la réponse spectrale d’un filtre passe-bande de type Fabry-Perot a été réalisée, démontrant ainsi le potentiel de cette nouvelle approche pour la réalisation de composants optiques optimisés. / In recent years, there has been a tremendous progress in the complexity of thin film optical filters but also an important improvement in the deposition techniques. However, some filters require ultimate performances especially in terms of uniformity and absolute position of their spectral responses. Achieving these characteristics requires a precise and local control of the optical thickness of each of the layers. To overcome some of these fabrication constraints, the use of a material which index of refraction or thickness can be locally changed after deposition is an attractive solution. The chosen material is a chalcogenide glass : AMTIR-1, a commercial glass which refractive index decreases when exposed to light source. Thin films of this material were deposited by electron beam deposition and optical properties were characterized by spectrophotometric measurements. Photo-induced refractive index changes of ~ 4.10-2 were recorded at λ = 1 μm. These refractive index variations were then used to fabricate spatially structured thin films. In particular, diffractive optical elements were recorded in the volume of a thick chalcogenide single layer. This is performed by structured exposure using an optical arrangement based on a digital micromirror device. A close to perfect agreement between theory and experiment has been obtained. The insertion of these chalcogenide-based photosensitive layers in multilayer optical interference filters has also been investigated. A demonstration of the local control of the spectral response of a Fabry-Perot bandpass filter was performed, demonstrating the potential of this new approach for the production of optimized optical components

<p>U ovom radu prikazani su rezultati ispitivanja termičkih, mehaničkih, električnih i optičkih karakteristika kvazibinarnih halkogenida iz sistema Bi-As2S3. Na osnovu termičkih merenja analizirana je kinetika kristalizacionih i predkristalizacionih procesa i utvrđen je mehanizam dekompozicije za različite sastave dobijenih stakala. Primenom impedansne spektroskopije kvantitativno su ocenjeni doprinosi relaksacionih procesa na pojedinim temperaturama u ukupnoj polaraziciji za stakla sa 5 i 7 at.% Bi. Na osnovu merenja Raman spektroskopije identifikovane su nastale strukturne jedinice i konstatovana pojava nanofazne separacije u staklima sa 1.5 i 3 at.% Bi. Mehanička merenja ispitivanih halkogenida različitog sastava ukazala su na povećanje Vickers-ove tvrdoće sa povećanjem udela primesnih atoma. Na osnovu procenjene vrednosti modula elastičnosti ustanovljeno je da uzorak sa 5 at.% Bi odlikuje najgu&scaron;će atomsko pakovanje. Merenja električnih karakteristika u jednosmernom režimu (DC) pokazala su da je udeo lokalizovanih stanja u ukupnom mehanizmu provođenja značajan samo za manje koncentracije primesnih atoma, a da za veće koncentracije dominantan faktor postaju preskoci između delokalizovanih stanja. Skok u provodljivosti za nekoliko redova veličine kod sastava sa složenijom strukturom protumačen je kao posledica fazne separacije. Rezultati&nbsp; ACmerenja dobijeni za sastav sa 5 at.% Bi ukazali su da je u mernom frekventnom intervalu i dalje dominantan mehanizam termičke aktivacije nosilaca naelektrisanja. Kod sastava sa maksimalnim sadržajem Bi uočena je promena provodljivosti u funkciji frekvencije na svim temperaturama, a dobijeni rezultati su u skladu sa postavkama modela korelisanih preskoka barijere (CHB model).</p> / <p>This paper presents the results of investigation ofthermal, mechanical, electrical and optical propertiesof quasibinar chalcogenides from the system Bi-As2S3.&nbsp;Kinetics analysis of softening and crystallizationprocesses was done on the basis of thermalmeasurements, as well the analysis of decompositionmechanism for different compositions of obtainedglasses. The application of impedance spectroscopy enabled quantitative description of relaxation process contributions at selected temperatures in the overallpolarization for the samples with 5 and 7 at.% Bi.&nbsp;Based on measurements of Raman spectroscopy identification of structural units in the investigated chalcogenides was made, as well as the appearance of&nbsp;nano-scale phase separation in the glasses with 1.5 and 3 at.% Bi. Mechanical measurements pointed to the increase of the Vickers hardness with increase of&nbsp;doping atoms content. &nbsp;Based on the estimated value of the modulus of elasticity it was found that the sample &nbsp;with 5 at.% Bi is characterized by the densest atomic&nbsp;arrangement. Measurements of the electrical properties in dc regime (DC) pointed out that the share of localized states in the whole mechanism of conduction&nbsp;is significant only for the smaller concentrations of doping atoms. For the samples with higher concentrations dominant &nbsp;factor in conductivity are transitions between delocalized states. The jump in conductivity by few orders of magnitude, noticed for&nbsp;the compound with heterogeneous structure was interpreted as a consequence of micro-scale phase&nbsp; separation. Results of&nbsp; ACmeasurements for the&nbsp; composition with 5 at.% Bi showed that the mechanism of thermal activation of charge carriers is&nbsp;still dominant in the measured frequency range. For&nbsp;&nbsp; the composition with the maximum content of Bi changes in conductivity versus frequency were observed at all temperatures, and the results were interpreted in accordance with the model of correlated hopping over the barrier (CHB).</p>

Ce travail est consacré à la synthèse et à la caractérisation de composés chalcogénures. Pour la plupart nouveaux, ces composés ont la particularité de présenter des structures complexes ou dont le désordre amène une certaine complexité. La première partie de ce manuscrit est consacré à l’étude du nouveau composé monocristallin Ba0,5Cr5Se8 et de la solution solide polycristalline BaxCr5Se8 (0,5 ≤ x ≤ 0,55). Ce composé fait partie de la famille des pseudo-hollandites. Sa structure cristalline a été déterminée par diffraction des rayons X sur monocristal, un abaissement de la symétrie est observé par rapport aux pseudo-hollandites usuelles. Ces composés sont antiferromagnétiques avec une température de transition unique à 58 K, la structure magnétique du composé a été déterminée par diffraction des neutrons sur échantillon polycristallin, et sa maille magnétique correspond à une maille cristalline doublée selon b et c. Les propriétés thermoélectriques des composés sont étudiées, Ba0.5Cr5Se8 présente une ZT de 0,12 à 800 K. La deuxième partie s’est d’abord focalisée sur une structure similaire à la précédente, TlIn5Se8. Toutefois trop résistif, les structures de deux nouveaux composés ont été étudiées : TlIn4,8Cr0,2Se8 et Tl0,98In13,12Se16,3Te2,7. Ce dernier présente sur certains sites un désordre considéré statique. Finalement, le dernier chapitre a permis de mettre en avant des composés de la famille de composé lamellaire MnPSe3, ayant la particularité de présenter une paire P2. La structure du nouveau composé In2Ge2Te6 est résolue et les propriétés thermoélectriques des composés InSiTe3, Cr2Si2Te6, Cr2Ge2Te6 et In2Ge2Te6 sont étudiées. Des défauts d’empilement ont été mis en lumière et expliquent l’impact sur le libre parcours moyen des phonons. L’ensemble des composés dont les propriétés thermoélectriques ont été étudiées présentent des conductivités thermiques faibles, bien en deçà du W.m-1.K-1 dans de nombreux cas. Des ZTs de 0,18 à 673 K et 0,43 à 773 K sont trouvées pour In2Ge2Te6 et Cr2Ge2Te6. / This work has been focused on synthetizing and characterising chalcogenide compounds. Most new, those compounds show complex structures or where disorder bring complexity. The first part of this manuscript is dedicated to the study of the new single-cristalline Ba0.5Cr5Se8 and of the related polycristalline solid-solution BaxCr5Se8 (0.5 ≤ x ≤ 0.55). This compound is part of the pseudo-hollandite family. Its cristalline structure has been resolved by means of single-crystal X-ray diffraction, a lowering of symetryis observed compared to usual pseudo-hollandites. All antiferromagnetic, the compounds exhibit a transition at 58 K, the magnetic structure has been resolved using neutron diffraction on polycrystal and is twice the cristalline one along b and c. Thermoelectric properties of the compounds have been studied and a maximum ZT of 0.12 is observed at 800 K for Ba0.5Cr5Se8. The second section has first focused on a similar structure to the previous one, TlIn5Se8. Although too resistive to be interesting, two new compounds have been studied: TlIn4.8Cr0.2Se8 and Tl0.98In13.12Se16.3Te2.7. The latter quaternary exhibits static disorder on specific crystallographic sites. The last chapter highlights compounds from the lamellar compound MnPSe3 family, with the particularity to possess P2 pairs. The structure of the new In2Ge2Te6 has been resolved and thermoelectric properties of the InSiTe3, Cr2Si2Te6, Cr2Ge2Te6 and In2Ge2Te6 have been studied. Stacking faults were observed in In2Ge2Te6 and explain the impact on the phonon mean free path. All the compounds whose thermoelectric properties have been studied exhibit low thermal conductivity, below 1 W.m-1.K-1 for most of them. ZTs of 0.18 at 673 K and 0.43 at 773 K were found for In2Ge2Te6 and Cr2Ge2Te6.

No description available.

The advent of ultrafast lasers has enabled micromachining schemes that cannot be achieved by other current techniques. Laser direct writing has emerged as one of the possible routes for fabrication of optical waveguides in transparent materials. In this thesis, the advantages and limitations of this technique are explored. Two extended-cavity ultrafast lasers were built and characterized as the laser sources for this study, with improved performance over existing systems. Waveguides are fabricated in oxide glass, chalcogenide glass, and polymers, these being the three major classes of materials for the telecommunication industry. Standard waveguide metrology is performed on the fabricated waveguides, including refractive index profiling and mode analysis. Furthermore, a finite-difference beam propagation method for wave propagation in 3D-waveguides is proposed. The photo-structural modifications underlying the changes in the material optical properties after exposure are investigated. The highly nonlinear processes of the light/matter interaction during the writing process are described using a free electron model. UV/visible absorption spectroscopy, photoluminescence spectroscopy and Raman spectroscopy are used to assess the changes occurring at the atomic level. Finally, the impact of laser direct writing on nonlinear waveguide applications is discussed.

The development of optical sources and components suitable for the mid-infrared is crucial for applications in this spectral range to reach the maturity level of their counterparts in the visible and near-infrared spectral regimes. The recent commercialization of quantum cascade lasers is leading to further interest in this spectral range. Wideband mid-infrared coherent sources, such as supercontinuum generation, have yet to be fully developed. A mid-infrared supercontinuum source would allow for unique applications in spectroscopy and sensing. Over the last decade, it has been shown that high-index confinement in highly nonlinear fibers pumped with high-peak-power pulses is an excellent approach to supercontinuum generation in the visible and near-infrared. Nonlinear waveguides such as fibers offer an obvious advantage in increasing the nonlinear interaction length maintained with a small cross section. In addition, fiber systems do not require optical alignment and are mechanically stable and robust with respect to the environmental changes. These properties have made fiber systems unique in applications where they are implemented in a harsh and unstable environment. In extending this approach into the mid-infrared, I have used chalcogenide glass fibers. Chalcogenide glasses have several attractive features for this application: they have high refractive indices for high optical-confinement, have a wide transparency window in the mid-infrared, and have a few orders-of-magnitude higher nonlinearity than silica glass and other mid-IR glasses. Producing chalcogenide glass fiber tapers offer, furthermore, the possibility of dispersion control and stronger field confinement and hence higher nonlinearity, desired for supercontinuum generation.

D. Tech. (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / Nanoscience receives a lot of attention in the 21 century and is one of the most advancing technology in our days. It provides many new and advanced technological opportunities. This field involves many disciplines which include chemical, physical, and biological related fields. The advancement of nanoscience makes life to be better and bring about new inventions which can solve many problems in our day to day life. Although there are reservations about the use of these materials in other fields. Some researchers believe that these materials can be a problem to the environment and humanity at large. Therefore, more research needs to be done to fully understand these materials. Polymer science is another field that has been advancing every day. Many problems in our lives require material which have properties from nanomaterials and polymers. The combination of these technologies can leads to new materials which have many possibilities in solving most problems. Some researchers have taken advantage of these two powerful fields and merge them. There has been a lot of work done that involves combination of nanotechnology and polymer science. The current project is an initiative to manufacture nanofibers. These fibers are prepared using polymer solution mixed with metal oxide and metal selenide nanomaterials. The polymer solution is incorporated with nanoparticles and electrospunned to make nanofibers. The electrospinning afford the material prepared to be at nanoscale. The fact that the material formed is at nanoscale opens many possibilities to be used in various fields. The study is about fabrication of polymer nanofibers embedded with metal chalcogenide nanoparticles. The metal oxide and metal selenide nanoparticles were prepared using complexes. These complexes contain both the metal and the chalcogenide of interest. The complexes are prepared from oxygen-based (urea), and selenium-based (diphenyldiselenide) ligands. The urea complexes co-ordinates with metal using oxygen for iron, however in silver complexes both nitrogen and oxygen are used. These complexes allow easy control of reaction parameters, and thermal decomposes to form metal oxide, metal selenide, and metal. The complexes are very stable and decomposes at about 200 °C. These compounds are thermal decomposed to form metal chalcogenides, and metal nanoparticles. The complexes are characterized with FTIR, TGA, and elemental analysis. The metal chalcoginedes (copper oxide, iron oxide, silver oxide, copper selenide, iron selenide, and silver selenide) nanoparticles were prepared using thermal decomposition of a single source (complexes or metal salts). The prepared chalcogenides nanoparticles have good absorption and emission properties consistent with small sizes. These nanoparticles are composed of various phased and stoichiometry. Some metal chalcogenides have a mixture of stoichiometry and phase. The metal chalcogenides nanoparticles are dominated by spheres, and other shapes such as rods. These metal chalcogenides have a particles size in the range of 1-36 nm. The metal chalcogenides nanoparticles were tested against bacteria and fungi. These nanoparticles show highest activity in gram positive compared to gram negative bacteria. Metal oxide nanoparticles show the highest activity compared to metal selenide. All the metal chalcogenides show the highest against fungi. The nanoparticles are able to inhibit the fungi at lowest concentration. The nanoparticles are characterized with various instruments which includes UV-Vis, PL, XRD, and TEM. Nanofibers of poly(methyl methacrylate) (PMMA) incorporated with metal selenide and metal oxide nanoparticles were prepared by electrospinning. The nanofibers incorporated with metal chalcogenide are more thermal stable than PMMA nanofibers. Therefore, incorporation of metal chalcogenides nanoparticles leads to more thermal stability nanofibers. The PMMA are coordinated to the metal oxide and metal selenide through carbonyl oxygen atom. The PMMA incorporated with metal oxide and metal selenide leads to the formation of nanofibers with uneven surface with a diameter in the range of 30 to 200 nm. The prepared fibers are characterized using FTIR, TGA, SEM.