Les nanoparticules (NPs) bimétalliques présentent des propriétés catalytiques très intéressantes qui justifient leur utilisation dans des procédés industriels de catalyse hétérogène. Leur structure (chimique, géométrique, électronique) est néanmoins susceptible d’évoluer dans des conditions environnementales réelles et modifier leurs propriétés. L’objectif de cette thèse pluridisciplinaire est de suivre la réactivité de ces NPs en atmosphère réactive contrôlée. Pour cela, on a développé un dispositif de spectroscopie in situ à modulation spatiale afin de suivre l’évolution de la structure sur une grande population de NPs via l’étude de leur résonance du plasmon de surface (RPS) localisée. Ces observations ont été couplées avec une approche locale (NPs individuelles) par microscopie électronique à transmission environnemental (MET-E). La MET-E a permis de révéler des effets de composition et d’environnement sur la structure chimique de NPs Ag-In. Des alliages stables pauvres en indium se forment, puis une coquille d’oxyde d’indium dont l’épaisseur augmente avec la concentration atomique d’indium. D’autre part, des domaines de structures stables (coeur@coquille, Janus, système réduit) ont été mis en évidence selon les conditions locales de température et de pression d’hydrogène. Enfin, l’oxydo-réduction de NPs Ag-Fe a été suivie in situ via l’étude de leur RPS. La MET, la plasmonique environnementale et les nombreuses simulations (réponse optique, simulations Monte-Carlo) suggèrent une ségrégation du fer et de l’argent avec une surface enrichie en argent. L’oxydation semble induire la diffusion du fer en surface, directement suivie de la formation de magnétite (Fe3O4) / Bimetallic nanoparticles (NPs) are known to present interesting catalytic properties justifying their use in several industrial processes in the domain of heterogeneous catalysis. However, their (chemical, geometrical, electronical) structure may evolve under realistic reactive atmosphere, involving a modification of their properties. In this multidisciplinary work, the aim is focused on the surface reactivity monitoring of these NPs under controlled gaseous environment. For this purpose, we developed an in situ spectrophotometer based on spatial modulation to monitor the structure evolution of a large assembly of NPs through the study of their localized surface plasmon resonance (LSPR). This global approach has been coupled with a more local approach by environmental transmission electronic microscopy (E-TEM). E-TEM observations have shown both composition and environmental effects on the chemical structure of Ag-In NPs. This structure evolves from a stable low-enriched indium alloy to a core@shell configuration with a shell composed of indium oxide as the indium atomic concentration increases. Furthermore, stable structure (core@shell, Janus, reduced system) domains were evidenced under reducing atmosphere, depending on the temperature and hydrogen pressure. Lastly, Ag-Fe NP oxido-reduction was monitored on the new setup through LSPR modifications. MET observations, environmental plasmonics and simulations (optical response, Monte-Carlo simulations) suggest that these metals are initially segregated, with an enriched-silver surface. The exposure to an oxidative atmosphere seems to induce the diffusion of iron onto the surface, followed by the formation of magnetite (Fe3O4)

Les détecteurs infrarouges InSb sont composés d'un circuit intégré Si et d'une matrice InSb qui sont connectés électriquement et mécaniquement par des billes de soudure en indium, préalablement déposées sur une métallisation. La jonction établie entre ces deux substrats est sollicitée thermomécaniquement à chaque utilisation à la température de l'azote liquide. Cette sollicitation thermomécanique est propice à la fatigue limitant la durée de vie du détecteur. Ce travail de thèse a pour objet l'amélioration des métallurgies de la métallisation et de la soudure au vu de la tenue en cyclage thermique de composants assemblés. L'effet des conditions de dépôt sur la microstructure, les propriétés électrique et de diffusion de la barrière de diffusion est évalué pour les métaux réfractaires suivants : alliage tungstène-titane (WTi) et tantale (Ta). L'élaboration par voie physique conduit à l'apparition inopinée d'une phase métastable néfaste, qui peut cependant être contrôlée par l'intermédiaire d'une sous couche. Un alliage indium-argent (eutectique) est déposé par évaporation qui permet de diminuer la température de fusion, et par conséquent les contraintes résiduelles du composant. L'effet de l'élément d'alliage Ag est évalué au vu de la résistance de contact et de la tenue mécanique de l'assemblage. Les résultats ont montré que la métallurgie est affectée par la méthode de fabrication, qui conditionne la tenue thermomécanique du composant optoélectronique. / InSb based infra-red (IR) detectors are constituted by a Si integrated circuit and an InSb matrix which are electrically and mechanically connected thanks to solder balls in pure indium deposited on underbump metallic layers (UBM). IR detectors are cooled down to liquid nitrogen for each use. This thermomechanical solicitation affects the device reliability. The thesis purpose is to improve the UBM and solder metallurgies taking into account thermal cycling behavior of industrial components. The effect of deposition conditions on the diffusion barrier microstructure, electrical properties and diffusion efficiency is estimated for several refractory metals : tungsten-titanium alloy (WTi) and tantalum (Ta). The physical vapor deposition yield unexpected and harmful metastable phase formation, which can be controlled using a sub-layer. An indium-silver eutectic alloy is deposited by evaporation which allows to reduce the melting temperature and hence residual stresses within the component. The effect of Ag alloying is estimated by both the contact resistance and mechanical shear resistance. Results emphasize that the metallurgy is affected by the deposition technique, which impinges on IR detectors thermomechanical behavior.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / This work describes our results on the use of indium(I) bromide in Organic Synthesis, namely the reaction mechanisms and stereochemical outcome. Indium enolates, generated from the reaction between indium(I) bromide and α,α-dichloroketones, react with carbonyl compounds. The primary coupling with aldehydes leads to the diastereoselective synthesis of (syn+anti)-2-chloro-3-hydroxypropan- 1-ones, which can be converted to the respective trans-epoxyketones, exclusively. The indium(III) alkoxides of the 2-chloro-3-hydroxy-propan-1-ones are transformed into their (E)-prop-2-en-1-ones derivatives upon reaction with InBr according to a sequenced reaction mechanism. The most relevant feature of these reactions is that although the primary coupling with aldehydes affords a mixture of the two diastereoisomers of the indium(III) alkoxides, both the trans-epoxyketones and the E-enones were produced with rigorous stereoselectivity. These results are understood in terms of the enolate geometry (E or Z) and the retro-aldol reaction (kinetic/thermodynamic control) relating both forms of the enolate. / Este trabalho descreve os resultados dos estudos realizados sobre aplicações de brometo de índio(I) em Síntese Orgânica. Especificamente os aspectos pertinentes aos mecanismos reacionais e estereoquímicos. A reação entre brometo de índio(I) e α,α-diclorocetonas produz, in situ, enolatos de índio que reagem com compostos carbonílicos. O acoplamento com aldeídos leva à formação diastereosseletiva de (syn+anti)-2-cloro-3-hidroxi-propan-1-onas, que podem ser convertidas às respectivas oxiranas, exclusivamente trans. O aldolato de índio dos compostos 2-cloro-3-hidroxi-propan-1-onas é transformado, pela ação de um equivalente extra de InBr, nos respectivos derivados (E)-prop-2-en-1-onas, segundo um mecanismo de reações seqüenciais. Embora o acoplamento primário com aldeídos leve a uma mistura diastereoisomérica dos aldolatos de índio, as transoxiranas e as E-enonas são produzidas com rigorosa estereosseletividade. Estas são as características mais relevantes e podem ser compreendidas em termos da geometria do enolato (E ou Z) e do equilíbrio retro-aldol (controle cinético ou termodinâmico) entre as duas formas do enolato.

No description available.

Le premier projet de ce travail de doctorat a consisté à étudier l’activité catalytique de complexes à base de gallium(I), pour continuer à rechercher des alternatives aux catalyseurs à base de métaux nobles, plus communs, mais réputés coûteux et/ou toxiques. Le savoir-faire de l’équipe en catalyse par des complexes de gallium(III) a pu être réinvesti dans l’étude de ce bas degré d’oxydation du gallium, rarement étudié dans la littérature scientifique, dans l’espoir de détecter des réactivités et/ou sélectivités différentes d’avec des complexes de gallium(III). Ainsi, le complexe cationique bien défini de gallium(I) [Ga(PhF)2][Al(OC(CF3)3)4] a été employé dans une large gamme de réactions dans lesquelles les catalyseurs à base de gallium(III) avaient déjà fait leurs preuves, telles que l’hydroarylation d’arénynes, la réaction de Friedel-Crafts ou encore l’hydrogénation d’alcènes par transfert, pour laquelle une réactivité supérieure à celle des complexes usuellement utilisés au sein de l’équipe a été observée. Un analogue à base d’indium(I), [In(PhF)2][Al(OC(CF3)3)4], a également été étudié dans ces réactions, sans succès. En revanche, il s’est avéré efficace dans le cadre de réactions d’hydroamination d’aminoalcènes.En parallèle a été conduit un projet basé sur l’étude en tant qu’abstracteurs d’halogénures de complexes de divers métaux (argent, lithium, potassium, thallium(I)) comportant l’anion perfluoré, très volumineux et très faiblement coordinant [Al(OC(CF3)3)4]-. Dans le cadre de l’activation de pré-catalyseurs à base d’or(I), de gallium(III) ou d’indium(III) par abstraction d’halogénures, les sels d’argent sont les plus communément employés dans la littérature. Cependant, ces sels d’argents ne sont pas innocents en termes de réactivité. Par ailleurs, si les cations métalliques des sels employés en abstraction d’halogénures font l’objet d’un nombre raisonnable d’études dans la littérature, ce n’est pas autant le cas des anions qui leur sont associés : notre étude s’oriente selon ces deux problématiques. Il s’est avéré que les propriétés très faiblement coordinantes de l’anion [Al(OC(CF3)3)4]- ont mené à des réactivités et sélectivités différentes de celles obtenues avec l’emploi de sels plus usuels, AgSbF6 plus particulièrement, dans le cadre de réaction classiquement catalysées par l’or(I) ou le gallium(III) et déjà étudiées dans le premier projet de ce travail de thèse. Les complexes à base de gallium(I) et d’indium(I) impliqués dans le premier projet ont également été, succinctement, étudiés dans ce projet parallèle. / In the main project of this thesis work, the catalytic activity of gallium(I)-based complexes was explored. The aim was to keep on looking for alternatives to noble metals-based, more common catalysts, which have a reputation for being expensive and/or toxic. The know-how developed in the team on gallium(III)-based catalysis was reinvested into the study of this low oxidation degree of gallium, only scarcely studied in the literature. It was hoped to then detect different reactivity and/or selectivity than with gallium(III) complexes. Thus, the well-defined, cationic, gallium(I)-based complex [Ga(PhF)2][Al(OC(CF3)3)4] was used in a large array of reactions that were already successfully studied with gallium(III)-based catalysts, such as the hydroarylation of arenynes, the Friedel-Crafts reaction or the transfer hydrogenation of alkenes. In this later reaction in particular, the observed reactivity was superior to that achieved with the catalysts more commonly used in the team. An indium(I)-based analogue, [In(PhF)2][Al(OC(CF3)3)4], was also tested in these reactions, without any success. However, it was actually efficient in the context of aminoalkenes hydroamination reactions.The side-project of this work consisted in the study as halide abstractors of complexes, based on diverse metals (silver, lithium, potassium, thallium(I)) and containing the perfluorinated, very bulky and very weakly coordinating anion (WCA) [Al(OC(CF3)3)4]-. In the frame of the activation of gold(I), gallium(III) or even indium(III)-based pre-catalysts by halide abstraction, silver salts are the most frequently used. However, these silver salts are not non-innocent in terms of reactivity. Besides, if the cationic metal of the salts used in halide abstraction are the subject of a reasonable amount of studies in the literature, it is not the case of their anionic counterparts: we planned to address these two problematics with this project. It appeared that the very weakly coordinating properties of the anion [Al(OC(CF3)3)4]- in the context of the previously referred to reactions classically catalyzed by gold(I) or gallium(III)-based complexes led to different reactivity and selectivity than those achieved with the usual salts and in particular AgSbF6. The gallium(I) and indium(I)-based complexes involved into the main project were also briefly studied in this side-project.

ITO is widely regarded as the optimal TCO for serving as front window layer in PSK/c-Si tandem solar cells. It is known to effectively mitigate several stability issues present in perovskite solar cells while demonstrating excellent lateral conductivities and optical transparency across the entire solar spectrum. However, due to the damaging effects of traditional magnetron sputtering methods on the underlying cell precursor and the limited range of annealing temperatures viable for maintaining the stability of Perovskite Solar cells, realizing the full capability of ITO layer is constrained. This investigation focuses on developing and optimizing the front Indium Tin Oxide (ITO) layer properties for high-efficiency monolithic Perovskite/PERC tandem solarcells. The study employs two widely employed industrial techniques, Magnetron Sputtering and Screen Printing for the deposition of ITO thin-films and subsequent metallization of Ag front contacts. The sputtering process parameters, namely the carrier speed, O2 : Ar ratio, and the sputter power were varied to obtain an optimized ITO layer, which exhibited a thickness of 53nm, Rsheet of 107 ohm/□, mobility of 37 cm2/V s, and 90 % average optical transparency between 400−1200nm. A low contact resistivity of 5.4mΩ·cm2 was achieved between the ITO and metal contacts which is the lowest reported value for ITO annealed at low temperature (140 °C). Champion cells, featuring Perovskite on Ohmic substrate and 2T perovskite/PERC tandem cells, exhibited high VOC values of 1.116 V and 1.75 V on 0.97 cm2 cell aperture areas and cell efficiencies of 17.2 % and 23.85 %. Additionally, a large area (158.7 cm2) tandem cell was also fabricated which demonstrated an excellent VOC of 1.75 V . The results of this investigation demonstrates the versatility of ITO layer properties achievable at low-temperatures through Magnetron sputtering and underscores the potential of existing commercialized technologies for the fabrication of high-efficiency tandem solar cells. / ITO anses allmänt vara den optimala TCO för användning som frontfönsterskikt i PSK/c-Si tandemsolceller. Den är känd för att effektivt mildra flera stabilitetsproblem som finns i perovskitsolceller samtidigt som den uppvisar utmärkt lateral konduktivitet och optisk transparens över hela solspektrumet. På grund av de skadliga effekterna av traditionella magnetronförstoftningsmetoder på den underliggande cellprekursorn och det begränsade intervallet av glödgningstemperaturer som är användbara för att upprätthålla stabiliteten hos perovskitsolceller, begränsas dock ITO-skiktens fulla kapacitet. Denna undersökning fokuserar på att utveckla och optimera egenskaperna hos det främre Indium Tin Oxide (ITO)-skiktet för högeffektiva monolitiska Perovskite/PERC tandemsolceller. I studien används två allmänt använda industriella tekniker, magnetronförstoftning och screentryckning, fördeponering av ITO-tunnfilmer och efterföljande metallisering av Ag-frontkontakter. Parametrarna för sputteringsprocessen, nämligen bärarhastigheten, förhållandet O2 : Ar och sputterkraften varierades för att få ett optimerat ITO-lager, som uppvisade en tjocklek på 53nm, Rsheet på 107 ohm/□, rörlighet på 37 cm2/V s och 90 % genomsnittlig optisk transparens mellan 400 − 1200 nm. En låg kontaktresistivitet på 5.4mΩ.cm2 uppnåddes mellan ITO och metallkontakterna, vilket är de lägstarapporterade värdena för ITO glödgat vid låg temperatur (140 °C). Champion-cellerna, med perovskit på ohmskt substrat och 2T perovskit/PERC tandemkonfigurationer, uppvisade höga VOC-värden på 1.116 V och 1.75 V på 0.97 cm2 cellaperturområden och cellverkningsgrader på 17.2 % och 23.85 %. Dessutom tillverkades en tandemcell med stor area (158.7 cm2) som uppvisade en utmärkt VOC på 1.75 V . Resultaten av denna undersökning visar mångsidigheten hos ITO-skiktets egenskaper som kan uppnås vid låga temperaturer genom magnetronförstoftning och understryker potentialen hos befintliga kommersialiserade tekniker för tillverkning av högeffektiva tandemsolceller.

No description available.

The optical properties of InAs/GaSb heterostructures under applied magnetic fields are studied in experimental and theoretical detail. The InAs/GaSb system is a type-II "crossed-gap" system, where the valence band edge of GaSb lies higher in energy than the conduction band edge of InAs. This leads to a region of energy above the InAs conduction band where conduction and hole states mix. Thin-layer superlattices remain semiconducting due to confinement effects, but thick-layer superlattices experience charge transfer which leads to intrinsic carrier densities approaching 10¹² cm^-2 per layer. Existing multi-band modeling techniques based on the <strong>k·p</strong> formalism are discussed, and a method of solving superlattice band structure (the "momentum-matrix" technique) is presented. The quantizing effects of the superlattice layers and applied magnetic fields are investigated, and the selection rules for optical transitions are derived. Standard cyclotron resonance (CR) is used to study effective masses in InAs/GaSb structures. The heavy hole mass is found to be strongly orientation-dependent, with a mass in the [111] orientation reduced 25% from the [001] mass. The electron mass is found to be roughly isotropic with respect to growth orientation, but shows variation with the InAs width due to quantum confinement effects. CR of InAs/GaSb heterojunctions display hitherto unexplained oscillations in linewidth, intensity, and effective mass. A model is proposed which explains the oscillations, based on the intrinsic nature of the InAs/GaSb system. CR is performed on an InAs/GaSb heterojunction using a free-electron laser, where due to the high intensities (on the order of MW/cm²) the absorption process saturates. This saturation allows for a determination of non-radiative relaxation lifetimes, and through the energy dependence of these lifetimes the magnetophonon effect is observed, allowing a direct measurement of LO-phonon-assisted energy relaxation rates. Coupling is introduced into the standard CR experiment, either by tilting the sample with respect to the magnetic field, or by applying a metal grating to the surface. These coupled CR experiments have striking qualitative results which allow for determination of subband separation energies and coupling matrix elements. Photoconductivity experiments are performed on thin-layer (semiconducting) superlattices, showing optical response at far-infrared wavelengths (5-20 μm). The results are compared with <strong>k·p</strong> calculations. One sample is processed for vertical transport, in which conduction occurs perpendicular to the superlattice layers. Strong optical response from this sample indicates the viability of InAs/GaSb-based far-infrared detectors. The momentum-matrix technique is used to predict optimum parameters for semiconducting superlattices with band gaps in the far-infrared. Semimetallic structures are studied via a multi-band self-consistent model, with results corroborating with and extending previous work. Intrinsic structures under applied magnetic field are modeled theoretically for the first time.

Ternary indium aluminum nitride (InXAl1-XN) semiconductor is an attractive material with a wide-range bandgap energy varied from ultraviolet (Eg(AlN): 6.2 eV) to near infrared (Eg(InN): 0.7 eV). With tuning composition, it can be widely used to many optoelectronic device applications. In this thesis, I have studied InXAl1-XN film deposited on Si (111) substrate using natural and isotopically enriched nitrogen as reactive gas by reactive magnetron sputter epitaxy (MSE). Four series of experiments were performed, which are I. InAlN presputtering, II. InAlN sputter deposition, III. InAlN direct deposition, and IV. InAlN direct deposition using isotopically enriched nitrogen. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and energy-dispersive X-ray spectroscopy (EDX). The θ-2θ XRD scan confirms that the designed composition x = 0.17 of InXAl1-XN film was obtained. TEM images shows that an amorphous interlayer with a thickness ranging from 1.2 nm to 1.5 nm was formed between Si substrate and InXAl1-XN film. However, high-resolution TEM shows that the interlayer actually contains partial crystalline structures. EDX line profile indicates that the chemical composition of the amorphous interlayer is silicon nitride (SiNX). By comparing d-spacing measurement of partial crystalline structures with EDX line profile, it reveals that partial SiNX crystal is formed in the interlayer. Nonetheless, the samples (IAD01, IAD02, IAD03, IAD04), grown without presputtering procedure, contain both crystalline SiNX and InXAl1-XN embedded in the amorphous interlayer. It means that SiNX and InXAl1-XN film can be directly grown on the substrate in the beginning of deposition. Moreover, the samples (IAD01, IAD03), quenched directly after deposition, have less crystalline structures in the interlayer then the samples (IAD02, IAD04), maintained at 800℃ for 20 min.

No description available.