京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21113号 / 工博第4477号 / 新制||工||1696(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 田中 勝久, 教授 三浦 清貴, 教授 作花 哲夫 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

No description available.

Materiais vítreos com propriedades similares às do cristal germanato de bismuto de composição Bi4Ge3O12, material cintilador que possui estrutura do tipo eulitita, são de interesse devido as suas propriedades luminescentes, que os tornam promissores para aplicação como dispositivos ópticos. Vidros do sistema GeO2-Bi2O3 (BGO) também tem sido tema de inúmeras pesquisas por combinarem um típico formador vítreo (GeO2) a um formador condicional composto intermediário (Bi2O3), o que os proporciona características estruturais únicas, resultantes da mudança de coordenação dos átomos de germânio (fenômeno de anomalia do germânio) e também dos átomos de bismuto. Neste trabalho, estudou-se a influência da adição de CeO2, comumente conhecido como agente oxidante, nas propriedades físico-químicas de vidros de germanato de bismuto do sistema [100-x].[(1-y)GeO2-yBi2O3]:xCeO2 (para x = 0,2 ou 1 e y = 0,2 ou 0,3 % em mol), preparados pelo método de fusão e moldagem. O escurecimento inomogêneo das amostras, associado à termoredução do íon Bi3+, foi evitado com a adição de céria, que se mostrou um modificador da estrutura local dos vidros, mesmo para uma dopagem de 0,2 % em mol. Foi observada, pela primeira vez, a cristalização da fase de estrutura eulitita cintiladora induzida pela presença de Ag na superfície do vidro de composição 99,8[0,8GeO2- 0,2Bi2O3 ]:0,2CeO2 % em mol, referido pela sigla 80BGO:0,2Ce, abaixo da temperatura de transição vítrea (Tg). A difusão de Ag no vidro é condição necessária para que o fenômeno da cristalização aconteça, uma vez que esse elemento pode ser considerado um efetivo agente nucleante para a fase cintiladora. A cristalização induzida é favorecida pela tensão gerada na interface cristal/vidro, devido a uma diferença de volume molar entre essas duas fases, o que permite que o fenômeno da cristalização seja observado em temperturas inferiores à Tg. / Glassy materials with similar properties to those of the bismuth-germanate crystal in the composition of Bi4Ge3O12, a scintillator material with the eulytite structure, are of interest due to their luminescent properties that makes them promising materials to application as optical devices. Glasses from the system GeO2-Bi2O3 (BGO) has also being subjects of numerous studies, by combining a typical glass former oxide (GeO2) with the conditional one intermediate compound (Bi2O3). The presence of these two oxide compounds in the glass composition provides them a unique structural characteristic resulting from the coordination changes of germanium atoms (germanium anomaly phenomenon) and also of the bismuth atoms. In the present work, it was studied the influence of CeO2 addition, commonly known as an oxidant agent, in the physical-chemical properties of the bismuth-germanate glasses up to the system [100-x].[(1-y)GeO2-yBi2O3 ]:xCeO2 (for x = 0.2 or 1 and y = 0.2 or 0.3 mol %), prepared by the melting/molding method. The inhomogeneous darkening of the samples, associated to the thermal reduction of the Bi3+ ions, was avoided by the ceria addition that acts as a local modifier of the glass structure even for concentrations of 0.2 mol %. It was observed, by the first time, the crystallization of the eulytite scintillator phase, induced by the presence of Ag in the surface of the glass in the 99[0.8GeO2- 0.2Bi2O3 ]:0.2CeO2 mol % composition, referred to as 80BGO:0.2Ce, below the glass transition temperature (Tg). The Ag diffusion into the glass is a necessary condition to the crystallization phenomenon since this element can be considered as an effective nucleating agent to the scintillator phase. The crystallization is favored by the tension generated in the crystal/glass interface, due to a difference in molar volume of these two phases, allowing that the crystallization phenomenon be observed at temperatures below Tg.

This thesis focuses on two topics: thermal limitations of volume Bragg gratings (VBGs) employed as laser-cavity mirrors and formation of color centers in KTiOPO4 and its isomorphs. To explore the mechanisms of the thermal limitations of VBGs in high power lasers, I designed and constructed a diode-pumped, solid‑state laser with a VBG as cavity mirror that had a significantly higher absorption than what is typical. Thereby I could study the limiting thermal effects by using only moderate intra-cavity power. Additionally, I designed a computer model to numerically investigate the thermal effects in VBGs. Both the experiments and the simulations showed that the laser became successively more unstable when the power was increased. Absorption of the reflected laser beam causes broadening of the grating spectrum accompanied by decreasing diffraction efficiency. The reduced reflectivity leads to a leakage of the radiation through the grating. Moreover, the simulations showed that this increased instability was due to a reshaping of the intensity distribution profile inside the grating, which, in turn, leads to a sharp reduction of the diffraction efficiency. High-intensity visible radiation induces color centers in KTiOPO4, which can lead to severe decrease in the performance of the crystal and can cause catastrophic breakdown. The formation of color centers was investigated by measuring picosecond, blue-light induced infrared absorption (BLIIRA) in periodically-poled KTiOPO4, Rb:KTiOPO4, RbTiOPO4, KTiOAsO4 and RbTiOAsO4 through thermal lens spectroscopy using a common-path interferometer. This setup is capable of measuring absorption as low as 10-5 cm-1. The dependence of the BLIIRA signal on blue light average power and intensity as well as on the crystal temperature was studied. The results show the presence of at least two different types of color centers. A higher level of remnant absorption was observed in the phosphates compared to that of the arsenates. The largest portion of the induced absorption is attributed to photo-generated electrons and holes being self-trapped in the proximity to the Ti4+ and O2- ions, respectively, forming polaron color centers. Stabilization of these centers is aided by the presence of mobile alkali metal vacancies in the crystal. / Denna avhandling fokuserar på både volymbraggitters (VBGs) termiska begränsningar, i tillämpning som speglar i laserkaviteter, och på bildandet av färgcentra i KTiOPO4 och isomorfa kristaller. För att undersöka de termiska effekterna i VBGer som medför begränsningar på högeffektlasrar utfördes både experiment och simuleringar. För experimenten konstruerades en diod-pumpad Yb:KYW laser med ett VBG som har betydligt högre absorption än vad som är typiskt. Därmed kunde de termiska effekterna studeras vid måttliga intrakavitetseffekter. Simuleringarna bestod av två delmodeller; gitterstrukturen modelerades med överföringsmatriser och värmeflödet med en tredimensionell modell baserad på finita elementmetoden. Både experimenten och simuleringarna visade att en laser blir successivt mer instabil när den optiska effekten ökar. Absorptionen av laserstrålen i VBGt förändrade dess spektrala egenskaper, vilket i sin tur påverkade laserns stabilitet och prestanda. De huvudsakliga effekterna var en breddning av gittrets spektrum med en minskad reflektans. Simuleringarna visade även att den ökade instabiliteten berodde på en förändring av strålningens intensitetsfördelning inuti gittret, vilket accelererade reduktionen av gittrets reflekterande förmåga. I termer av den effekt som faller in mot gittret, har lasern en tydlig övre effektgräns. När den gränsen har uppnåtts leder vidare ökning av pumpeffekten i huvudsak till ökat läckage genom volymbraggittret, i stället för till ökad uteffekt hos laserstrålen. Kortvågigt synlig ljus av hög intensitet inducerar färgcentra i KTiOPO4, vilket kan leda till kraftigt reducerad transparens och kan orsaka permanent skada i kristallen. För att undersöka skapandet av dessa färgcentra mättes den termiska lins som uppstår vid blå-ljus-inducerad infraröd absorption (Eng: blue-light induced infrared absorption = BLIIRA) inducerad av blåa laserpulser vid en våglängd av 398 nm och vid pulslängder i storlek av pikosekunder i periodiskt‑polad KTiOPO4, Rb:KTiOPO4, RbTiOPO4, KTiOAsO4 och RbTiOAsO4. Den termiska linsen mättes med en metod kallad gemensam-vägsträcka-interferometer (Eng: common-path interferometer), en metod känslig nog för att mäta absorption så låg som 10-5 cm-1. Dessutom undersöktes hur nivån av BLIIRA beror på medeleffekten och intensiteten hos den blåa laserstrålen samt på kristalltemperaturen. Resultaten visar att det bildas minst två typer av färgcentra med olika livslängder. Vidare observerades en högre grad av långsamt avklingande absorption i fosfaterna jämfört med arsenaterna. Den största delen av den inducerade absorptionen tillskrivs fotogenererade elektroner och hål som ”självfångas” i närheten av Ti4+ respektive O2- joner, och bildar färgcentra av polaron karaktär. Stabilisering av dessa centra underlättas av lättrörliga alkalivakanser i kristallerna. / <p>QC 20150922</p>

Organic solar cells have the potential to become a low-cost photovoltaic technology. One approach to further increase the device efficiency aimsvto cover the near-infrared region of the sunvspectrum. However, suitable absorber materials are rare. This thesis focuses on the material class of aza-bodipy and dibenzo-aza-bodipy as near-infrared absorber materials for organic solar cells. Besides the synthesis of novel thiophene-substituted aza-bodipys, azadiisoindomethenes were prepared by the addition of Grignard reagents to phthalodinitrile an subsequent reduction with formamide. Starting from these azadiisoindomethenes as precursors, complexes with borondifluoride, boroncatechole and transition metals were synthesized. The optical and electrochemical properties of all compounds prepared were investigated by experimental and theoretical methods. The (dibenzo-)aza-bodipys are characterized by their electronic structure, comprising a central electron acceptor core and peripheral electron donor units. The substituents at the donor units offer a stronger impact on the HOMO energy than on the LUMO energy. Electron donating substituents at the donor units result in an overall decreased HOMO-LUMO gap. This allows to redshift the absorption maximum up to 800 nm. The corresponding dibenzo-analogues already demonstrate a bathochromic shift of the absorption compared to the (non-annulated) aza-bodipys. Yet, the central acceptor is weakened and a further redshift by substituents is less distinct. The compounds can be thermally evaporated in high vacuum. The required thermal stability is increased in some cases by boroncatechol compared to borondifluoride complexes, without significant influence on the optical and electrochemical properties. Besides the characterization of the molecular properties, promising materials were evaluated in thin fifilms and solar cell devices. The charge carrier mobility in the measured compounds were found to be between 10E-6 and 10E-4 cm2V-1s-1. The charge transport parameters were calculated on the basis of obtained single crystal structures. It was found that a high charge carrier mobility may be attributed to a better molecular overlap and a short intermolecular distance in the corresponding solid state structure. Selected materials were characterized in organic solar cells. In solution processed devices, the dibenzo-aza-bodipys reached efficiencies of 1.6 % and 2.1 %, as donor materials in combination with PC61BM and PC71BM as acceptor. The main limiting factor in these devices turned out to be the low fill factor of 30 %. From a series of vacuum processed devices with aza-bodipys and dibenzo-aza-bodipys, increased voltages were obtained with decreasing HOMO energy of the bodipy derivatives. A suitable near-infrared absorbing dibenzo-aza-bodipy exhibited a contribution to the photocurrent from 750 - 950 nm. / Die organische Photovoltaik hat das Potential eine kostengünstige Solarzellentechnologie zu werden. Ein Ansatz die Effizienz weiter zu steigern besteht darin den aktiven Spektralbereich in den nahen Infrarotbereich zu erweitern. Bisher gibt es jedoch nur wenige geeignete Materialien. In dieser Arbeit werden Verbindungen aus der Materialklasse der Aza-Bodipy und Dibenzo-Aza-Bodipy als Absorbermaterialien für den nahen Infrarotbereich zur Verwendung in organischen Solarzellen untersucht. Neben der Synthese von neuen Thiophen-substituierten Aza-Bodipys wurden Azadiisoindomethine durch die Addition von Grignardverbindungen an Phthalodinitril und anschließender Reduktion mit Formamid dargestellt. Ausgehend von den Azadiisoindomethinen sind neue Bordifluorid, Borbrenzcatechin und Übergangsmetallkomplexe synthetisiert worden. Alle Substanzen sind mit experimentellen und theoretischen Methoden auf ihre optischen und elektrochemischen Eigenschaften hin untersucht worden. Die elektronische Struktur der (Dibenzo-)Aza-Bodipys ist charakterisiert durch periphere Elektronendonoreinheiten um einen zentralen Elektronenakzeptor. Die langwelligste Absorptionsbande kann in beiden Systemen durch Elektronen schiebende Gruppen an den Donoreinheiten bathochrom, auf über 800 nm verschoben werden. Die Ursache liegt in einem stärkeren Einfluss der Substituenten auf das HOMO als auf das LUMO und einem damit einhergehenden stärkeren Anstieg der HOMO-Energie woraus eine verkleinerte HOMO-LUMO Lücke resultiert. Die Dibenzo-Aza-Bodipys zeichnen sich durch eine rotverschobene Absorption gegenüber den (nicht benzannulierten) Aza-Bodipys aus. Jedoch ist der Akzeptor in den Dibenzo-Aza-Bodipys abgeschwächt, so dass die Rotverschiebung durch die selben Substituenten weniger stark ausgeprägt ist und die Energieniveaus tendenziell höher liegen. Die Verbindungen lassen sich thermisch im Vakuum verdampfen. Die für das Verdampfen wichtige thermische Stabilität, kann durch Austausch von Bordifluorid mit Borbrenzcatechol erhöht werden, ohne die optischen und elektronischen Eigenschaften wesentlich zu beeinflussen. Neben der Charakterisierung der molekularen Eigenschaften, sind einige Verbindungen im Dünnfifilm auf ihre elektrischen Eigenschaften und in Solarzellen untersucht worden. Die Ladungsträgerbeweglichkeit liegt bei den gemessenen Verbindungen zwischen 10E-6 und 10E-4 cm2V-1s-1. Durch Berechnung der Ladungstransportparameter auf Basis erhaltener Kristallstrukturen ist eine höhere Beweglichkeit auf eine günstigere Packung und einen geringeren intermolekularen Abstand zurückgeführt worden. Ausgewählte Verbindungen sind als Donormaterialien in organischen Solarzellen charakterisiert worden. Aus Lösungsmittel prozessierte Solarzellen mit Dibenzo-Aza-Bodipys erreichen eine Effifizienz von 1.6 % mit PC61BM, und 2.1 % mit PC71BM als Akzeptor. Der Effizienz limitierende Faktor ist hierbei der niedrige Füllfaktor von ca. 30 %. In vakuumprozessierten Solarzellen mit planarem Dono-Akzeptor-Übergang von Aza-Bodipys und Dibenzo-Aza-Bodipys hat sich gezeigt, dass die erhaltene Spannung mit abnehmender HOMO Energie der Materialien gesteigert wird. Ein geeignetes Dibenzo-Aza-Bodipy Material ist mit einen Beitrag zum Photostrom im nahen Infrarotbereich, von 750 - 950 nm, gezeigt worden.

No description available.

Materiais vítreos com propriedades similares às do cristal germanato de bismuto de composição Bi4Ge3O12, material cintilador que possui estrutura do tipo eulitita, são de interesse devido as suas propriedades luminescentes, que os tornam promissores para aplicação como dispositivos ópticos. Vidros do sistema GeO2-Bi2O3 (BGO) também tem sido tema de inúmeras pesquisas por combinarem um típico formador vítreo (GeO2) a um formador condicional composto intermediário (Bi2O3), o que os proporciona características estruturais únicas, resultantes da mudança de coordenação dos átomos de germânio (fenômeno de anomalia do germânio) e também dos átomos de bismuto. Neste trabalho, estudou-se a influência da adição de CeO2, comumente conhecido como agente oxidante, nas propriedades físico-químicas de vidros de germanato de bismuto do sistema [100-x].[(1-y)GeO2-yBi2O3]:xCeO2 (para x = 0,2 ou 1 e y = 0,2 ou 0,3 % em mol), preparados pelo método de fusão e moldagem. O escurecimento inomogêneo das amostras, associado à termoredução do íon Bi3+, foi evitado com a adição de céria, que se mostrou um modificador da estrutura local dos vidros, mesmo para uma dopagem de 0,2 % em mol. Foi observada, pela primeira vez, a cristalização da fase de estrutura eulitita cintiladora induzida pela presença de Ag na superfície do vidro de composição 99,8[0,8GeO2- 0,2Bi2O3 ]:0,2CeO2 % em mol, referido pela sigla 80BGO:0,2Ce, abaixo da temperatura de transição vítrea (Tg). A difusão de Ag no vidro é condição necessária para que o fenômeno da cristalização aconteça, uma vez que esse elemento pode ser considerado um efetivo agente nucleante para a fase cintiladora. A cristalização induzida é favorecida pela tensão gerada na interface cristal/vidro, devido a uma diferença de volume molar entre essas duas fases, o que permite que o fenômeno da cristalização seja observado em temperturas inferiores à Tg. / Glassy materials with similar properties to those of the bismuth-germanate crystal in the composition of Bi4Ge3O12, a scintillator material with the eulytite structure, are of interest due to their luminescent properties that makes them promising materials to application as optical devices. Glasses from the system GeO2-Bi2O3 (BGO) has also being subjects of numerous studies, by combining a typical glass former oxide (GeO2) with the conditional one intermediate compound (Bi2O3). The presence of these two oxide compounds in the glass composition provides them a unique structural characteristic resulting from the coordination changes of germanium atoms (germanium anomaly phenomenon) and also of the bismuth atoms. In the present work, it was studied the influence of CeO2 addition, commonly known as an oxidant agent, in the physical-chemical properties of the bismuth-germanate glasses up to the system [100-x].[(1-y)GeO2-yBi2O3 ]:xCeO2 (for x = 0.2 or 1 and y = 0.2 or 0.3 mol %), prepared by the melting/molding method. The inhomogeneous darkening of the samples, associated to the thermal reduction of the Bi3+ ions, was avoided by the ceria addition that acts as a local modifier of the glass structure even for concentrations of 0.2 mol %. It was observed, by the first time, the crystallization of the eulytite scintillator phase, induced by the presence of Ag in the surface of the glass in the 99[0.8GeO2- 0.2Bi2O3 ]:0.2CeO2 mol % composition, referred to as 80BGO:0.2Ce, below the glass transition temperature (Tg). The Ag diffusion into the glass is a necessary condition to the crystallization phenomenon since this element can be considered as an effective nucleating agent to the scintillator phase. The crystallization is favored by the tension generated in the crystal/glass interface, due to a difference in molar volume of these two phases, allowing that the crystallization phenomenon be observed at temperatures below Tg.

Les télescopes terrestres et spatiaux recueillent une énorme quantité d'informations dans le domaine infrarouge en provenance d'objets astrophysiques ''chauds'' (500-3000 K) tels que les atmosphères d'exoplanètes (Jupiters chauds), de naines brunes et les enveloppes circumstellaires d'étoiles AGBs. Cette thèse s'inscrit dans une approche d'astrophysique de laboratoire s'attachant à reproduire in situ certains aspects des conditions extrêmes rencontrées au sein de ce type d'environnements afin notamment de produire des données haute température de molécules clefs. Le nouveau dispositif mis en place à Rennes couple une Source Haute Enthalpie à un spectromètre par temps de déclin d'une cavité optique (CRDS). Le gaz étudié, chauffé dans le réservoir à une température avoisinant 2000 K, est expulsé dans une chambre basse pression au travers d'un injecteur circulaire. Le jet libre hypersonique ainsi formé est sondé en tout point et avec une très haute sensibilité. La simulation de nos écoulements stationnaires (CFD) associée à la modélisation du spectromètre a abouti à des spectres synthétiques en très bon accord avec les spectres expérimentaux. Ces données numériques ont été utilisées pour expliquer l'origine des profils de raie atypiques et plus généralement pour comprendre la structure des jets hypersoniques axisymétriques. Le cœur isentropique de ces écoulements est caractérisé par de fortes conditions hors équilibre. Une température de vibration très élevée (1350 K) et une température de rotation très basse (10 K) ont été obtenues à partir d’un jet de CO et d’argon. Ce découplage des degrés de liberté internes permet de simplifier la structure rotationnelle des spectres enregistrés et facilite l’étude des états vibrationnels excités des molécules en révélant la structure des bandes chaudes, absentes des bases de données spectroscopiques pour la plupart des molécules polyatomiques. Une approche complémentaire consiste à sonder la couche de choc produite par l'ajout d'un obstacle sur le trajet de l'écoulement. La température rotationnelle est brutalement élevée donnant ainsi accès aux transitions rotationnelles de hautes valeurs du nombre quantique J. Ces deux méthodes ont été appliquées avec succès au méthane qui joue un rôle majeur dans de nombreux environnements astrophysiques chauds. Enfin, outre la production de données spectroscopiques, ce dispositif expérimental a permis de mettre en évidence la relaxation des degrés de liberté internes du CO dans différents gaz porteurs (He et Ar) en suivant l’évolution des températures de rotation et vibration le long de l'écoulement hypersonique, aussi bien dans le cœur isentropique qu'au sein des couches limites. Ces températures sont comparées aux températures d'excitation obtenues par des méthodes ab initio afin de valider des calculs de taux de collision. Les données obtenues alimenteront à terme des bases de données, matière première au développement de codes de transfert radiatif permettant d'interpréter les observations en provenance des milieux astrophysiques ''chauds''. / A huge quantity of infrared spectra is collected by terrestrial and space telescopes from cool astrophysical objects (500-3000 K) like exoplanet (hot Jupiter) and brown dwarf atmospheres or circumstellar envelop of AGB stars. The main purpose of this thesis connected to experimental astrophysics is to provide high temperature data of key molecules by reproducing in the laboratory some aspects of such environments. A new setup built in Rennes couples a High Enthalpy Source to a highly sensitive Cavity Ring-Down Spectrometer. The gas studied, heated in the reservoir up to 2000 K, is expanded in a vacuum chamber through a circular nozzle and the resulting hypersonic jet can be probed at any location. Computational flow dynamics (CFD) calculations associated to a modeling of the infrared absorption lead to synthetic lines which are in very good agreement with the observed spectra. These numerical data were used to attribute the unusual double peak line shapes to the particular flow structure of axisymmetric hypersonic jets. Strong out-of-equilibrium conditions were evidenced in the isentropic core of the expansion. High vibrational temperature (1350 K) and rotational temperature lower than 10 K were recorded inside a jet of CO seeded in Ar. This degrees-of-freedom decoupling greatly simplifies the rotational structure of the recorded infrared spectra and unveils the presence of hot bands stemming from highly excited vibrational states which are significantly populated at high temperature. Our approach is therefore well suited for the study of rotationally cold hot bands of polyatomic molecules which are virtually missing in spectroscopic databases. A complementary approach consists in probing the shock layer formed upstream of an obstacle set perpendicularly to the hypersonic flow axis. Rotational temperature raises abruptly downstream the shock, revealing transitions associated with high J quantum numbers. These two methods were successfully applied to methane which plays an important role in numerous astrophysical environments. In addition to the acquisition of infrared spectroscopic data, the relaxation of internal degrees-of-freedom of CO seeded in different carrier gases (Ar and He) was studied by following the evolution of rotational and vibrational temperatures along the flow, in the isentropic core as well as in the peripheral viscous layers. These temperatures were compared to excitation temperatures calculated by an ab initio method in order to validate collision rates. These data will feed databases needed for the development of radiative transfer codes with a view to a better modeling of spectra observed from "hot" astrophysical environments.

Hyperdoping of Si with deep-level impurities has attracted renewed interest for its unique physical properties, such as the broad sub-bandgap absorption in the infrared wavelength at room temperature. In this thesis, tellurium (Te) hyperdoped Si has been prepared by ion implantation and pulsed laser melting with the Te doping concentration several orders of magnitude above the solid solubility limit. The structural, electrical and optical properties were systematically investigated. A strong room-temperature broadband infrared absorption down to 0.048 eV (25 μm) is observed in the resulting Te-hyperdoped Si layers. The room-temperature operation of a mid-infrared photodetector is demonstrated based on Te-hyperdoped Si. In addition, an impurity-induced insulator-to-metal transition in Te-hyperdoped Si has been identified via the electrical transport measurements. Besides, the electron concentration in Te-hyperdoped Si layers is approaching 1021 cm-3 and does not show saturation. Combining density functional calculations and Rutherford backscattering/channeling measurements, the microscopic mechanism for yielding the outstanding physical properties listed above has been unveiled. The Te-dimer complex sitting on adjacent Si lattice sites has the smallest formation energy and is thus the preferred configuration at high doping concentration. Those substitutional Te are effective donors, leading to the non-saturating carrier concentration as well as to the insulator to metal transition. Finally, a comprehensive study regarding the thermal stability has been performed and the Te-hyperdoped Si layers exhibits thermal stability up to 400 °C with a duration of at least 10 minutes. Therefore, Te-hyperdoped Si opens two perspectives for opto/micro-electronics. One is realization of broadband infrared photodetection at room temperature by using only Si materials, which may be integrated into on-chip Si-based photonic systems. The second is to achieve ultra-high n-type carrier concentrations for nano-electronics by forming Te-dimer dopants, which can overcome the saturation problem of conventional shallow n-type dopants.

Ce travail est une contribution à l'étude spectroscopique de deux gaz d'origine anthropique pour lesquels la modélisation de la signature infrarouge pourra permettre une quantification dans rejets dans l'atmosphère. L'hexafluorure de soufre (SF₆) est principalement rejeté par l'industrie électrique, qui l'utilise comme isolant gazeux et sa concentration augmente rapidement dans l'atmosphère (de l'ordre de 7 % par an). C'est un gaz à effet de serre puissant listé dans le protocole de Kyoto car ses absorptions intenses vers 10 μm placées dans une fenêtre de transparence atmosphérique et sa durée de vie élevée dans la haute atmosphère(environ 3200 ans) lui confèrent un coefficient de transfert radiatif exceptionnellement élevé (Global Warming Potential, ou GWP égal à 23900 fois celui du dioxyde de carbone, CO₂). La détection et la quantification de ce gaz par sa signature infrarouge via des mesures par satellite nécessitent une très bonne modélisation des spectres d'absorption, incomplètement connus. SF6 est un molécule lourde qui présente un grand nombre de niveaux vibrationnels de basse énergie, donnant lieu à des bandes chaudes dans le domaine des absorptions atmosphériques autour de sa vibration fondamentale la plus intense et celles-ci impliquent des états excités peu ou pas caractérisés. Ainsi, à température ambiante, seules 32 %des molécules se trouvent dans l'état vibrationnel de base. Les bases de données actuelles ne contiennent que les données des bandes de vibration fondamentales. Pour pallier ce manque, il est donc nécessaire d'observer un certain nombre de transitions depuis l'état fondamental vers les niveaux excités de basse énergie servant d'état initial aux bandes chaudes et d'acquérir des données permettant de modéliser aussi les niveaux à deux quanta de vibration constituant les niveaux d'arrivée de ces bandes chaudes.Ce travail est une contribution à l'étude spectroscopique de deux gaz d'origine anthropique pour lesquels la modélisation de la signature infrarouge pourra permettre une quantification dans rejets dans l'atmosphère. L'hexafluorure de soufre (SF6) est principalement rejeté par l'industrie électrique, qui l'utilise comme isolant gazeux et sa concentration augmente rapidement dans l'atmosphère (de l'ordre de 7 % par an). C'est un gaz à effet de serre puissant listé dans le protocole de Kyoto car ses absorptions intenses vers 10 μm placées dans une fenêtre de transparence atmosphérique et sa durée de vie élevée dans la haute atmosphère(environ 3200 ans) lui confèrent un coefficient de transfert radiatif exceptionnellement élevé (Global Warming Potential, ou GWP égal à 23900 fois celui du dioxyde de carbone, CO₂). La détection et la quantification de ce gaz par sa signature infrarouge via des mesures par satellite nécessitent une très bonne modélisation des spectres d'absorption, incomplètement connus. SF₆ est un molécule lourde qui présente un grand nombre de niveaux vibrationnels de basse énergie, donnant lieu à des bandes chaudes dans le domaine des absorptions atmosphériques autour de sa vibration fondamentale la plus intense et celles-ci impliquent des états excités peu ou pas caractérisés. Ainsi, à température ambiante, seules 32 %des molécules se trouvent dans l'état vibrationnel de base. Les bases de données actuelles ne contiennent que les données des bandes de vibration fondamentales. Pour pallier ce manque, il est donc nécessaire d'observer un certain nombre de transitions depuis l'état fondamental vers les niveaux excités de basse énergie servant d'état initial aux bandes chaudes et d'acquérir des données permettant de modéliser aussi les niveaux à deux quanta de vibration constituant les niveaux d'arrivée de ces bandes chaudes. / This work is a contribution to the spectroscopic study of two gases of anthropogenic origin for which the modeling of the infrared signature may allow a quantification in releases in the atmosphere. Sulfur hexafluoride (SF₆) is mainly rejected by the electrical industry, which uses it as a gaseous insulator and its concentration increases rapidly in the atmosphere (of the order of 7 per cent per year). It is a potent greenhouse gas listed in the Kyoto Protocol because its intense absorption around 10 μm issituated in a window of atmospheric transparency and its lifetime in the upper atmosphere (approximately 3200 years) confers an exceptionally high radiative transfer coefficient (Global WarmingPotential, or GWP equal to 23900 times that of carbon dioxide,CO2). The detection and quantification of this gas by its infrared signature via satellite measurements requires a very accurate modeling of the absorption spectra, incompletely known. For SF₆,in particular because of the fact that this heavy molecule presents a large number of vibrational levels of low energy, there exist hotbands in the region of atmospheric absorption around its most intense fundamental absorption (v₃); these involve excited states little or not characterized. Thus, at ambient temperature, only 32% of the molecules are located in the vibrational ground state. Current databases contain only data for the fundamental vibrationband. To compensate for this lack, it is therefore necessary toobserve a number of transitions from the ground state to the excited levels of low energy used corresponding to initial states of the hot bands and to acquire data for modeling also levels with two quanta of vibration constituting the upper levels of arrival of thes ehot bands.This work is a contribution to the spectroscopic study of two gases of anthropogenic origin for which the modeling of the infrared signature may allow a quantification in releases in the atmosphere.Sulfur hexafluoride (SF₆) is mainly rejected by the electricalindustry, which uses it as a gaseous insulator and its concentration increases rapidly in the atmosphere (of the order of 7 per cent peryear). It is a potent greenhouse gas listed in the Kyoto Protocolbecause its intense absorption around 10 μm is situated in awindow of atmospheric transparency and its lifetime in the upper atmosphere (approximately 3200 years) confers an exceptionally high radiative transfer coefficient (Global Warming Potential, orGWP equal to 23900 times that of carbon dioxide, CO2). The detection and quantification of this gas by its infrared signature via satellite measurements requires a very accurate modeling of theabsorption spectra, incompletely known. For SF6, in particular because of the fact that this heavy molecule presents a largenumber of vibrational levels of low energy, there exist hot bands in the region of atmospheric absorption around its most intensefundamental absorption (v3); these involve excited states little or not characterized. Thus, at ambient temperature, only 32 % of themolecules are located in the vibrational ground state. Current databases contain only data for the fundamental vibration band. Tocompensate for this lack, it is therefore necessary to observe a number of transitions from the ground state to the excited levels oflow energy used corresponding to initial states of the hot bands andto acquire data for modeling also levels with two quanta ofvibration constituting the upper levels of arrival of these hot bands.