Dans une première partie nous explorerons les effets d'impuretés désordonnées et paramagnétiques sur l'effet spin-Hall intrinsèque dans un gaz d'électrons bi-dimensionnel avec un couplage spin-orbite de Rashba. A faible désordre, la conductivité de spin-Hall reste proche de sa valeur d'échantillon pur, comme le montrent un calcul analytique de réponse linéaire et une étude numérique. De fortes fluctuations sont toutefois observées, elles augmentent avec l'importance du désordre. Pour caractériser la dynamique d'un paquet d'onde sur un réseau, nous mesurons sa taille, le taux de participation inverse, et sa dimension de corrélation. Le système subit une transition de localisation à une valeur critique du désordre. Dans le régime localisé, la densité locale d'états n'est plus uniforme et ne coïncide plus avec la densité totale d'états. Une corrélation antiferromagnétique entre les impuretés et les électrons de conduction est observée. Après la transition de localisation, la conductivité de spin augmente significativement. La première correction quantique dans le formalisme de réponse linéaire, contribue positivement à la conductivité de spin-Hall. Dans une seconde partie, le modèle de Hubbard avec double échange avec corrélations électroniques est étudié par la méthode du champ moyen dynamique (DMFT) dans l'approximation de non-croisement pour la résolution du problème d'impureté (NCA). Autour du quart remplissage, un polaron orbital est observé et décrit à l'aide d'un Hamiltonien effectif. Le double échange dans les semi-conducteurs magnétiques dilués est étudié dans l'approximation du potentiel cohérent (CPA). / Spintronics is a research area that is concerned with the storage and transfer of information by means of electron spins. In the first part we investigated the intrinsic spin Hall effect in the presence of disordered magnetic impurities in a paramagnetic state in a two dimensional electron gas with Rashba spin-orbit coupling. In the presence of weak magnetic disorder the spin Hall conductivity stays close to its universal (clean system) value, as shown by analytical linear response calculations and numerical simulations. Heavy spin conductivity fluctuations are observed, that increase with disorder strength. To investigate the spreading of a wavepacket on a lattice we measure the wavepacket width, the inverse participation ratio and the (2)-fractal dimension. It is shown the system undergoes a localization transition at a critical disorder strength. In the localized regime the local density of states is not uniform anymore. An anti-ferromagnetic correlation between electron spins and impurity magnetic moments is observed. Beyond the localization transition the spin conductivity increases significantly. The first quantum (Cooperon) corrections in the linear response formalism are shown to contribute positively to the spin Hall conductivity. In the second part the double exchange Hubbard model for correlated electron systems is studied using dynamical mean field theory (DMFT) with the non-crossing approximation (NCA). Around quarter filling an orbital polaron is observed, numerically and in an effective Hamiltonian. Double exchange in dilute magnetic semiconductors is studied using the coherent potential approximation (CPA).

A new approach to the discovery of high absorbing semiconductors for solar cells was taken by working under a set of design principles and taking a systemic methodology. Three transition metal chalcogenides at varying states of development were evaluated within this framework. Iron pyrite (FeS���) is well known to demonstrate excellent absorption, but the coexistence with metallic iron sulfides was found to disrupt its semiconducting properties. Manganese diselenide (MnSe���), a material heavily researched for its magnetic properties, is proposed as a high absorbing alternative to iron pyrite that lacks destructive impurity phases. For the first time, a MnSe��� thin film was synthesized and the optical properties were characterized. Finally, CuTaS���, a known but never characterized material, is also proposed as a high absorbing semiconductor based on the design principles and experimental results. / Graduation date: 2013

No description available.

Optically transparent carbon based nanomaterials including graphene and carbon nanotubes(CNTs) are promising candidates as transparent conductive electrodes due to their high electrical conductivity coupled with high optical transparency, can be flexed several times with minimal deterioration in their electronic properties, and do not require costly high vacuum processing conditions. CNTs are easily solution processed through the use of surfactants sodium dodecyl sulfate(SDS) and sodium cholate(SC). Allowing CNTs to be deposited onto transparent substrates through vacuum filtration, ultrasonic spray coating, dip coating, spin coating, and inkjet printing. However, surfactants are electrically insulating, limit chemical doping, and increase optical absorption thereby decreasing overall performance of electrodes. Surfactants can be removed through nitric acid treatment and annealing in an inert environment (e.g. argon). In this thesis, the impact of surfactant removal on electrode performance was investigated. Nitric acid treatment has been shown to p-dope CNTs and remove the surfactant SDS. However, nitric acid p-doping is naturally dedoped with exposure to air, does not completely remove the surfactant SC, and has been shown to damage CNTs by creating defect sites. Annealing at temperatures up to 1000°C is advantageous in that it removes insulating surfactants. However, annealing may also remove surface functional groups that dope CNTs. Therefore, there are competing effects when annealing CNT electrodes. The impacts on electrode performance were investigated through the use of conductive-tip atomic force microscopy, sheet resistance, and transmittance measurements. In this thesis, the potential of graphene CNT composite electrodes as high performing transparent electrodes was investigated. As-made and annealed graphene oxide CNT composites electrodes were studied. Finally, a chemical vapor deposition grown graphene CNT composite electrode was also studied.

This thesis is devoted to the study of operators on discrete structures. The operators are supposed to be self-adjoint and obey a certain translation invariance property. The discrete structures are given as Cayley graphs via finitely generated groups. Here, sofic groups and amenable groups are in the center of our considerations. Note that every finitely generated amenable group is sofic. We investigate the spectrum of a discrete self-adjoint operator by studying a sequence of finite dimensional analogues of these operators. In the setting of amenable groups we obtain these approximating operators by restricting the operator in question to finite subsets Qn , n ∈ N. These finite dimensional operators are self-adjoint and therefore admit a well-defined normalized eigenvalue counting function. The limit of the normalized eigenvalue counting functions when |Qn | → ∞ (if it exists) is called the integrated density of states (IDS). It is a distribution function of a probability measure encoding the distribution of the spectrum of the operator in question on the real axis. In this thesis, we prove the existence of the IDS in various geometric settings and for different types of operators. The models we consider include deterministic as well as random situations. Depending on the specific setting, we prove existence of the IDS as a weak limit of distribution functions or even as a uniform limit. Moreover, in certain situations we are able to express the IDS via a semi-explicit formula using the trace of the spectral projection of the original operator. This is sometimes referred to as the validity of the Pastur-Shubin trace formula. In the most general geometric setting we study, the operators are defined on Cayley graphs of sofic groups. Here we prove weak convergence of the eigenvalue counting functions and verify the validity of the Pastur-Shubin trace formula for random and non-random operators . These results apply to operators which not necessarily bounded or of finite hopping range. The methods are based on resolvent techniques. This theory is established without having an ergodic theorem for sofic groups at hand. Note that ergodic theory is the usual tool used in the proof of convergence results of this type. Specifying to operators on amenable groups we are able to prove stronger results. In the discrete case, we show that the IDS exists uniformly for a certain class of finite hopping range operators. This is obtained by using a Banach space-valued ergodic theorem. We show that this applies to eigenvalue counting functions, which implies their convergence with respect to the Banach space norm, in this case the supremum norm. Thus, the heart of this theory is the verification of the Banach space-valued ergodic theorem. Proceeding in two steps we first prove this result for so-called ST-amenable groups. Then, using results from the theory of ε-quasi tilings, we prove a version of the Banach space-valued ergodic theorem which is valid for all amenable groups. Focusing on random operators on amenable groups, we prove uniform existence of the IDS without the assumption that the operator needs to be of finite hopping range or bounded. Moreover, we verify the Pastur-Shubin trace formula. Here we present different techniques. First we show uniform convergence of the normalized eigenvalue counting functions adapting the technique of the Banach space-valued ergodic theorem from the deterministic setting. In a second approach we use weak convergence of the eigenvalue counting functions and additionally obtain control over the convergence at the jumps of the IDS. These ingredients are applied to verify uniform existence of the IDS. In both situations we employ results from the theory of large deviations, in order to deal with long-range interactions.

Die fortwährende Verkleinerung der Strukturbreiten in der Mikroelektronik erfordert es, herkömmliche SiO2 Dielektrika durch Materialien mit kleinerer Dielektrizitätskonstante zu ersetzen. Dafür sind verschiedene „low-k Materialien“ entwickelt worden. Unter diesen sind die Organosilikatgläser, die aus SiO2 Netzwerken mit eingelagerten Methylgruppen bestehen wegen ihrer ausgezeichneten Eigenschaften besonders interessant als Dielektrika zwischen metallischen Leiterbahnen. In dieser Arbeit sind fünf verschiedene dieser „low-k Materialien“ untersucht worden: ein dichtes und vier poröse Materialien, die alle durch plasmagestützte chemische Gasphasenabscheidung hergestellt wurden. Die strukturellen, chemischen und dielektrischen Eigenschaften der Materialien wurden mit Hilfe der analytischen Durchstrahlungselektronenmikroskopie unter Verwendung eines abbildenden GATAN-Energiespektrometers untersucht. Die Bestimmung der radialen Verteilungsfunktion (RDF) zur Charakterisierung der atomaren Nahordnung ermöglicht uns die Ermittlung mittlerer Bindungslängen und – winkel sowie der mikroskopischen Dichte des Materials. Gegenüber SiO2 wurden in den untersuchten „low-k Materialien“ stark veränderte mittlere Si-O, O-O und Si-Si Bindungslängen gefunden. Dieses wirkt sich natürlich auch auf die mittleren Si-O-Si bzw. O-Si-O Bindungswinkel aus, und wie erwartet war auch die mikroskopische Dichte der „low-k Materialien“ kleiner als die Dichte des SiO2. Elektronen Energieverlustspektroskopie (EELS) und Photoelektronenspektroskopie (XPS) wurden zur Charakterisierung der chemischen Umgebung der Atome in den „low-k Materialien“ herangezogen. Die Energien von Ionisationskanten und die Bindungsenergien der Silizium-2p und Sauerstoff-1s Elektronen waren in den „low-k Materialien“ größer als im SiO2. Die Kohlenstoffatome kamen in den „low-k Materialien“ sowohl sp2 als auch sp3 hybridisiert vor. sp2-Hybridisierung liegt vor, wenn Bindungen wie Si=CH2 und C=C im Netzwerk vorkommen, während sp3 Hybridisierung z.B. dann vorkommt, wenn freie Si-Bindungen durch –CH3 Gruppen abgesättigt werden. Die Anteile an sp2- bzw. sp3-hybridisierten Kohlenstoffatome wurden aus der Feinstruktur der K-Energieverlustkanten des Kohlenstoffs abgeschätzt. Das ergab, daß die meisten Kohlenstoffatome in den „low-k Materialien“ sp2-hybridisiert sind. Die dielektrischen Eigenschaften wurden durch Kramers-Kronig-Transformation einer Energieverlustfunktion ermittelt, die aus dem Niedrigverlust-EELS-Spektrum im Bereich der Plasmonenanregungen gewonnen wurde. Die Bandlücke des SiO2 beträgt ungefähr 9 eV während dichte „low-k Materialien“ aufgrund der Unregelmäßigkeiten in ihrem SiO2-Netzwerk zusätzliche Zustandsdichten innerhalb der Bandlücke aufweisen. Die Erzeugung von Poren im „low-k Material“ vermindert offenbar die Zustandsdichte im Bereich der Bandlücke und erweitert diese im Vergleich zum SiO2. Eine Modellrechnung mit der Dichtefunktionaltheorie für ein Strukturmodell, das den „low-k Materialien“ nahe kommt, ist zum Vergleich mit der experimentell gefundenen kombinierten Zustandsdichte herangezogen worden und zeigt eine gute Übereinstimmung. Die im Standard-Herstellungsprozeß vorkommenden Verfahren des Plasmaätzens und der Plasmaveraschung können die Struktur des „low-k Materials“ z.B. an den Seitenwänden von Ätzgräben verändern. Die gestörten Bereiche wurden mit der energiegefilterten Elektronenmikroskopie untersucht. Dabei wurde gefunden, daß sich die Strukturveränderungen der Seitenwände bis zu einer Tiefe in der Größenordnung von ungefähr 10 Nanometern erstrecken. Diese Bereiche sind verarmt an Kohlenstoff und ähneln folglich mehr einem SiO2-Dielektrikum. Die Kohlenstoffverarmung erstreckt sich in die „low-k Schicht“ in Form eines gaussartigen Profils mit maximaler Kohlenstoffkonzentration in der Mitte der Schicht. Die Sauerstoffkonzentration und die mikroskopische Dichte steigen in der Nähe der Seitenwände.

This thesis describes the measurement of rate constants for gas phase reactions as a function of temperature (285 ≤ T/K ≤ 850) and pressure (48 ≤ P/Torr ≤ 700). One or both reactants was monitored directly in real time, using time–resolved resonance fluorescence (for atoms) and u.v. absorption (for radicals). Reactants were produced by exciplex laser flash photolysis. The technique was used to measure rate constants to high precision for the following reactions under the stated conditions: • H+O2+He->HO2+He and H+O2−→OH+O, for 800 ≤ T/K ≤ 850 and 100 ≤ P/Torr ≤ 259. A time–resolved study was performed at conditions close to criticality in the H2–O2 system. The competition between the two reactions affected the behaviour of the system after photolysis, and the rate constants were inferred from this behaviour. • H+C2H4+He<-->C2H5+He (T = 800 K, 97 ≤ P/Torr ≤ 600). The reactions were well into the fall–off region at all conditions studied. At 800 K, the system was studied under equilibrating conditions. The study provided values of the forward and reverse rate constants at high temperatures and enabled a test of a new theory of reversible unimolecular reactions. The controversial standard enthalpy of formation of ethyl, DH0f,298 (C2H5), was determined to be 120.2±0.8 kJ mol−1. Master Equation calculations showed that reversible and irreversible treatments of an equilibrating system should yield the same value for both thermal rate constants. • H+C3H5+He->C3H6+He (T = 291 K, 98 ≤ P/Torr ≤ 600) and O+C3H5 −→ products (286 ≤ T/K ≤ 500, 48 ≤ P/Torr ≤ 348). Both reactions were pressure–independent, and the latter was also independent of temperature with a value of (2.0±0.2) ×10−10 cm3 molecule−1 s−1. • H+C2H2+He<-->C2H3+He (298 ≤ T/K ≤ 845, 50 ≤ P/Torr ≤ 600). At 845 K, both reactions were in the fall–off region; rate constants were used to determine the standard enthalpy of formation of vinyl, ¢H0f,298 (C2H3), as 293±7 kJ mol−1. The value of this quantity has until recently been very controversial. • H+CH4 <--> CH3+H2. The standard enthalpy of formation of methyl, DH0 f,298 (CH3), was determined by re–analysing existing kinetic data at T = 825 K and 875 K. A value of 144.7±1.1 kJ mol−1 was determined. Preliminary models were examined to describe the loss of reactants from the observation region by diffusion and pump–out. Such models, including diffusion and drift, should prove useful in describing the loss of reactive species in many slow–flow systems, enabling more accurate rate constants to be determined.

Cette thèse fait partie d’un projet franco-keyan dénommé ELEPHOX (ELEctrochemical and PHOto Properties of Some Remarkable Ruthenium and Iron CompleXes). En particulier, notre focus est la continuation du travail de C. Muhavini Wawire, Damien Jouvenot, Fréd erique Loiseau, Pablo Baudin, Sébastien Liatard, Lydia Njenga, Geoffrey Kamau, et Mark E. Casida, “Density-Functional Study of Lumininescence in Polypyridine Ruthenium Complexes,” J. Photochem. and Photobiol. A 276, 8 (2014). Cet article a proposé une indice orbitalaire de temps de luminescence pour les complexesde ruthénium. Cependant cet article n’était limité qu’à quelques mnolecules. Afin d’avoir une théorie plus fiable et donc potentiellement plus utile, il faudra tester l’indice de luminescence sur beaucoup plus de molécules. Ayant établi le protocol, il était “évident” mais toujours un défi de le tester sur encore une centaine de molécules pour démonter ou infirmer l’indice proposée. Pour ce faire, j’ai examainé les 98 pages de la Table I de A. Juris, V. Balzani, F. Bargelleti, S. Campagna, P. Belser, et A.V. Zelewsky, “Ru(II) polypyridine complexes: Photophysics, photochemistry, electrochemistry, and chemiluminescence,” Chem. Rev. 84, 85 (1988) et j’ai extrait un nombre important de données susceptibles à comparaison avec les résultats des calculs de la théorie de la fonctionelle de la densité (DFT) et la DFT dépendante du temps (TD-DFT). Comme les résultats étaient suffisament encourageant, le modèle DFT était examiné de plus près avec la méthode d’une théorie de champs de ligands (LFT) à la base de la densité des états partielle (PDOS). Ainsi j’ai pu tester l’indice de luminescence proposée précédement par laméthode PDOS-LFT et j’ai trouvé des difficultés avec l’indice initialement proposée. Par contre, nous avons pu proposer une nouvelle indice de luminescence qui, à quelques exceptions près, a une corrélation linéaire avec une barrière énergétique moyenne pour l’état triplet excité dérivée à partir des données experimentales. À l’avenir nous pouvons proposer une investigation plus directe de la barrière sur la surface triplet excité pour remplacer la valeur approximative déduite de l’expérience. Puis nous voulons voir sinotre indice de luminescence s’appliquent aux cas des complexes d’iridium. / This thesis is part of the Franco-Kenyan project ELEPHOX (ELEctrochemicaland PHOto Properties of Some Remarkable Ruthenium and Iron CompleXes)project. In particular, it focused on the continuation of the work ofC. Muhavini Wawire, Damien Jouvenot, Fréd erique Loiseau, Pablo Baudin,Sébastien Liatard, Lydia Njenga, Geoffrey Kamau, and Mark E. Casida,“Density-Functional Study of Lumininescence in Polypyridine RutheniumComplexes,” J. Photochem. and Photobiol. A 276, 8 (2014). That paperproposed a luminescence index for estimating whether a ruthenium complexwill luminesce or not. However that paper only tested the theory ona few molecules. In order for the theory to have a significant impact, itmust be tested on many more molecules. Now that the protocol has beenworked out, it was a straightforward but still quite challenging matter todo another 100 or so molecules to prove or disprove the theory. In order todo so, I went through the 98 pages of Table I of A. Juris, V. Balzani, F.Bargelleti, S. Campagna, P. Belser, and A.V. Zelewsky, “Ru(II) polypyridinecomplexes: Photophysics, photochemistry, electrochemistry, and chemiluminescence,”Chem. Rev. 84, 85 (1988) and extracted data suitable for comparingagainst density-functional theory (DFT) and time-dependent (TD-)DFT.Since the results were sufficiently encouraging, the DFT model was examinedin the light of partial density of states ligand field theory (PDOS-LFT) andthe previously proposed luminescence indices were tested. In fact, the originallyproposed indices were not found to be very reliable but we were able topropose a new luminescence index based upon much more data and in analogywith frontier-molecular orbital ideas. Except for a few compounds, this index provides a luminescence index with a good linear correlation with anexperimentally-derived average excited-state activation energy barrier. Futurework should be aimed at both explicit theoretical calculations of thisbarrier for ruthenium complexes and extension of the luminescence indexidea to iridium complexes.

No description available.

Cette thèse est consacrée à l'étude du transport électronique dans des modèles désordonnés non ergodiques, dans le cadre de la théorie des opérateurs de Schrödinger aléatoires.Pour commencer, nous reformulons l'outil principal pour notre étude, l'analyse multi-échelles, dans le cadre non ergodique. Nous établissons les conditions d'homogénéité que l'opérateur doit vérifier pour appliquer cette méthode. Ensuite, nous étudions les propriétés spectrales des opérateurs de Delone-Anderson non ergodiques. Ces systèmes modélisent l'énergie d'une particule en interaction avec un milieu dont la structure atomique est quasi-cristalline et la nature des impuretés est désordonnée. Dans le cas où les mesures de probabilité associées au potentiel de simple site sont régulières, en dimension 2 et sous l'effet d'un champ magnétique, nous établissons une transition métal-isolant et l'existence d'une énergie de mobilité qui sépare les régions de localisation et de délocalisation dynamiques. Pour des mesures de simple site régulières et celle de Bernoulli, nous démontrons la localisation dynamique en bas du spectre. De plus, nous obtenons une description quantitative de la région de localisation dynamique en termes de paramètres géométriques de l'ensemble de Delone de base.Nous concluons ce travail avec l'étude de la densité d'états intégrée pour des modèles de Delone-Anderson, en combinaison avec des outils de la théorie des systèmes dynamiques associés aux quasi-cristaux. Sous certaines conditions sur la géométrie de l'ensemble de Delone sous-jacent, nous montrons l'existence de la densité d'états intégrée. De plus, dans le cas d'une perturbation de Delone-Anderson du Laplacien libre, nous démontrons qu'elle a un comportement asymptotique de Lifshitz en bas du spectre. / His thesis is devoted to the study of electronic transport in non ergodic disordered models, in the framework of random Schrödinger operators.We start by reformulating the main tool in our study, the multiscale analysis, in the non ergodic setting. We establish suitable homogeneity conditions on the operator, in order to apply this method.Next, we study the spectral properties of non ergodic Delone-Anderson operators. These models represent a particle interacting with a medium whose atomic structure is quasi-crystalline and the nature of its impurities is disordered. In the case where the probability measures associated to the single-site potential are regular, in dimension 2 and under the effect of a magnetic field, we establish a metal-insulator transition and the existence of a mobility edge that separates the localization and delocalization regions. In arbitrary dimension, for regular and for Bernoulli single-site measures, we show dynamical localization at the bottom of the spectrum. Moreover, we obtain a quantitative lower bound on the size of the localization region in terms of the geometric parameters of the underlying Delone structure.We conclude this essay by studying the integrated density of states for Delone-Anderson models, using tools from the theory of dynamical systems associated to quasicrystals. Under certain conditions on the geometry of the underlying Delone set, we show the existence of the integrated density of states. Furthermore, in the case of a Delone-Anderson perturbation of the free Laplacian, we show it exhibits Lifshitz tails at the bottom of the spectrum.