Magister Scientiae - MSc (Chemistry) / Although cadmium and lead chalcogenide quantum dot have excellent optical and photoluminescent properties that are highly favorable for biological applications, there still exists increasing concerns due to the toxicity of these metals. We, therefore, report the synthesis of new aqueous soluble IrSe quantum dot at room temperature utilizing a bottom-up wet chemistry approach. NaHSe and H2IrCl6 were utilized as the Se and Ir source, respectively. High-resolution transmission electron microscopy reveals that the synthesized 3MPA-IrSe Qd are 3 nm in diameter. The characteristics and properties of the IrSe Qd are investigated utilizing, Selected Area electron diffraction, ATR- Fourier Transform Infra-Red Spectroscopy, Energy Dispersive X-ray spectroscopy, Photoluminescence, Cyclic Voltammetry and chronocoulometry. A 3 fold increase in the optical band gap of IrSe quantum dot in comparison to reported bulk IrSe is observed consistent with the effective mass approximation theory for semiconductor materials of particles sizes < 10 nm. The PL emission of the IrSe quantum dot is at 519 nm. Their electro-activity is studied on gold electrodes and exhibit reduction and oxidation at - 107 mV and +641 mV, with lowered reductive potentials. The synthesized quantum dot are suitable for low energy requiring electrochemical applications such as biological sensors and candidates for further investigation as photoluminescent biological labels.

Na primeira parte do trabalho, foram investigados materiais ativos para eletro-oxidar etanol e acetaldeído seletivos para a rota C2 (Carbono 2) e, também, ativos para eletro-oxidar hidrogênio molecular, visando a aplicação em células a combustível de hidrogênio indireto. Neste tipo de célula, um processador de combustível externo desidrogena o etanol e os produtos desta reação, contendo H2, acetaldeído e, possivelmente, etanol residual, são direcionados para alimentar o ânodo. Neste sentido, o eletrocatalisador anódico pode ser ativo para a eletro-oxidação de etanol residual, bem como acetaldeído, mas este deve catalisar a reação via C2 com o objetivo de evitar a formação de espécies que envenenam a superfície catalítica (CO ou CHx), ou seja, a ligação C-C deve permanecer intacta. Os eletrocatalisadores bimetálicos foram formados por M/Pt/C (onde M = W, Ru ou Sn) e os produtos reacionais foram analisados por DEMS On-line. Os resultados mostraram que Ru/Pt/C e Sn/Pt/C apresentaram maiores taxas de reação global, no entanto, eles não foram seletivos. Por outro lado, W2/Pt3/C foi mais seletivo para a rota C2, dada a não formação de CH4 e CO2. Além disso, este material também foi ativo e estável para a eletro-oxidação de H2, mesmo na presença de acetaldeído, o que o torna um potencial catalisador para aplicação no ânodo de células a combustível de hidrogênio indireto. Na segunda parte do trabalho, o objetivo foi relacionado com o estudo de eletrocatalisadores seletivos para a rota C1 (Carbono 1). A oxidação eletroquímica do etanol e de seus produtos reacionais foram investigados por DEMS on-line em temperatura ambiente e intermediária (245oC). Para temperatura ambiente, utilizou-se solução aquosa de ácido sulfúrico (H2SO4) e, para temperatura intermediária, utilizou-se ácido sólido (CsH2PO4) como eletrólito. Os eletrocatalisadores investigados foram formados por SnOxRuOx-Pt/C e Pt/C. Em temperatura ambiente, os resultados de polarização potenciodinâmica mostraram uma maior atividade eletrocatalítica para o material SnOxRuOx-Pt/C, com eficiência de corrente para formação de CO2 de 15,6% contra 15,2% para Pt/C, sob condições estagnantes, sem controle por transporte de massa. O stripping de resíduos reacionais, após a eletro-oxidação de etanol bulk, sob condições de fluxo, mostraram o acúmulo de espécies com 1 átomo de carbono (CO e CHx) que causam o bloqueio dos sítios ativos e são oxidadas eletroquimicamente somente em mais altos potenciais (ca. 1,0 V). Por outro lado, as curvas de polarização a 245oC mostraram maiores valores de eficiências de correntes para formação de CO2 (45% para Pt/C em ambos potenciais 0,5 V e 0,8 V contra 36% e 50% para SnOxRuOx-Pt/C em 0,5 V e 0,8 V respectivamente) quando comparado com os valores obtidos em temperatura ambiente, mas com atividades similares para SnOxRuOx-Pt/C e Pt/C. Para ambos os eletrocatalisadores, os estudos de espectrometria de massas a 245oC evidenciaram que as rotas eletroquímicas ocorrem em paralelo com rotas puramente químicas, envolvendo catálise heterogênea, de decomposição do etanol, produzindo H2 e CO2 como produtos majoritários. / In the first part of this study were investigated active materials to electro-oxidize ethanol and acetaldehyde selective for the C2 route (Carbon 2), besides active to electro-oxidize molecular hydrogen, in order to apply into indirect hydrogen fuel cells. In this type of cell, ethanol can be dehydrogenated in the external fuel processor and the products generated in this reaction, containing H2, acetaldehyde and, possibly, unreacted ethanol are used to feed the fuel cell anode. Therefore, the anode electrocatalyst has to be active to electro-oxidize residual ethanol and acetaldehyde, however, it has to catalyze the reaction via C2 route aiming to avoid the species formation that poison the catalyst surface (CO and CHx), in the other words, the C-C bond should remain intact. The bimetallic electrocatalysts were formed by W, Ru and Sn-modified Pt nanoparticles. The reaction products were followed by on-line differential electrochemical mass spectrometry (DEMS) experiments. The results showed that Ru/Pt/C and Sn/Pt/C presented higher overall reaction rate when compared to the other studied materials, however, they were non-selective. On the other hand, W/Pt/C with high W content was more selective to the C2 route, evidenced by the absence of the DEMS signals for molecules with one carbon atom such as CH4 and CO2. Additionally, this material was active and stable for H2 electro-oxidation even in the acetaldehyde presence, what turns it into a potential electrocatalyst for application in the anode of indirect hydrogen fuel cells. In the second part of this work, we investigated conditions and electrocatalysts selective to the C1 route. The ethanol electro-oxidation and its reaction products were investigated by on-line DEMS at room and intermediate temperature. At room, and intermediate temperature (245oC), the electrolytes were aqueous sulfuric acid and solid-state acid (CsH2PO4), respectively. The catalysts investigated were SnOxRuOx-Pt/C and Pt/C. The results of potentiodynamic polarizations at room temperature showed much higher electrocatalytic activity for the SnOxRuOx-Pt/C material, with current efficiency for CO2 formation of 15.6% against 15.2% for Pt/C under stagnant conditions. The reaction residues stripping after the ethanol electro-oxidation, under continuous flow conditions, showed the accumulation of species containing 1 carbon atom (CO and CHx), which are oxidized just at high potentials (ca. 1.0 V) and they cause the obstruction of the active sites. On the other hand, the polarization curves at 245oC showed higher values of current efficiencies (45% for Pt/C for both potentials 0.5 V and 0.8 V against 36% and 50% to SnOxRuOx-Pt/C at 0.5 V and 0.8 V respectively) for the CO2 formation than at ambient condition, however, with similar activities for SnOxRuOx-Pt/C and Pt/C. For both electrocatalysts, in parallel with the electrochemical pathways, heterogeneous chemical catalysis of ethanol decomposition also takes place, producing H2 and CO2, as major products.

abstract: This thesis concerns the flashover issue of the substation insulators operating in a polluted environment. The outdoor insulation equipment used in the power delivery infrastructure encounter different types of pollutants due to varied environmental conditions. Various methods have been developed by manufacturers and researchers to mitigate the flashover problem. The application of Room Temperature Vulcanized (RTV) silicone rubber is one such favorable method as it can be applied over the already installed units. Field experience has already showed that the RTV silicone rubber coated insulators have a lower flashover probability than the uncoated insulators. The scope of this research is to quantify the improvement in the flashover performance. Artificial contamination tests were carried on station post insulators for assessing their performance. A factorial experiment design was used to model the flashover performance. The formulation included the severity of contamination and leakage distance of the insulator samples. Regression analysis was used to develop a mathematical model from the data obtained from the experiments. The main conclusion drawn from the study is that the RTV coated insulators withstood much higher levels of contamination even when the coating had lost its hydrophobicity. This improvement in flashover performance was found to be in the range of 20-40%. A much better flashover performance was observed when the coating recovered its hydrophobicity. It was also seen that the adhesion of coating was excellent even after many tests which involved substantial discharge activity. / Dissertation/Thesis / M.S. Electrical Engineering 2013

L’objectif de cette étude est le développement d’un capteur de gaz à base de couche hybrideSnO2/SWNTs dans le but d’améliorer les performances des capteurs chimiques « classiques »uniquement constitués de dioxyde d’étain. En premier lieu, afin de maîtriser la synthèse dumatériau sensible, nous avons validé l’élaboration d’une couche sensible à base de dioxyded’étain préparée par procédé sol-gel. Le matériau synthétisé a été déposé par la technique ‘microgoutte’sur une micro-plateforme permettant simultanément le chauffage de la couche sensible etla mesure de sa conductance. L’étude des réponses électriques du capteur de gaz en présence dubenzène a permis de valider la possibilité d’utilisation du sol d’étain préparé pour la réalisation decouches sensibles aux gaz. En effet, des traces de benzène (500 ppb) ont été détectées à latempérature optimale de couche sensible de 420°C.Le second volet de cette étude repose sur la fabrication du matériau hybride obtenu par dispersiondes nanotubes de carbone dans un sol d’étain. Les couches sensibles élaborées par dip-coating àpartir du sol d’étain modifié par les nanotubes de carbone ont clairement montré la possibilité dedétection de divers gaz (ozone et ammoniac) à température ambiante. Ce résultat constitue l’undes points importants de ce travail de thèse dans la mesure où jusqu’à présent les capteurschimiques à base de dioxyde d’étain ne présentaient une forte sensibilité aux gaz que pour destempératures de fonctionnement de l’ordre de 350-400°C. Pour les deux gaz cibles étudiés dans lecadre de ce travail, la limite de détection à température ambiante a été évaluée à 1 ppm enprésence de NH3 et est inférieure à 20 ppb en présence d’ozone.La dernière partie de ce travail a porté sur l’optimisation des performances de détection descouches hybrides. Dans ce cadre, les expérimentations ont porté sur l’étude de l’influence dedivers paramètres tels que la quantité de nanotubes dans le matériau hybride, la température decalcination de la couche sensible, la température de fonctionnement ou encore les propriétésphysico-chimiques des nanotubes de carbone (mode de synthèse, diamètre,…) sur l’efficacité dedétection des couches sensibles. Les résultats ainsi obtenus en termes de performance de détectionont été discutés en relation avec les paramètres expérimentaux utilisés. / The objective of this study is to develop a gas sensor based on a hybrid layer of SnO2/SWNTs inorder to improve the performance of “Conventional” chemical sensors basically made from tinoxide. First, in order to control the synthesis of the sensitive material, we validated the elaborationof a sensitive layer based on tin dioxide prepared using the sol-gel process. The synthesizedmaterial was deposited by the 'microdrop' technique on a micro-platform which simultaneouslyallows the heating of the sensitive layer whilst also measuring its conductance. The study of theelectrical responses of the gas sensor in the presence of benzene has allowed us to validate thepossibility of using our prepared tin sol for the realization of gas sensitive layers. In fact, it waspossible to detect benzene at traces with an optimal temperature of the sensing layer found to be420ºC.The second part of this study describes the synthesis of the hybrid sensor obtained by dispersingSWNTs in the tin-oxide based sol. The sensitive layers made by dip-coating from the carbonnanotubes modified tin sol have clearly shown the possibility of detecting various gases (ozoneand ammonia) at room temperature. This result is one the most important points of this work tothe extent that until now the chemical sensors based on tin dioxide only showed a high sensitivityto gases when they were operated at temperatures in the range of 350 - 400ºC. Concerning the twotarget gases tested in this work, the detection limit at room temperature was evaluated at 1 ppm inthe presence of NH3 and was lower than 20 ppb in the presence of ozone.The last part of this work has focused the optimization of the detection performance of thesensitive layers. In this case, the experimental study was oriented towards examination of theeffect of various parameters such as the amount of nanotubes in the hybrid material, thecalcination temperature of the sensitive layer, the sensor working temperature and also thephysico-chemical properties of the carbon nanotubes (synthesis method, diameter...) on thedetection efficiency of the sensing layers. The results obtained in terms of detection performancewere discussed in relation to the experimental parameters used.

La modification des surfaces revêt un intérêt primordial dans de nombreux champs d'applications de la chimie, comme la chimie analytique et l'électronique moléculaire. Ce travail a porté sur l'étude de différentes monocouches liées de façon covalente à des surfaces conductrices (principalement le carbone) et préparées à partir de l'électroréduction de sels d'aryldiazonium. Ces monocouches organiques ont été fonctionnalisées avec des groupements terminaux électroactifs différents, et l'on s'est intéressé aux propriétés de transfert de charge (au sens large) des couches résultantes. Tout d'abord des couches portant un système redox simple à base de ferrocène ont été étudiées dans différents milieux organiques conventionnels et en milieu liquides ioniques. L'effet de l'éloignement du système redox vis-à-vis de la surface a été également analysé en variant la longueur du pont ancrant. Dans un second temps, les monocouches organiques ont été fonctionnalisées par des unités tétrathiafulvalène (TTF). Les TTF sont des molécules (donneur d'électrons) connues pour former des complexes à transfert de charge avec le tétracyanoquinodiméthane (TCNQ), accepteur d'électrons. La formation de complexes à transfert de charge entre des TTF immobilisées dans la monocouche et des dérivés TCNQ a été étudiée et modulée selon l'éloignement du TTF vis-à-vis de la surface (variation de la longueur du lien ancrant) et en fonction de la force de l'accepteur. Enfin, des monocouches avec des groupements terminaux de type fluorène ou spirobifluorène (SBF) ont été préparées. Le comportement bloquant vis-à-vis-du transfert d'électron a été étudié par microscopie électrochimique (SECM) en présence de deux médiateurs redox différents et la conductivité des couches a été évaluée par CP-AFM (microscopie à force atomique – mesure de courants locaux). Il est montré que les propriétés de transfert/transport de charges sont influencées par l'encombrement stérique associé au fluorène ou au SBF (variation de la substitution). Ces monocouches organiques stables, bien organisées apparaissent très prometteuses comme composants dans des dispositifs d'électronique moléculaire. / Surface modification is of paramount importance in many fields of chemistry like analytical chemistry and molecular electronics. This work deals with the study of different monolayers covalently bound on conducting (mainly carbon) surfaces, and produced from the electroreduction of aryldiazonium salts. By introducing electroactive components in the resulting monolayers, the different studies in this work mainly focused on charge-transfer properties (in a large sense). First, monolayers bearing simple redox-active ferrocenyl terminal groups were investigated. The electrochemical behavior of these monolayers was analyzed in different conventional organic media and in ionic liquids (RTILs) and by varying the length of the bridging unit between the surface and the ferrocene groups. Second, redox-active tetrathiafulvalene (TTF) molecules were used to functionalize the monolayers. TTF molecules are well-known donor molecules able to form charge-transfer complexes with tetracyanoquinodimethane (TCNQ) as an electron-acceptor. The formation of charge-transfer complexes between immobilized TTF and TCNQ derivatives was studied and modulated by varying the chain length of the bridging unit between the TTF donor and the surface and by varying the electron-withdrawing ability of the TCNQ acceptors. Third, monolayers with fluorene and spirobifluorene (SBF) terminal groups were prepared. The blocking behavior towards electron transfer was studied by electrochemical microscopy (SECM) with two redox mediators and the conductivity of the layers was investigated by CP-AFM (Conducting Probe-Atomic Force Microscopy). Effects due to the steric hindrance of the fluorene or SBF derivatives were evidenced. Such stable, organized and organic monolayers seem to be promising candidates for molecular electronic devices.

Developing next generation secondary batteries has attracted much attention in recent years due to the increasing demand of high energy and high power density energy storage for portable electronics, electric vehicles and renewable sources of energy. This dissertation investigates sulfur based advanced electrode materials in Lithium/Sodium batteries. The electrochemical performances of the electrode materials have been enhanced due to their unique nano structures as well as the formation of novel composites. First, a nitrogen-doped graphene nanosheets/sulfur (NGNSs/S) composite was synthesized via a facile chemical reaction deposition. In this composite, NGNSs were employed as a conductive host to entrap S/polysulfides in the cathode part. The NGNSs/S composite delivered an initial discharge capacity of 856.7 mAh g-1 and a reversible capacity of 319.3 mAh g-1 at 0.1C with good recoverable rate capability. Second, NGNS/S nanocomposites, synthesized using chemical reaction-deposition method and low temperature heat treatment, were further studied as active cathode materials for room temperature Na-S batteries. Both high loading composite with 86% gamma-S8 and low loading composite with 25% gamma-S8 have been electrochemically evaluated and compared with both NGNS and S control electrodes. It was found that low loading NGNS/S composite exhibited better electrochemical performance with specific capacity of 110 and 48 mAh g-1 at 0.1C at the 1st and 300th cycle, respectively. The Coulombic efficiency of 100% was obtained at the 300th cycle. Third, high purity rock-salt (RS), zinc-blende (ZB) and wurtzite (WZ) MnS nanocrystals with different morphologies were successfully synthesized via a facile solvothermal method. RS-, ZB- and WZ-MnS electrodes showed the capacities of 232.5 mAh g-1, 287.9 mAh g-1 and 79.8 mAh g-1 at the 600th cycle, respectively. ZB-MnS displayed the best performance in terms of specific capacity and cyclability. Interestingly, MnS electrodes exhibited an unusual phenomenon of capacity increase upon cycling which was ascribed to the decreased cell resistance and enhanced interfacial charge storage. In summary, this dissertation provides investigation of sulfur based electrode materials with sulfur/N-doped graphene composites and MnS nanocrystals. Their electrochemical performances have been evaluated and discussed. The understanding of their reaction mechanisms and electrochemical enhancement could make progress on development of secondary batteries.

Le but de cette thèse a été d'étudier les propriétés structurales et optiques de puits quantiques (PQs) d’InGaN/(Al)GaN obtenus par épitaxie en phase vapeur d’organométalliques. Différentes approches ont été mises en œuvre pour atteindre une émission dans le vert-jaune: la première utilisant une concentration d'indium ≥ 20% avec un PQ d’InGaN d’épaisseur <3.0 nm et vice versa. L'effet d'une couche d’encapsulation a également été étudié. Les techniques de microscopie à force atomique, de diffraction des rayons X, de photoluminescence (PL) et surtout de microscopie électronique à transmission (MET) ont été utilisées pour caractériser ces structures. Les épaisseurs des PQs et les compositions en indium ont été déterminées par le traitement numérique des franges de réseau dans les images MET haute résolution en section transverse. Un traitement original a été développé pour analyser quantitativement les fluctuations de l’épaisseur des PQs. L'analyse structurale des PQs ayant une composition en In élevé a montré que les défauts structuraux sont créés dans les PQs. La nature et la densité de ces défauts ont été déterminées et différents mécanismes pour leur formation ont été proposés. Il a également été montré que quelques monocouches d’encapsulation de GaN ou d’AlGaN déposées à la température de croissance des PQs limitent l’évaporation et/ou la diffusion d’indium. Ce procédé permet d’étendre la longueur d'onde d'émission avec une réduction de la dégradation de l'efficacité de la PL. Mon travail propose quelques pistes afin d'obtenir un bon compromis entre les paramètres contradictoires qui régissent l'efficacité des PQs émettant dans le vert-jaune. / The goal of this thesis was to study the structural and optical properties of InGaN/(Al)GaN multiple QWs grown by metal organic chemical vapor deposition. Different approaches have been implemented to achieve green-yellow emission: high indium concentration (≥ 20%) with low InGaN QW thickness (< 3 nm) or vice versa. Moreover, the effect of a capping layer on top of the QWs has also been investigated. Atomic force microscopy, X-ray diffraction, room temperature photoluminescence (RTPL) and mainly transmission electron microscopy (TEM) techniques have been used to characterize these structures. The QW thicknesses and indium compositions have been determined by digital processing of lattice fringes in cross-sectional high resolution TEM images. An original treatment has been developed to analyze quantitatively InGaN QW thickness fluctuations. The structural analysis of multiple QWs with high indium composition has shown that structural defects are created in the QWs. The nature and the density of these defects have been determined and different mechanisms for their formation have been proposed. It has also been shown that a few monolayers of AlGaN or GaN capping layers deposited at the InGaN QW growth temperature prohibited indium evaporation and/or diffusion. It therefore helps to extend the emission wavelength with a reduced degradation of the RTPL efficiency. My work offers a few ways to obtain a good compromise between the conflicting parameters that govern the efficiency of QWs emitting in the green-yellow spectrum range.

The effects of ambient room temperature on social cognition were examined in the current study. This study included 202 participants who completed a computer-based survey consisting of eight items measuring participants’ self-perception and desired social dynamics. I included these constructs because they serve to empirically examine the claims put forth by the Socio-Relational Framework of Expressive Behavior (Vigil, 2009). Participants completed the survey in experimental settings with the ambient room temperature ranging from 67.8 °F to 77.2 °F. I identified several important relationships that support the current theoretical framework, such as the differential desire for either affiliative or avoidant social responses, and the differential inflation of either empowerment or trustworthiness descriptors in colder and warmer conditions, respectively. Implications of the findings for future research are discussed.

In der vorliegenden Dissertation geht es um die Synthese und Charakterisierung chiraler, redoxaktiver (Raumtemperatur-)Ionischer Flüssigkeiten basierend auf Ferrocen und der natürlich vorkommenden Aminosäure S-Prolin. Diese Baueinheiten sind entweder über eine Ether- oder über eine Esterverbrückung verknüpft. Auch der Anionenaustausch vom I– - zum CF3SO3– - sowie (CF3SO2)2N– -Salz (kurz NTf2–) wird dargelegt und der Einfluss des Anions auf den Schmelzpunkt der Verbindungen untersucht und diskutiert. Die Redoxaktivität wird durch das im Ferrocen enthaltene Fe II eingebracht, das reversibel zu Fe III oxidiert werden kann. Aufgrund des Pyrrolidin-Rings sind die dargestellten Verbindungen stets chiral und bilden nach der Quaternisierung mit Halogenalkanen Diastereomere, soweit die Alkylkette größer als Methyl ist. Das Diastereomerenverhältnis wurde mittels 1H-NMR-Spektroskopie und in einem Fall anhand von Röntgenpulverdiffraktogrammen durch Rietveld-Verfeinerung analysiert. Die Verbindungen wurden thermisch anhand simultaner thermischer Analysenund Tieftemperaturversuchen untersucht, die belegen, dass die Synthese von insgesamt sechs neuen Raumtemperatur-Ionischen Flüssigkeiten gelang. Davon basiert eine Verbindung, (1S2S)- und (1R2S)-2-[(Ferrocenylcarbonyl)oxy]methylen-N-methyl-N-pentylpyrrolidin-1-iumiodid, auf I– und fünf Verbindungen enthalten NTf2– als Gegenion. Das Diastereomerengemisch der Verbindungen (1S2S)- und (1R2S)-N-Butyl-2-[(ferrocenylcarbonyl)oxy]methylen-N-methylpyrrolidin-1-ium NTf2– besitzt den größten Flüssigkeitsbereich von -25 bis +263 °C und auch die höchste Zersetzungstemperatur aller hier dargestellten Verbindungen. Insgesamt werden in dieser Arbeit elf Einkristallstrukturanalysen vorgestellt, wobei es sich um drei Verbindungen des Typs FcCH2N(CH3)2(CnH2n+1)I (Fc = Ferrocenyl, n = 1,2,3), Ferrocenmonocarbonsäurechlorid, zwei ether- sowie fünf esterverbrückte Verbindungen handelt. Mikrokristalline Proben wurden mittels Röntgenpulverdiffraktometrie charakterisiert. Ergänzende Analysen wurden mittels UV-Vis- und IR-Spektroskopie sowie Massenspektrometrie und Elementaranalyse durchgeführt. Ein wichtiger Aspekt bei Ferrocenverbindungen ist das Redoxpotential, welches mittels Cyclovoltammetrie bestimmt wurde. Hierbei liegt das Formalpotential des Fe II /Fe III -Redoxpaars der etherverbrückten Verbindungen bei +0,05 V und bei den esterverbrückten Verbindungen unabhängig vom Anion bei +0,28 V vs. Ferrocen/Ferrocenium in Acetonitril. Bei den iodidhaltigen Verbindungen zeigt das I– -Ion ebenfalls eine Redoxaktivität bei E(0,f,Fc) = -0,18 V und 0,22V. Die Diffusionskoeffizienten der esterverbrückten Triflat- und NTf2– -Verbindungen liegen in der Größenordnung von 7·10−6 cm2/s und die heterogenen Geschwindigkeitskonstanten bei 0,01 cm/s. / The present dissertation deals with the synthesis and characterization of chiral, redoxactive room temperature ionic liquids (RTILs) based on ferrocene and the naturally occurring amino acid S-proline. These building blocks are coupled either via an ether- or an ester-bridge. The anion exchange from I– to CF3SO3– and (CF3SO2)2N– salts (abbreviated as NTf2–) is presented. The influence of the anion on the melting point of the compound is investigated and discussed. The redox activity is introduced into the molecule via the Fe II -containing ferrocenyl groups, which can be oxidized reversibly to Fe III . The synthesized compounds based on the pyrrolidine ring are chiral. After quaternization with alkyl halides, they form diastereomers in case of alkyl chains longer than methyl. The ratio of the different diastereomers was analyzed by 1H NMR spectroscopy and, in one case, by Rietveld refinement of the X-ray powder diffraction pattern. The thermal behavior of the compounds was studied by simultaneous thermal analysis and low temperature experiments. The results show the successful synthesis of six new RTILs. One of them is based on iodide ((1S2S)- and (1R2S)-2-[(ferrocenylcarbonyl)oxy]methylene-N-methyl- N-pentylpyrrolidine-1-ium iodide) and six RTILs contain NTf2– as counter ion. The diastereomeric mixture of compounds (1S2S)- and (1R2S)-N-butyl-2-[(ferrocenylcarbonyl)oxy]methylene-N-methylpyrrolidine-1-ium NTf2– exhibits the widest liquid range from -25 to +263 °C and the highest decomposition temperature of all compounds presented herein. Eleven single crystal structure analyses are presented. Three of them belong to compounds FcCH2N(CH3)2(CnH2n+1)I (with Fc = ferrocenyl and n = 1,2,3), then ferrocene monocarboxylic acid chloride, two of ether- as well as five ester-bridged compounds. Microcrystalline samples were characterized by X-ray powder diffractometry. Supplementary analyses by UV/Vis and IR spectroscopy as well as mass spectrometry and elemental analyses have been carried out. An important feature of ferrocene containing compounds is their redox potential which is determined with cyclic voltammetry. The formal potential of the Fe II /Fe III redox couple in the ether-bridged compounds is at +0.05 V and in the ester-bridged compounds independent from the type of anion at +0.28 V vs. ferro- cene/ferrocenium in acetonitrile. The I– anion shows as well redox activity with formal potentials at E(0,f,Fc) = -0.18 V and 0.22 V. The diffusion coefficients of the ester-bridged triflate and NTf2– compounds are in the order of 7·10−6 cm2/s, the heterogeneous rate constants in the order of 0.01 cm/s.

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.