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Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-06-06T20:07:41Z No. of bitstreams: 1 RaffaelPinto.pdf: 7905766 bytes, checksum: 7f7997961e840698d9d936cdea00b602 (MD5) / Made available in DSpace on 2017-06-06T20:07:41Z (GMT). No. of bitstreams: 1 RaffaelPinto.pdf: 7905766 bytes, checksum: 7f7997961e840698d9d936cdea00b602 (MD5) Previous issue date: 2008-05-21 / Fundação de Amparo à Pesquisa e ao Desenvolvimento Científico e Tecnológico do Maranhão (FAPEMA) / In this work have been investigated the dielectric and vibrational properties of the ORMOSIL membranes based on PDMS and TEOS doped with MDS using the Di erential Scanning Calorimetry (DSC), impedance, Raman and infrareds spectroscopy technics. Such membranes are hybrid organic-inorganic materials with potential application in PEMFC (Proton Exchange Membrane Fuel Cell) and were doped with concentrations 0%(Pure Membrane), 5%, 10%, 20% e 30% of MDS. The thermal measurements were performed in the range from room temperature and 550 oC. The results showed that, after the MDS inclusion, the membranes absorb water. Besides, then thermal stability of the membranes decreased with the MDS inclusion. The dielectrics measurements were performed in temperature range of 313K-373K. The results showed that room temperature conductivity increases linearly with the frequency, until 353K, suggesting a hopping conduction and leaving this linear behavior above 353K. Besides, it was observed that conductivity doesn't increases linearly with MDS concentration, but increases until maximal value for 20% MDS concentration and decreases again for 30% MDS concentration de ning a synergetic e ect, which probably is associate with con gurational arrange of microcristallites MDS. Another feature of that membranes is a relaxation process visible in the electrical module graphics which appear just in doped membranes, being however, due to the MDS. The vibrational properties of hybrids membranes were obtained through Raman scattering and infrared. The results con rmed the presence of Si¡O¡Si, Si¡C, Si¡OH, C2H5, Si¡CH3, CH3, CH2, C¡H, S=O and S¡O groups. Where the S=O and S¡O groups are presents just in MDS compound. Consequently, their respective peaks appear only in the doped membrane spectra. / Neste trabalho foram investigadas as propriedades térmicas, dielétricas e vibracionais das membranas de ORMOSIL baseadas em PDMS e TEOS dopadas com MDS através das técnicas de calorimetria diferencial de varredura, espectroscopias de impedância, Raman e infravermelho. Essas membranas são materiais híbridos orgânico-inorgânico com grande potencialidade de aplicação em células combustíveis do tipo PEM (Proton Exchange Membrane) e foram dopadas nas concentrações de 0%(Pura), 5%, 10%, 20% e 30% de MDS. As medidas térmicas foram realizadas entre a temperatura ambiente e 500 oC e mostraram que as membranas passam a absorver água quando o MDS é inserido. Mostraram também que as membranas têm sua estabilidade térmica reduzida quando o MDS é inserido. As medidas dielétricas foram realizadas no intervalo de temperatura entre 40 e 100oC. Os resultados mostraram que a condutividade à temperatura ambiente aumenta de maneira praticamente linear com a freqüência, mantendo-se assim até 80±C sugerindo uma condução por hopping e deixando de ter esse comportamento linear para temperaturas acima de 80±C. Observou-se também que a condutividade não aumenta linearmente com a concentração de MDS, mas atinge um valor máximo para a membrana com 20% de MDS e diminui novamente para a membrana com 30% de MDS caracterizando assim um efeito sinergético, que provavelmente está associado ao arranjo configuracional dos microcristalitos do MDS. Uma outra característica interessante dessas membranas, é um processo de relaxação visível nos grá cos do módulo elétrico o qual consta apenas nas membranas dopadas, sendo portanto, característico do MDS. As propriedades vibracionais desses materiais híbridos foram determinadas através de medidas do espalhamento Raman. Os resultados da espectroscopia Raman e infravermelho confirmaram a presença dos grupos Si¡O¡Si, Si¡C, Si¡OH, C2H5, Si¡CH3, CH3, CH2, C¡H, S=O e S¡O. Onde estes dois últimos estão presentes somente no MDS e, por essa razão, seus respectivos picos só se apresentaram no espectro das membranas dopadas.

L’objectif principal a été d’élaborer de nouveaux revêtements hybrides O/I de morphologie contrôlée afin de répondre des exigences de haute stabilité thermique (300°C) et résistance à la rayure et ayant des propriétés mécaniques spécifiques. Pour répondre à ces attentes, une phase inorganique est générée in-situ par des réactions d’hydrolyse/condensation d’un précurseur inorganique silicié (TEOS) au sein de matrices organiques de microstructures variées : polyesters hyperramifiés (Boltorn H20 and H40), oligoesters ramifiés (Synthoester et dérivés tanniques). Les nombreuses fonctions hydroxyles de la composante organique et leur forme spécifique permettent, dans les conditions de synthèse choisies, de contrôler les interactions entre les phases organiques et inorganiques et retarder les mécanismes de séparation de phases induite lors de la condensation du TEOS. Les matériaux hybrides ont été analysés par TEM, SAXS, ATG et DMA, microscratch testeur. L’influence de la masse molaire, de la teneur en composés inorganiques, de la teneur en fonctions hydroxyle de la composante organique sur la morphologie finale et les propriétés thermiques et mécaniques de surface. / This study focuses on coatings based on news O/I hybrid coatings having a specific morphology to improve resistance to heat, abrasion and scratch as well as mechanical properties. To obtain and control the hybrid morphology, inorganic domains are generated in-situ via sol-gel chemistry based on hydrolysis/condensation reactions of metal alcoxydes (TEOS) into an organic polymer: hyperbranched polyesters (HBP Boltorn H20 and H40) and branched oligoesters (Synthoester, tannic acids). Which ones are high hydroxy functionalized, dense structure and peculiar shape are exploited to control the interactions between the organic and inorganic phases. The hybrid materials were characterized by TEM, SAXS, TGA, DMA, and microscratch tester. We investigated the influence of weight fraction of silica and of hydroxyl functionality of organic component on one side, and the influence of condensation degree on the other side, on the final morphology and thermal and mechanical properties.

Ce travail de thèse a porté sur le développement de revêtements organiques/inorganiques photopolymérisables superhydrophobes à partir de procédés d’élaboration simples associés à des produits commerciaux largement diffusés. Pour cela, des revêtements à matrice polyuréthane acrylate (PUA), intrinsèquement hydrophiles, incluant différents composés à base de silicium ont été élaborés par enduction ou pulvérisation. L’objectif a été d’apporter en surface des revêtements une structuration multi-échelle et une chimie à caractère hydrophobe nécessaires pour atteindre la superhydrophobie, c’est-à-dire un angle de contact avec l’eau supérieur à 150° et une hystérésis de mouillage inférieure à 10°. L’introduction de molécules de polysilsesquioxane polyédrique (POSS), présentant un ligand acrylate et sept ligands isobutyle, a apporté une nanostructuration et un comportement hydrophobe aux revêtements PUA à des concentrations très faibles (≤ 1% en masse.). Cependant, la rugosité apportée se révèle trop faible et cette stratégie ne peut aboutir à la superhydrophobie des revêtements. L’introduction de particules de silice pyrogénée, modifiées en surface par des chaînes polydiméthylsiloxane, a permis d’établir une structuration multi-échelle et une chimie à caractère hydrophobe à la surface des revêtements PUA, leur conférant ainsi la superhydrophobie. De plus, le procédé d’élaboration a joué un rôle majeur sur les modifications physico-chimiques de surface des revêtements : la superhydrophobie est obtenue à une concentration relativement élevée de 30 et 60% en masse de silice pyrogénée respectivement par pulvérisation et enduction. Afin de diminuer ces concentrations, la combinaison des deux stratégies précédentes, c’est-à-dire l’introduction simultanée de POSS et de silice pyrogénée, a été considérée. Ceci a permis d’exacerber le caractère hydrophobe des revêtements tout en préservant la rugosité établie par la silice pyrogénée. Cette approche a conduit à la diminution de la concentration de silice nécessaire pour obtenir la superhydrophobie dans le cas des revêtements élaborés par pulvérisation. / This work deals with the development of organic/inorganic superhydrophobic UV-curable coatings manufactured through simple processes and from commercially available products. To achieve this goal, a hydrophilic polyurethane acrylate matrix (PUA) was used, in which several silicon-based compounds were introduced. The coatings were deposited using either bar- or spray-coating. The main objective was to structure the surface thanks to a multiscale roughness, while bringing a hydrophobic character, two properties needed to obtain a superhydrophobic coating (defined by a water contact angle superior to 150° and a water contact angle hysteresis inferior to 10°). The introduction of polyhedral oligomeric silsesquioxane molecules (POSS), presenting one acrylate and seven isobutyl ligands, brought a nanostructuration and a hydrophobic behavior to PUA coatings, even at low concentrations (≤ 1%wt.). However, the roughness obtained was not sufficient to bring the superhydrophobicity to the coatings.The introduction of fumed silica particles, functionalized by PDMS chains, established multiscale roughness and hydrophobic behavior at the surface, leading to superhydrophobic coatings. Moreover, the process had a high influence on physico-chemical modifications at the coatings’surface: superhydrophobicity is obtained for a relatively high concentration of fumed silica, 30%wt. and 60%wt. respectively for spray and bar-coating. In order to decrease these concentrations, we tried the combination of the two previous strategies: introduction of POSS molecules and fumed silica particles. This path raised the hydrophobic behavior of the coatings while keeping intact the roughness brought by fumed silica particles. This approach allowed to decrease the silica concentration needed to obtain superhydrophobicity for spray-coated coatings.

Efterfrågan på bättre och mer hållbart material ökar. Mer effektivt material kommer att behövas för att möta den ökande, globala efterfrågan. Hybrida organiska-oorganiska material är en typ av material som har varit av stort intresse nyligen, och kan beskrivas som en typ av material som består av både organiska och oorganiska komponenter. Denna avhandling har fokuserat på hybrida organiska-oorganiska material inspirerade av den klassiska perovskitstrukturen ABX3, där komponent A är en organisk katjon, komponent B är en divalent metalkatjon och komponent X är en anjon. Hybrida organiska-oorganiska material som är utgår från den klassiska perovskitstrukturen kan ha olika funktionella egenskaper och en bred variation av tänkbara applikationer. Några exempel på dessa egenskaper och möjliga applikationer inkluderar god fotokonduktivitet för solceller, utmärkt emissionsegenskaper för ljusdioder och justerbara dielektriska egenskaper för elektroniska växlar och sensorer.  De fysiska egenskaperna av det hybrida organiska-oorganiska materialet beror på kristallstrukturen av materialet, som i sig bestäms av valet av komponenter. På grund av de många möjligheter av organiska och oorganiska komponenter så finns det möjlighet att syntetisera helt nya hybrida organiska-oorganiska föreningar som kan ha nya eller förbättrade fysiska egenskaper.  Nuvarande hybrida organiska-oorganiska material som utgår från perovskitstrukturen använder huvudsakligen bly som divalent metalkatjon, och det beror på att den ger den bästa funktionella effekten. Blys toxicitet är dock en stor nackdel för nuvarande blybaserade hybrid oorganiska material. Möjligheten att ersätta bly med en annan divalent metall har undersökts under detta projekt. I denna avhandling så har den organiska katjonen cyclohexylammonium (CHA) varit i fokus som den organiska komponenten. Målet med detta examensarbete var att designa, syntetisera och karakterisera nytt hybrid organisk-oorganiskt material. De hybrida organiska-oorganiska föreningarna CHAZnBr3 och (CHA)2ZnBr4 syntetiserades för den första gången, så vitt författaren vet, och kommer vara i fokus i denna avhandling. De två nya hybrida organiska-oorganiska föreningarna blev strukturellt karakteriserade med X-ray Diffraction (XRD) och termiskt karakteriserade med Thermal Gravimetric Analysis (TGA) och Differential Scanning Calorimetry (DSC).  Den första föreningen, CHAZnBr3, kunde bestämmas att vara ortorombisk vid 298 K. Föreningen bestämdes vara termisk stabil upp till 490 K, och genomgår en fasövergång vid 445 K. Den andra föreningen, (CHA)2ZnBr4, kunde inte bestämmas strukturellt vid varken 100 K eller 298 K. Föreningen bestämdes vara termisk stabil upp till 490 K, och genomgår en fasövergång vid 230 K. Ytterligare karakterisering krävs för att bättre förstå egenskaperna hos dessa föreningar och deras möjliga användningsområden. / The demand for better and more sustainable material is increasing. More efficient materials will be needed to meet the growing global need. Hybrid organic-inorganic materials are one type of materials that have been of great interest recently, which can be described as a class of materials that mix organic and inorganic components. This thesis focused on hybrid organic-inorganic materials inspired by the classical perovskite crystal structure ABX3, where component A is an organic cation, component B is a divalent metal cation and component X is an anion. Hybrid organic-inorganic materials based on the classical perovskite structure may have various functional properties and may have a broad range of potential applications. Some examples of those properties as well as some and possible applications include good photoconductivity and power conversion efficiency for photovoltaic devices, excellent emission properties for light emitting diodes and tunable dielectric properties for electronic switches and sensors.  The physical properties of the hybrid organic-inorganic material are determined by the crystal structure of the material, which in turn will be decided by the choice of components. With the many possible choices for organic and inorganic components, there is an opportunity to synthesize completely new hybrid organic-inorganic compounds that may display new or superior physical properties. Current hybrid organic-inorganic materials based on the perovskite crystal structure mainly use lead as the divalent metal, since it currently gives the best performance. The toxicity of lead is a major drawback for current lead-based hybrid organic-inorganic materials. The possibility to replace lead with another divalent metal has been explored during this project. For this thesis, the organic cation cyclohexylammonium (CHA) has been of focus as the organic component. The aim of this thesis was to design, synthesize and characterize novel hybrid organic-inorganic compounds. The hybrid organic-inorganic compounds CHAZnBr3 and (CHA)2ZnBr4 were synthesized for the first time, to the best of our knowledge, and will be the focus of this thesis. The two new hybrid organic-inorganic compounds were structurally characterized by X-ray Diffraction (XRD) and thermally characterized by Thermal Gravimetric Analysis (TGA) and Differential Scanning Calorimetry (DSC).  The first compound, CHAZnBr3, could be determined to be orthorhombic at 298 K. The compound was found to be thermally stable up 490 K, and to undergo a phase transition at 445 K.  The second compound, (CHA)2ZnBr4, could not be fully structurally solved at either 100 K or 298 K. The compound was found to be thermally stable up to 490 K, and to undergo a phase transition at 230 K.  Further characterization will be needed to better understand the properties of these two compounds and their possible applications.

Η δυνατότητα να συνδυαστούν οι ιδιότητες οργανικών και ανόργανων συστατικών σε ένα μοναδικό νανοδομημένο υβριδικό υλικό αποτελεί μία σημαντική επιστημονική πρόκληση στο σχεδιασμό υλικών, τα οποία μπορούν να εμφανίζουν νέες βελτιωμένες ιδιότητες και να τύχουν προηγμένων εφαρμογών. Τα υβριδικά υλικά, γενικά, μπορούν να ταξινομηθούν σε δύο μεγάλες κατηγορίες: στην κατηγορία I (class I), όπου οι δύο φάσεις συνδυάζονται μέσω ασθενών αλληλεπιδράσεων, και στην κατηγορία II (class II), όπου οι δύο φάσεις είναι σταθερά συνδεδεμένες. Στην παρούσα εργασία διερευνήθηκε η δυνατότητα εφαρμογής νανοδομημένων υβριδικών υλικών ως ετερογενείς καταλύτες στη διεργασία παραγωγής βιοντίζελ από διαφόρων ειδών έλαια. Κατά τη διεργασία αυτή, η οποία καλείται μετεστεροποίηση ή μεθανόλυση, τριγλυκερίδια αντιδρούν με μια αλκοόλη παρουσία ισχυρού οξέος ή βάσης προς παραγωγή εστέρων και γλυκερίνης. Σε πρώτη φάση, εστιάσαμε στη σύνθεση και το χαρακτηρισμό class I και class II υβριδικών οργανικών/ανόργανων υλικών αποτελούμενων από έναν ανόργανο πυρήνα διοξειδίου του πυριτίου (silica), ο οποίος θα περιβάλλεται από πολυμερικές αλυσίδες. Έτσι, στην προσπάθεια σύνθεσης υβριδικών υλικών class I αξιοποιήθηκαν οι πιθανές αλληλεπιδράσεις καθαρών και αμινοτροποποιημένων νανοσωματιδίων διοξειδίου του πυριτίου με υδατοδιαλυτά συμπολυμερή P(SSΗ-co-MA) του στυρενοσουλφονικού οξέος (SSH), με το μηλεϊνικό οξύ (ΜΑ), τα οποία φέρουν τόσο καρβοξυλικές όσο και σουλφονικές ομάδες. Ως αποτέλεσμα του όξινου χαρακτήρα των πολυμερών, τα υβριδικά νανοσωματίδια θα μπορούσαν δυνητικά να χρησιμοποιηθούν ως όξινοι καταλύτες κατά την παραγωγή του βιοντίζελ. Στην προσπάθεια σύνθεσης class II υβριδικών υλικών αξιοποιήθηκε κυρίως ο πολυμερισμός ελευθέρων ριζών μέσω μεταφοράς ατόμου (ATRP), μονομερών όπως στυρενοσουλφονικό νάτριο (SSNa), Ν-ισοπροπυλακρυλαμίδιο (NIPAM) και 2-(διμεθυλαμινο)μεθακρυλικός αιθυλεστέρας (DMAEMA). Για την εκκίνηση του πολυμερισμού χρησιμοποιήθηκαν νανοσωματίδια silica χημικά τροποποιημένα με 3-αμινοπροπυλοτριαιθοξυσιλάνιο και ακολούθως με 2-χλωροπροπιονυλοχλωρίδιο. Εναλλακτικά, χρησιμοποιήθηκαν νανοσωματίδια silica χημικά τροποποιημένα με 3-χλωροπροπυλoτριαιθοξυσιλάνιο (ATRP πολυμερισμός), ή βινυλοτριμεθοξυσιλανιο (πολυμερισμός ελευθέρων ριζών, FRP). Ο χαρακτηρισμός των δειγμάτων κατά περίπτωση έγινε με φασματοσκοπία πυρηνικού μαγνητικού συντονισμού υδρογόνου (1H NMR), φασματοσκοπία υπερύθρου με μετασχηματισμό Fourier (FTIR), θερμοσταθμική ανάλυση (TGA) και τιτλοδότηση οξέος-βάσεως. Στο τελευταίο μέρος της εργασίας ελέγχθηκε η καταλυτική δράση κάποιων εκ των συντεθέντων υλικών στην αντίδραση μεθανόλυσης της τριοξικής γλυκερόλης, χρησιμοποιώντας την τεχνική 1H NMR. Διαπιστώθηκε πως τα αμινοτροποποιημένα νανοσωματιδία silica εμφανίζουν σημαντική καταλυτική δράση. Αντίθετα η ικανότητα των υβριδικών οργανικών/ανόργανων υλικών silica-NH2(B)/P(SSH50-co-MA50), silica-NH2(D)/P(SSH75-co-MA25), και silica-VTMS-PDMAEMA να δρουν ως όξινοι ή βασικοί καταλύτες της ίδιας αντίδρασης είναι πολύ περιορισμένη. / The possibility to combine the properties of organic and inorganic components in a unique nanostructured hybrid material is a major scientific challenge in designing novel materials exhibiting improved properties and finding advanced applications. Hybrid materials generally can be classified into two categories: class I, where the two phases are combined through weak interactions, and class II, where the two phases are covalently connected. The aim of the present study was to develop novel hybrid organic/inorganic nanomaterials, potentially applied as heterogeneous catalysts in the biodiesel production process. In this process, called transesterification or methanolysis, triglycerides from various oils react with an alcohol in the presence of a strong acid or base to produce the respective esters and glycerin. In the first part of this work, we focused on the synthesis and characterization of class I and class II hybrid organic/inorganic nanomaterials consisting of an inorganic silicon dioxide (silica) core and a polymer shell. Thus, for the class I hybrid materials we took advantage of the weak interactions between net or amino-functionalized silica nanoparticles and water-soluble P(SSH-co-MA) copolymers of styrene sulfonic acid (SSH), with maleic acid (MA), carrying both carboxyl and sulfonic groups. These hybrid nanoparticles could potentially be used as acidic catalysts in the production of biodiesel, as a consequence of the acidic nature of the polymer used. For the class II hybrid materials, we mostly applied atom transfer radical polymerization (ATRP) of monomers such as sodium styrene sulfonate (SSNa), N-isopropylacrylamide (NIPAM) and 2-(dimethylamino) ethyl methacrylate (DMAEMA). To initiate the polymerization, silica nanoparticles chemically modified with 3-aminopropyltriethoxysilane and subsequently with 2-chloropropionylchloride were used. Alternatively, we also used silica nanoparticles chemically modified with 3-chloropropyltriethoxysilane (ATRP polymerization), or vinyltrimethoxysilane (free radical polymerization, FRP). In all cases, the products were characterized through a combination of techniques, such as proton nuclear magnetic resonance spectroscopy (1H NMR), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and acid-base titration. In the latter part of this work, the catalytic activity of some materials in the methanolysis process of glycerol triacetate was investigated, using the 1H NMR technique. It was found that the aminofunctionalized silica nanoparticles exhibit significant catalytic activity, whereas the ability of the hybrid materials silica-NH2(B)/P(SSH50-co-MA50), silica-NH2(D)/P(SSH75-co-MA25) and silica-VTMS-PDMAEMA to act as acidic or basic catalysts is very limited.

Crystal growth and characterization of few multifunctional materials with perovskite (ABX3) structure are discussed in this thesis. Efforts were made to modify the magnetic and electric behaviour of these materials by selective tuning of A, B and X components. Structural, magnetic and dielectric characterization are detailed in various chapters for doped (A and B site) rare-earth manganites and organometallic compounds with different (Chloride or formate) anions. The relevant aspects of crystal structure and its relationship with ordered ground states are discussed in the introductory chapter. A detailed review of prominent theories pertaining to magnetic and ferroelectric ordering in the literature is provided. Growth of various inorganic compounds by solid-state reaction and floating zone method as well as use of solvothermal techniques for growing organometallic compounds are discussed. Material preparation, optimization of crystal growth processes and results of characterization are addressed in various chapters. The effect of Yttrium doping on structural, magnetic and dielectric properties of rare-earth manganites (RMnO3 where R = Nd, Pr) has been investigated. Neutron diffraction studies (Pr compounds) confirm A-type antiferromagnetic structure and fall in transition temperature as the Yttrium doping level increases. Diffraction experiments in conjunction with dc magnetization and ac susceptibility studies reveal magnetic frustration in excess Yttrium dopedcompounds. When mutliglass properties of 50% B-site doped Nd2NiMnO6 were investigated, evidence of re-entrant cluster glass phase was seen probably due to presence of anti-site disorder. The relaxor-like dielectric behaviour arises from crossover of relaxation time in grain and grain boundary regions. Multiferroic behaviour of the organometallic compound (C2H5NH3)2CuCl4 as well as the ferroelectric transition were investigated in detail. The role of Hydrogen bond ordering in driving structural transitions is elucidated by low temperature dielectric and Raman studies in (C2H5NH3)2CdCl4. It was found possible to tune the magnetic and ferroelectric properties in metal formate compounds (general formula AB(HCOO)3) by selectively choosing organic cations [(CH3)2NH2+; C(NH3)3+] and transition metal ion [B = Mn, Co and Cu]. The nature of magnetic ordering and transition temperature could be altered by the transition metal ion. The effect of reorientation of organic cations which leads to ferroelectric nature is discussed using dielectric and pyroelectric data. Significant results are summarized in the chapter outlining general conclusions. Future prospects of work based on these observations are also provided. The conclusions are corroborated by detailed analysis of experimental data.

Der Schwerpunkt der vorliegenden Arbeit liegt in der Charakterisierung der elektronischen Eigenschaften von hybriden organisch-anorganischen Perowskit (HOIP)-Schichten während der Schichtbildung und in verschiedenen Umgebungen mittels Photoelektronenspektroskopie (PES). Insbesondere wird der Methylammonium-Blei-Iodid-Chlorid-Perowskit (MAPbI3-xClx) untersucht. Als erstes werden Änderungen in den elektronischen Eigenschaften, der Zusammensetzung, sowie der Kristallstruktur mittels PES, Flugzeit-Sekundärionenmassenspektrometrie, sowie Röntgendiffraktometrie mit streifendem Einfall analysiert. Die Resultate weisen auf die entscheidende Rolle von Chlor im texturierten Wachstum der Perowskitschicht hin. Die auskristallisierte Perowskitschicht weist eine stärkere n-Typ Eigenschaft auf, welche auf die Änderung der Zusammensetzung während der Schichtbildung zurückgeführt werden kann. Außerdem beweisen die Ergebnisse eindeutig die Ablagerung von Chlor an der Grenzfläche zwischen der Perowskitschicht und dem Substrat. Zweitens werden die separaten Einflüsse von Wasser, Sauerstoff, und Umgebungsluft auf die elektronischen Eigenschaften von MAPbI3-xClx-Schichtoberflächen untersucht. Bereits geringste Wassermengen ähnlich wie im Hochvakuum oder in inerter Umgebung können eine reversible Reduzierung der Austrittsarbeit hervorrufen. Höherer Wasserdampf-Partialdruck führt zu einer Verschiebung des Valenzbandmaximums (VBM) weit vom Fermi-Niveau, sowie zu einer Reduzierung der Austrittsarbeit. Im Gegensatz dazu führt eine Sauerstoffexposition zu einer Verschiebung des VBM in Richtung des Fermi-Niveaus und zu einer Steigerung der Austrittsarbeit. Analog kommt es zu einer Verschiebung von bis zu 0.6 eV bei einer Exposition gegenüber Umgebungsluft, was den vorwiegenden Einfluss von Sauerstoff demonstriert. Die vorliegenden Untersuchungen betonen den kritischen Einfluss der Schichtbildung, der Zusammensetzung, sowie der Umgebungsbedingungen auf die elektronischen Eigenschaften von HOIP. / The present thesis aims at characterizing the electronic properties of solution-processed hybrid organic-inorganic perovskites (HOIPs) in general, and the HOIP methyl ammonium (MA) lead iodide-chloride (MAPbI3-xClx) films, in particular, at different stages, namely from its formation to its degradation, by means of photoelectron spectroscopy (PES). Firstly, the formation of MAPbI3-xClx films upon thermal annealing is monitored by a combination of PES, time-of-flight secondary ion mass spectrometry, and grazing incidence X-ray diffraction for disclosing changes in electronic properties, film composition, and crystal structure, respectively. Overall, the results point to the essential mediating role of chlorine in the formation of a highly textured perovskite film. The film formation is accompanied by a change of composition which leads to the film becoming more n-type. The accumulation of chlorine at the interface between perovskite and the underlying substrate is also unambiguously revealed. Secondly, the separate effects of water and oxygen on the electronic properties of MAPbI3-xClx film surfaces are investigated by PES. Already low water exposure – as encountered in high vacuum or inert conditions – appears to reversibly impact the work function of the film surfaces. Water vapor in the mbar range induces a shift of the valence band maximum (VBM) away from the Fermi level accompanied by a decrease of the work function. In contrast, oxygen leads to a VBM shift towards the Fermi level and a concomitant increase of the work function. The effect of oxygen is found to predominate in ambient air with an associated shift of the energy levels by up to 0.6 eV. Overall, the findings contribute to an improved understanding of the structure-property relationships of HOIPs and emphasize the impact of least variation in the environmental conditions on the reproducibility of the electronic properties of perovskite materials.

Over the past two decades, organic semiconductors played a growing part as active layers in several electronic systems such as sensors, field‑effect transistors or light emitting diodes to cite a few. In fact, organic materials offer a high versatility and flexibility. However, pure organic systems often lack stability and robustness, which can be overcome by combining them with inorganic scaffolds. In this work, a conducting polymer, polypyrrole (PPy) is employed to create new sensor elements based on the combination of both inorganic and organic layers. Electrical measurements, infrared spectroscopy and current sensing atomic force microscopy provides a better understanding of the polymer behavior upon immersion in aqueous solutions. The observed discharge in water leads to a straightforward application of the device as an in‑flow sensor for several acids like HCl, H2SO4 and H3PO4. The wide range of sensing concentrations as well as the low detection limit place the present detector among the best reported so far in the literature. In a further step to turn towards lab‑in‑a‑tube devices, tubular‑shaped‑integrated microelectrodes are developed by using the rolled‑up technology. As a proof of concept, the successful integration of PPy as an active layer and its use as a gas sensor for volatile organic compounds (VOCs) is demonstrated. Finally, by adapting the rolled‑up top electrodes, as developed by Bof Bufon et al. for self‑assembled monolayers (SAMs), thin PPy films (<50 nm) are vertically contacted and their electrical characteristics measured as a function of temperature and electric field. From the transport investigations, it is observed that an insulating‑to‑metallic transition occurs in the polymeric film by increasing the bias voltage. Other molecular layers like CuPc can be incorporated in these platforms, opening the way towards emerging organic devices.

Das Verstehen der elektronischen Prozesse in Nano-Hybridsystemen, bestehend aus Molekülen und Halbleiterstrukturen, eröffnet neue Möglichkeiten für optoelektronische Bauteile. Dafür benötigt es nanoskopische und gleichzeitig atomare Modelle und somit angepasste Rechenmethoden. Insbesondere "Standard"-Ansätze für die Dynamik offener Quantensysteme werden mit zunehmender Systemgröße jedoch sehr ineffizient. In dieser Arbeit wird eine neue Methode basierend auf einer stochastischen Schrödinger-Gleichung etablieren. Diese umgeht die numerischen Limits der Quanten-Mastergleichung und ermöglicht Simulationen von imposanter Größe. Ihr enormes Potenzial wird hier in Studien zu Anregungsenergietransfer und Ladungsseparation an zwei realistischen Nano-Hybridsystemen demonstriert: para-sexiphenyl Moleküle auf einer flachen ZnO Oberfläche (6P/ZnO), und ein tubuläres C8S3 Farbstoffaggregat gekoppelt an einen CdSe Nanokristall (TFA/NK). Im 6P/ZnO System findet nach optischer Anregung Energietransfer vom 6P Anteil zum ZnO statt. Direkt an der Grenzfläche können Frenkel-Exzitonen zusätzlich Ladungsseparation initiieren, wobei Elektronen ins ZnO transferiert werden und Löcher im 6P Anteil verbleiben. Beide Mechanismen werden mittels laserpulsinduzierter ultraschneller Wellenfunktionsdynamik simuliert. Danach wird die langsamere dissipative Lochkinetik im 6P Anteil studiert. Hierfür wird die eigene Simulationstechnik der stochastischen Schrödinger-Gleichung verwendet. Die Studie an der TFA/NK Grenzfläche basiert auf einer gigantischen equilibrierten Aggregatstruktur aus 4140 Molekülen. Ein generalisiertes Frenkel-Exzitonenmodell wird benutzt. Der Ansatz der stochastischen Schrödinger-Gleichung ermöglicht bemerkenswerte Einblicke in die Aggregat-interne Exzitonenrelaxation. Danach werden inkohärente Raten des Exzitonentransfers zum NK berechnet. Unterschiedliche räumliche Konfigurationen werden untersucht und es wird diskutiert, warum das Förster-Modell hier keine Gültigkeit besitzt. / Understanding the electronic processes in hybrid nano-systems based on molecular and semiconductor elements opens new possibilities for optoelectronic devices. Therefore, it requires for models which are both nanoscopic and atomistic, and so for adapted computational methods. In particular, "standard" methods for open quantum system dynamics however become very inefficient with increasing system size. In this regard, it is a key challenge of this thesis, to establish a new stochastic Schrödinger equation technique. It bypasses the computational limits of the quantum master equation and enables dissipative simulations of imposing dimensionality. Its enormous potential is demonstrated in studies on excitation energy transfer and charge separation processes in two realistic nanoscale hybrid systems: para-sexiphenyl molecules deposited on a flat ZnO surface (6P/ZnO), and a tubular dye aggregate of C8S3 cyanines coupled to a CdSe nanocrystal (TDA/NC). After optical excitation, the 6P/ZnO system exhibits exciton transfer from the 6P part to the ZnO. Close to the interface, Frenkel excitons may further initiate charge separation where electrons enter the ZnO and holes remain in the 6P part. Both mechanisms are simulated in terms of laser-pulse induced ultrafast wave packet dynamics. Afterwards, slower dissipative hole motion in the 6P part is studied. For this purpose, the own stochastic Schrödinger equation simulation technique is applied. The study on the TDA/NC interface is based on a gigantic equilibrated nuclear structure of the aggregate including 4140 dyes. A generalized Frenkel exciton model is employed. Thanks to the stochastic Schrödinger equation approach, energy relaxation in the exciton band of the TDA is simulated in outstanding quality and extend. Then, incoherent rates for exciton transfer to the NC are computed. Different spatial configurations are studied and it is discussed why the Förster model possesses no validity here.