Kryptingas kietojo kūno darinių, naudojamų išorinio dujų poveikio detekcijai, savybių keitimas yra vienas iš aktualiausių uždavinių, sprendžiamų kuriant lakiųjų cheminių junginių poveikio atpažinimo ir matavimo sistemas. Šias savybes lemia darinių medžiaga, jų struktūra bei sąveikos su dujine aplinka ypatumai, kurie hibridiniuose dariniuose iš kietojo kūno ir biomolekulių gali būti lemiami dar ir biocheminiu atpažinimu. Šiame darbe tiriami dujoms jautrūs hibridiniai dariniai ir nanosistemos, integruotos metalo oksido plėvelėse, Skenuojančio zondo mikroskopijos (SZM) metodais. Disertacijoje susieti itin plonų (< 30-50 nm) SnOx sluoksnių varžos atsako į dujas bei elektrinių savybių ypatumai su sluoksnių morfologija, priklausančia nuo auginimo sąlygų ir trukmės. Eksperimentiškai įrodyta, jog SZM lokalinių srovių tyrimai, priklausomai nuo matavimo parametrų, leidžia atskirai aprašyti technologiškai keičiamas dujoms jautrių darinių charakteristikas ir tik nanosistemose vykstančius procesus, kurie, kai kuriais atvejais, gali būti stebimi ir tipiškuose dujoms jautrių darinių taikymuose. Sukurtas originalus metodas, tinkantis nanostruktūroms metalo oksidų paviršiuje formuoti bei tų struktūrų elektrinėms savybėms keisti. Skirtingai nuo literatūroje žinomo paviršiaus nanooksidinimo, pritaikyto formuoti cheminiam poveikiui atsparias dangas, mūsų metodas leidžia formuoti įvairaus elektrinio laidumo nanostruktūras metalo oksidų paviršiuje. / Modification of the properties of solid state structures, used for gas sensing is important task in making detection and measurement systems of volatile chemical compounds. These properties depend on material, inner structure and interaction with gas atmosphere. In hybrid materials (solid-biomolecular) biochemical recognition plays important role in gas sensing mechanism. In this work the methodologies of the SPM was applied for characterization of the local point and local area properties in the gas sensitive MO films with the nanoscaled thickness that can be used for nanosystems and hybrid materials in novel types of chemical detectors. In this dissertation morphology and physical properties of metal oxide films with thickness from a few to about 50 nm was investigated and described a relationship between the gas response and film thickness. It was experimentally shown that effects of external influence on the properties of the surface nanostructures can be described by the specific characteristics of the scanning probe spectroscopy displaying the dependences of the probe contact electric current on both the probe potential and the probe pressing force. An original method based on the SPM probe controlled electrical current was proposed for the formation of nanosystems with various electrical properties on the surfaces of thin MO films.

Cette thèse est constituée de deux parties indépendantes. La première partie traite du transport dans des gaz d'électrons bidimensionnels dans le régime de l'effet Hall quantique. Dans la deuxième partie, le courant et les corrélations croisées en courant sont étudiées pour des structures hybrides conducteur normal- supraconducteur- conducteur normal (NSN). Dans le régime de haute température de l'effet Hall quantique, la conductance longitudinale est calculée par un formalisme diagrammatique basé sur une approche de conductivité locale. Ce calcul prend en compte l'effet de dérive des électrons sur les lignes équipotentielles du potentiel de désordre et permet la dérivation microscopique de l'exposant critique de transport qui était auparavant seulement conjecturé à partir d'arguments géométriques qualitatifs. Des expressions microscopiques pour la dépendance en température et en champ magnétique de la conductance longitudinale sont dérivées et comparées avec des expériences récentes. Dans le régime de basse température de l'effet Hall quantique, le passage du courant par effet tunnel sur des points selles est étudié à partir de la diffusion de paquets d'onde d'états semi-cohérents. Nous dérivons analytiquement le coefficient de transmission d'un point selle pour le potentiel scalaire dans le graphène et trouvons que les points selles asymétriques brisent la symétrie particule-trou de la conductance. Dans des structures hybrides NSN, nous étudions l'influence de barrières additionnelles sur la conductance (non-locale) et sur les corrélations croisées en courant avec la théorie de diffusion. Dans les systèmes métalliques, où la phase est moyennée, des barrières additionnelles augmentent les processus locaux par réflexion Andreev résonante (reflectionless tunneling), mais ont peu d'influence sur les processus non-locaux et sur les corrélations croisées en courant. Dans les systèmes balistiques, des barrières additionnelles causent des oscillations Fabry-Pérot et permettent de distinguer les différents processus contribuant à la conductance et aux corrélations croisées en courant. / This thesis consists of two independent parts. The first one deals with transport in two dimensional electron gases in the regime of the quantum Hall effect. In the second part, current and current cross-correlations are studied in normal conductor-superconductor-normal conductor (NSN) hybrid structures. In the high temperature regime of the quantum Hall effect, the longitudinal conductance is calculated in a diagrammatic formalism based on a local conductivity approach. It takes the interplay between electron-phonon scattering and the drift motion along equipotential lines of the disorder potential into account and provides a microscopic derivation of the universal transport critical exponent that was up to now only conjectured from qualitative geometrical arguments. Microscopic expressions for the dependence in temperature and magnetic field of the longitudinal conductance are derived and compared to recent experiments. In the low temperature regime of the quantum Hall effect, tunneling over saddle points is studied from the scattering of semi-coherent state wave packets. We derive analytically the transmission coefficient of saddle-points in the scalar potential in graphene and find that asymmetric saddle-points break particle-hole symmetry in the conductance. In three-terminal NSN hybrid structures the influence of additional barriers on the (non-local) conductance and on current cross-correlations is studied with scattering theory. In metallic, phase averaged systems additional barriers lead to an enhancement of local processes by reflectionless tunneling but have little influence on non-local processes and on current cross-correlations. In ballistic systems, additional barriers lead to Fabry-Perot oscillations and allow to distinguish the different contributions to the conductance and to the current cross-correlations.

Neste trabalho, ligações entre vigas pré-moldadas de concreto e pilares mistos preenchidos foram propostas com a finalidade de transferir momento de flexão e força cortante das vigas para os pilares mobilizando os núcleos de concreto. Foi realizado um estudo numérico-experimental das ligações onde foi avaliada a viabilidade e a eficiência destas na transferência dos esforços. Em uma primeira fase, modelos compostos por pilar misto e consolo metálico (modelos 1 e 2) foram confeccionados, testados experimentalmente e modelados numericamente (método dos elementos finitos) para avaliar a eficiência do consolo na transferência da força cortante. Observou-se que a transferência da força cortante do consolo para o tubo metálico foi eficaz. O consolo se comportou de maneira previsível e suportou cargas elevadas. O uso de conectores de cisalhamento internos aos pilares aumentou a capacidade de carga e o desempenho dos mesmos. Na etapa seguinte da pesquisa foram confeccionados dois modelos, compostos por: pilar, viga pré-moldada, laje e consolo formando pórticos. Em um destes modelos (modelo 4) uma caixa metálica foi incorporada à viga pré-moldada e parafusado ao consolo metálico com a finalidade de transferir os momentos positivos, enquanto que outro modelo foi confeccionado e estudado sem este elemento (modelo 3). Nestes modelos foi avaliada a capacidade de transferência do momento de flexão (positivo e negativo) e forças cortantes com a ligação submetida a ciclos de carga. No modelo 3, a ligação transferiu de forma eficiente o momento negativo, porém o desempenho para o momento positivo não foi satisfatório, com baixa resistência e rigidez ao longo dos ciclos de carga. No modelo 4 foi observado considerável aumento da resistência e rigidez se comparado com o modelo anterior. Entretanto, a caixa metálica incorporada à viga pré-moldada não foi capaz de fazer com que a ligação resistisse aos momentos positivos como a mesma eficiência que resistiu aos negativos e houve degradação de suas características estruturais ao longo dos ciclos de carga. / In this work, connections of precast concrete beam to concrete-filled steel tube column were proposed to transfer the bending moment and shear forces from the beam to the composite column, mobilizing the concrete core. Was performed a numerical and experimental study of the proposed connections to evaluate the feasibility and effectiveness of them in the transfer of bending and shear forces from the beam to the column. In a first stage, models composed by column and steel corbel (models 1 e 2) were numerically and experimentally tested aiming the efficiency of the connection in shear transfer. It was observed that the transfer of shear to the steel tube was guaranteed. The corbel behaved in a predictable way and supported high loads. The use of shear connectors in the column increased the load capacity and improved the connection performance. In next stage of the research work, two models were prepared, composed by: column, precast concrete beam, steel corbel and slabs constituting frames. In one of these models (model 4) a steel box was incorporated into the precast beam and bolted to the steel corbel in order to transfer the positive moments, whereas another model was built and studied without this device (model 3). In this models were evaluated the efficiency in the transfer of bending moments (positive and negative) and shear forces with the models subjected to a cyclic loads. In the model 3, the connection transferred efficiently the negative bending, but the performance for the positive bending was not satisfactory, with reduced strength and stiffness over the load cycles. In model 4 was observed considerable increase in strength and stiffness compared with the previous model. However, the device incorporated in the precast beam was unable to make the connection resist to the positive moments with the same efficiency observed when subjected to the negative moments and a degradation of their structural characteristics was observed during the loading cycles.

Graphene and Carbon nanotubes (CNTs) have been researched for more than a decade due to their extraordinary properties and advantages towards applications like electronics, structural re-enforcements, thermal management and energy storage. Graphene-CNT hybrid structures have been predicted to further enhance the exceptional properties and overcome some of the shortcomings of the individual materials. Advantages of a structure consisting of vertically aligned carbon nanotubes (VACNTs) covalently bonded with graphene layers have been predicted to be especially favourable for applications like TIM, supercapacitors and battery electrodes. This project investigates two growth mechanisms for obtaining Graphene-VACNT structures using scalable processes. Shortcomings of previously done research on similar structures like graphene transfer and bad CNT alignment is solved. A novel growth mechanism is also investigated to set the foundation for research into a new approach to grow Graphene-CNT hybrid structures in the future. Chemical Vapor Deposition (CVD) was the method used to grow the graphene and CNT structures. The characterization was done using optical microscopy, Scanning electron microscopy (SEM) and Raman spectroscopy. / Grafen- och kolnanorör (CNT) har forskats i mer än ett decennium på grund av deras extraordinära egenskaper och fördelar gentemot applikationer som elektronik, strukturförstärkning, termisk hantering och energilagring. Grafen-CNT hybridstrukturer har förutspåtts ytterligare förbättra de exceptionella egenskaperna och övervinna några av bristerna i de enskilda materialen. Fördelar med en struktur som består av vertikalt inriktade kolnanorör (VACNT) som är kovalent bundna med grafenskikt har förutspåtts vara särskilt fördelaktiga för applikationer som TIM, superkondensatorer och batterielektroder. Detta projekt undersöker två tillväxtmekanismer för att erhålla Graphene-VACNT-strukturer med hjälp av skalbara processer. Brister i tidigare utförd forskning om liknande strukturer som grafenöverföring och dålig CNT-anpassning är lösta. En ny tillväxtmekanism undersöks också för att lägga grunden för forskning om ett nytt tillvägagångssätt för att växa Graphene- CNT hybridstrukturer i framtiden. Chemical Vapor Deposition (CVD) var metoden som användes för att odla grafen- och CNT-strukturerna. Karakteriseringen gjordes med optisk mikroskopi, Scanning electron microscopy (SEM) och Raman-spektroskopi.

Analytical models of wood-frame shear walls and diaphragms for use in monotonic, quasi-static (cyclic), and dynamic analyses are developed in this thesis. A new analytical model is developed to accurately represent connections between sheathing panels and wood framing members (sheathing-to-framing connections) in structural analysis computer programs. This new model represents sheathing–to–framing connections using an oriented pair of nonlinear springs. Unlike previous models, the new analytical model for sheathing-to-framing connections is suitable for both monotonic, cyclic, or dynamic analyses. Moreover, the new model does not need to be scaled or adjusted. The new analytical model may be implemented in a general purpose finite element program, such as ABAQUS, or in a specialized structural analysis program, such as CASHEW. The analytical responses of several shear walls and diaphragms employing this new model are validated against measured data from experimental testing. A less complex analytical model of shear walls and diaphragms, QUICK, is developed for routine use and for dynamic analysis. QUICK utilizes an equivalent single degree of freedom system that has been determined using either calibrated parameters from experimental or analytical data, or estimated sheathing-to-framing connection data. Application of the new analytical models is illustrated in two applications. In the first application, the advantages of diaphragms using glass fiber reinforced polymer (GFRP) panels in conjunction with plywood panels as sheathing (hybrid diaphragms) are presented. In the second application, the response of shear walls with improperly driven (overdriven)nails is determined along with a method to estimate strength reduction due to both the depth and the percentage of total nails overdriven.

[pt] A indústria de transporte tem enfrentado rigorosas políticas econômicas e ambientais para a redução do consumo de combustível e consequentemente redução na emissão de CO2. Uma solução promissora para suprir tais exigências encontra-se na redução do peso da estrutura de carros e aviões através do uso de estruturas híbridas. Técnicas de união convencionais geralmente são inadequadas para produzir juntas híbridas de metal e polímero. Sendo assim, tecnologias de junção inovadoras estão sendo desenvolvidas para surprir tais limitações, como por exemplo: União pontual por fricção (FSpJ), rebitagem por fricção (FricRiveting) e união por energia ultra-sônica (U-Joining). Esta dissertação de mestrado foi desenvolvida para avaliar juntas híbridas produzidas com baixo (BAE) e alto aporte energético (AAE). O monitoramento da temperatura, a análise microestrutural, a resistência mecânica e os respectivos modos de falhas das juntas foram avaliados para as três técnicas de fricção. Neste contexto, técnicas de microscopia, microtomografia de raio-x e ensaios de resistência mecânica foram escolhidas para tal finalidade. Juntas de AAE produzidas por união pontual de fricção apresentaram 43 porcento maior resitência mecânica comparado com juntas de BAE e ambas falharam no centro da área de junção. Juntas de AAE produzidas por rebitagem apresentaram 46 porcento maior resitência mecânica e falha do rebite metálico fora da placa polimérica, comparado com juntas de BAE que teve o rebite metálico arrancado da placa polimérica. A resitência ao cisalhamento das juntas de AAE (fratura da placa polimérica) produzidas por energia ultra-sônica foi 85 porcento maior que as juntas de BAE (fratura dos pinos combinado com falhas coesivas e adesivas). / [en] The transportation industry has been facing stringent environmental regulations to decrease fuel consumption and CO2 emissions. A promising solution to fulfill these demands is decreasing the structural weight of vehicles and airplanes by combining lightweight alloys and fiber-reinforced polymers in hybrid structures. Conventional joining technologies are usually inadequate to produce high performance joints. To overcome these limitations, advanced joining technologies are under development such as: Friction Spot Joining (FSpJ), Friction Riveting (FricRiveting) and Ultrasonic Joining (U-Joining). This master dissertation was devised to evaluate FSp, FricRiveting and U-Joining joints produced with different heat input levels (low and high) in terms of process temperature development, microstructural features, quasi-static mechanical performance and the respective failure mechanisms. In this context, microscopy techniques (i.e. optical, confocal laser and scanning electron), X-Ray micro-computed tomography (microCT), lap shear and T-Pull testing were chosen for this purpose. FSp joints produced under HHI joining condition achieved an ultimate lap shear force (ULSF) 43 percent higher than LHI joints, whereas HEI joints produced by FricRiveting process achieved ultimate tensile force (UTF) 46 percent higher than LEI joints. The lap shear strength of ultrasonically joined joints produced under HEI joining condition was up to 85 percent higher than LEI joints. FSp joints failured in the center of the overlap area while friction-riveted joints failured through the rivet (HEI) and full rivet pull-out (LEI). Ultrasonically joined joints failured through the polymer (HEI), whereas LEI joints failured through a combination of shearing of the metallic pins and a mixed cohesive (CF) and adhesive (AF) failure.

Zentrales Thema dieser Dissertation ist die Untersuchung anorganisch/organischer Hybridsysteme (HIOS) mit besonderem Fokus auf den speziellen Prozessen an der Grenzfläche beider Materialklassen. Organische Moleküle, in Verbindung mit anorganischen Halbleitern haben ein großes Potenzial für Anwendungen in zukünftigen optoelektronischen Hybridbauteilen, indem sie Vorteile zweier unterschiedlicher Welten kombinieren. Entscheidend für die Herstellung von hybriden Strukturen ist das Verständnis der Wechselwirkungen an der Grenzfläche zwischen organischem und anorganischem Material. In dieser Arbeit werden diese Wechselwirkungen analysiert, um eine Wachstumskontrolle an der Grenzfläche zwischen konjugierten organischen Molekül und anorganischem Halbleiter zu ermöglichen. Hierfür werden unterschiedliche Ansätze verfolgt: Im ersten Teil der Arbeit wird die Wechselwirkung des Modellsystems Sexiphenyl (6P) an der Grenzfläche zu ZnO untersucht, sowie das Wachstum des Moleküls mittels verschiedener Methoden kontrolliert. Das daraus gewonnene Wissen kann im zweiten Teil dazu verwendet werden einen hybriden ZnO/6P/ZnO-Stapel zu realisieren, bei dem die organische Schicht ohne Beeinträchtigung der Kristallstruktur, mit definierten Grenzflächen bis hin zur atomaren/molekularen Ebene, überwachsen werden kann. Der letzte Teil der Arbeit befasst sich mit der optischen Echtzeit-Beobachtung während des organischen Wachstums verschiedener Moleküle. Dadurch ist es möglich Veränderungen von Struktureigenschaften und Wechselwirkungen zwischen Molekülen und dem Substrat zerstörungsfrei zu bestimmen, während diese aufgewachsen werden. Hierdurch können schlussendlich mögliche Mechanismen aufgezeigt werden, um elektronische und optische Wechselwirkung an der Grenzfläche zwischen organischem Molekül und anorganischen Halbleitern zu analysieren, sowie Wachstumsprozesse weiter zu verstehen und kontrollieren. / The central subject of this thesis are hybrid inorganic/organic systems (HIOS) with a focus on the specific processes at the interface between the two material classes. Organic molecules used together with inorganic semiconductors, have a great potential for future optoelectronic applications in hybrid components, by combining the advantages of two dissimilar worlds. Decisive for the production of hybrid structures is the understanding of the interactions at the interface between organic and inorganic material. In this thesis, the interactions are analyzed to enable growth control at the interface between conjugated organic molecules and inorganic semiconductors. In the first part of the thesis, the interaction of the model system sexiphenyl (6P) at the interface with ZnO, as well as approaches to control the growth of the molecule are being investigated. The knowledge gained here is used in the second part to realize a hybrid ZnO/6P/ ZnO stack, in which the organic layer can be overgrown without affecting the crystal structure, exhibiting defined interfaces down to the atomic/molecular level. The last part of the thesis deals with real time optical observation during organic growth of different molecules. By this changes in structural properties and interactions between molecules and the substrate can be non-destructively determined as they are growing. Ultimately, a comprehensive insight into the optical and electronic interactions at the interface between organic molecules and inorganic semiconductors can be gained and possible control mechanisms are shown.

One-dimensional (1D) nanostructures have gained tremendous attention over the last decade due to their wide range of potential applications. Particularly, ZnO 1D nanostructures have been investigated with great interest due to their versatility in synthesis with potential applications in electronics, optics, optoelectronics, sensors, photocatalysts and nanogenerators. The thesis deals with the challenges and the answer to grow ZnO 1D nanostructure by vapor phase transport (VPT) continuously without any length limitation. The conventional VPT technique has been modified for the non-catalytic growth of ultralong ZnO 1D nanostructures and branched structures in large area with controllable aspect ratio. It has been shown that the aspect ratio can be controlled both by thermodynamically (temperature) and kinetically (vapour flux). The thesis also deals with the fabrication of carbon nanotube (CNT) -ZnO based multifunctional devices and the field emission performance of ZnO nanowires by employing various strategies. The entire thesis has been organised as follows: Chapter 1 deals with Introduction. In this chapter, importance of ultralong nanowires and significance of ultralong ZnO nanowires has been discussed. Various efforts to grow ultralong ZnO nanowire with their advantages and disadvantages have been summarised. Lastly the significance of forming ZnO nanowires based nano hybrid structures and importance of doping in ZnO nanowires and has also been discussed. Chapter 2 deals with experimental procedure and characterization. In this chapter, a single step VPT method for the growth of ultralong ZnO nanowires that incorporates local oxidation barrier for the source has been described. The synthesized nanowires were characterised by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Raman & photoluminescence. Chapter 3 deals with growth of ZnO nanowires, controlling the aspect ratio of ZnO nanowires, and role of other experimental aspects. In this chapter, a way to grow nanowires continuously without any apparent length limitation, a way to control the diameter of the nanowires kinetically without catalyst particle or seed layer and obtaining smaller diameter of the nanowires by non-catalytic growth as compared to that set by the thermodynamic limit has been discussed. Furthermore, the significance and importance of local oxidation barrier on source for protecting them from degradation, ensuring the continuous supply of vapour and enabling the thermodynamically and kinetically controlled growth of nanowires has been discussed. Lastly, the scheme for large area deposition and a method to use same source material for several depositions has been presented. Chapter 4 deals with multifunctional device based on CNT -ZnO Nanowire Hybrid Architectures same device can be used as a rectifier, a transistor and a photodetector. In this chapter, the fabrication of CNT arrays-ZnO nanowires based hybrid architectures that exhibit excellent high current Schottky like behavior with p-type conductivity of ZnO has been discussed. CNT-ZnO hybrid structures that can be used as high current p-type field effect transistors (FETs) and deliver currents of the order of milliamperes has been presented. Furthermore, the p-type nature of ZnO and possible mechanism for the rectifying characteristics of CNT-ZnO has been discussed. Lastly, the use of hybrid structures as ultraviolet detectors where the current on-off ratio and the response time can be controlled by the gate voltage has been presented and also an explanation for photoresponse behaviour has been provided. Chapter 5 deals with the substrate-assisted doping of ZnO nanowires grown by this technique. In this chapter, the non-catalytic growth of ZnO nanowires on multiwalled carbon nanotubes (MWCNTs) and soda lime glass (SLG) with controlled aspect ratio has been presented. The elemental mapping to confirm the presence and distribution of carbon and sodium in ZnO nanowires and the transport studies on both carbon and sodium doped ZnO has also been presented. Furthermore the stability of carbon doped ZnO has also been presented. Lastly, the advantage of growing ZnO nanowires on MWCNTs and overall advantage associated with this technique has been discussed. Chapter 6 deals with formation of ZnO nanowire branched structures. In this chapter, a possibility to grow ZnO nanowires on already grown ZnO nanowires has been demonstrated. The formation of branched structure during multiple growth of ZnO nanowire on ZnO nanowire has been presented and evolution of aspect ratio in these branched structures has been discussed. Furthermore, the advantage of using ZnO branched structures and also the ZnO nanoneedles on MWCNT mat for field emission has been presented. Chapter 7 summarizes all the findings of the thesis.

Diese Arbeit behandelt das Wachstum des ferromagnetischen Metalls MnAs auf halbleitendem GaAs. Die MnAs-Filme werden auf GaAs mittels der Molekularstrahlepitaxie (MBE) abgeschieden. Nukleation, Entwicklung von Gitterverzerrungen, Morphologie und Grenzflächenstruktur werden in-situ während des MBE Wachstums mit Hilfe von Beugung unter streifendem Einfall (GID) und der Beugung hochenergetischer Elektronen (RHEED) untersucht. Mit azimuthalen RHEED Messungen wurden vier Abschnitte des Nukleationsprozesses von MnAs auf GaAs(001) bestimmt. GID Messungen zeigen, dass das weitere Wachstum des MnAs Films bei einer nominellen Bedeckung von 2.5 ML über die Bildung relaxierter Inseln erfolgt, welche an Größe zunehmen und schließlich einen durchgängigen Film bilden. In einem Frühstadium bildet sich ein geordnetes Versetzungsnetzwerk an der Grenzfläche, welches die Verzerrungen aufgrund der Fehlanpassung bereits vor der vollständigen Ausbildung des durchgängigen Films abbauen. Der faszinierend komplexe Nukleationsprozess von MnAs auf GaAs(0 0 1) beinhaltet sowohl Elemente von Volmer-Weber, als auch von Stranski-Krastanov Wachstum. Die nicht einheitliche Gitterfehlanpassung beträgt 0.66% entlang der [1 -1 0] Richtung und 0.54% entlang der [1 1 0] Richtung, wie sich aus den Röntgenbeugungsmessungen ergibt. Entlang der [1 1 0] Richtung wird eine hohe Korrelation der Defekte beobachtet. Ein hochgradig periodisches Versetzungsnetzwerk mit einer Periode von 4.95 +- 0.05 nm entlang der [1 1 0] Richtung wird an der Grenzfläche gebildet und relaxiert 7.5% der Fehlanpassung. Die inhomogenen Verzerrungen aufgrund dieser periodischen Versetzungen an der Grenzfläche sind auf eine Schicht von 1.6nm Dicke beschränkt. Die Fehlanpassung entlang der [1 -1 0] Richtung wird durch die Bildung eines Koinzidenzgitters abgebaut. / The present work is devoted to the growth of the ferromagnetic metal MnAs on the semiconductor GaAs by molecular-beam epitaxy (MBE). The MnAs thin films are deposited on GaAs by molecular-beam epitaxy (MBE). Grazing incidence diffraction (GID) and reflection high-energy electron diffraction (RHEED) are used in situ to investigate the nucleation, evolution of strain, morphology and interfacial structure during the MBE growth. Four stages of the nucleation process during growth of MnAs on GaAs(001) are revealed by RHEED azimuthal scans. GID shows that further growth of MnAs films proceed via the formation of relaxed islands at a nominal thickness of 2.5 ML which increase in size and finally coalesce to form a continuous film. Early on, an ordered array of misfit dislocations forms at the interface releasing the misfit strain even before complete coalescence occurs. The fascinatingly complex nucleation process of MnAs on GaAs(0 0 1) contains elements of both Volmer-Weber and Stranski-Krastanov growth. A nonuniform strain amounting to 0.66%, along the [1 -1 0] direction and 0.54%, along the [1 1 0] direction is demonstrated from x-ray line profile analysis. A high correlation between the defects is found along the GaAs[1 1 0] direction. An extremely periodic array of misfit dislocations with a period of 4.95 +- 0.05 nm is formed at the interface along the [1 1 0] direction which releases the 7.5% of misfit. The inhomogeneous strain due to the periodic dislocations is confined at the interface within a layer of 1.6 nm thickness. The misfit along the [1 -1 0] direction is released by the formation of a coincidence site lattice.

Open–framework inorganic materials are an important class of compounds because of their many applications in the areas of ion–exchange, separation and catalysis. Ever since the discovery of microporous aluminophosphates by Flanigen and co–workers in the early 80’s, the field of open–framework compounds has witnessed explosive growth. It is now established that the open–framework compounds comprise of almost all the elements of the periodic table. In addition, it has been shown that the inorganic anions in the open–framework compounds can be partially substituted by rigid organic linkers such as the oxalate. The resulting inorganic–organic hybrid structures are interesting due to the variable nature of the binding properties of the organic and inorganic moieties. The present thesis consists of systematic studies on the formation of amine–templated inorganic open–framework structures and inorganic–organic hybrid compounds based on the main group, transition metal and actinide elements. In Chapter 1 of the thesis an overview of inorganic open-framework materials is presented, with an emphasis on the elements that have been employed in the present study. Chapter 2 has two parts (Parts A and B) describing the synthesis and structure of open-framework tin(II) containing compounds. In Part A, the syntheses and structures of amine–templated tin(II) phosphates are presented, and in Part B, the syntheses and structures of a family of tin(II) oxalate compounds are discussed. Weak intermolecular forces such as hydrogen-bond interactions, π•••π interactions, and lone-pair–π interactions have been observed in these compounds, and appear to lend structural stability. As part of this study, efforts have been made to evaluate the energies associated with the π•••π interactions and the lone-pair–π interactions using suitable theoretical models. In Chapter 3, a new family of organically templated hybrid materials based on indium, synthesized by partially substituting the inorganic anion (phosphite/phosphate/suphate) by the oxalate group, is presented. These compounds exhibit a wide range of structures in which the oxalates play a variety of roles. The observation of the first zero-dimensional molecular hybrid structure and the isolation of concomitant polymorphic compounds is noteworthy. The molecular hybrid structure is reactive and undergoes transformation reactions under both acidic and basic conditions. In Chapter 4, the synthesis and structural studies of five new open–framework phosphate and phosphite compounds of gallium are presented. All the compounds have three-dimensional structures, and the formation of a gallium phosphate based on only one type of building unit (spiro–5) is noteworthy. While a large number of organically templated transition metal phosphates have been synthesized, studies on transition metal phosphites are not many. In Chapter 5, the synthesis, structure and magnetic properties of a family of transition metal (cobalt, vanadium, manganese) phosphite structures templated by the organic amines are presented. A previously known vanadyl phosphite has also been isolated and investigated by temperature dependent ESR and magnetic susceptibility studies. All the transition metal compounds exhibit antiferromagnetic behavior. In Chapter 6, the synthesis, structure, and transformation reactions in amine-templated actinide phosphonoacetates are presented. The compounds, which are based on uranium and thorium, are built up from the connectivity between the metal polyhedra and the phosphonoacetate/oxalate units, forming two– and three–dimensional structures. It has been shown that the two–dimensional uranyl phosphonoacetate–oxalate compound can be prepared by two different synthetic approaches: (i) solvent–free solid state reaction at 150˚C and (ii) room temperature mechanochemical (grinding) route. The formation of oxalate hybrids using the phosphonocarboxylate ligand is a new approach in the synthesis of multi-component hybrid compounds.