<p>This thesis explores the ablation and texturing of synthetic single crystal diamond under ultrashort laser pulse irradiation in rough vacuum ambient conditions. Experiments were performed with a 1 kHz repetition rate titanium sapphire laser system producing pulses at 800 nm central wavelength and 150 fs pulse duration. First, the production of ordered periodic nanostructures (ripples) on the diamond surface was characterized and the periodicity of these structures was analyzed against irradiation parameters. Ripples were usually found to fall into one of two categories: one with a spatial period near the irradiation wavelength and one with a spatial period near λ/2n, where λ is the central laser wavelength in air and n is the refractive index of diamond at λ. The spatial periods were plotted against irradiation conditions including the peak fluence, number of incident pulses, and the angle of incidence. Unique outcomes arising out of complex irradiation conditions were also explored. Second, the ablation thresholds for single pulse up to 1000 pulse irradiation were determined using the <em>D</em>² method at both the fundamental central wavelength (800 nm) and the second harmonic (400 nm). The single 800 nm pulse ablation threshold for synthetic single crystal diamond was determined to be 2.3 J/cm² with an incubation coefficient of 0.54. The single 400 nm pulse ablation threshold was determined to be 1.5 J/cm² with an incubation coefficient of 0.73.</p> / Master of Applied Science (MASc)

Nanodiamonds are a promising platform for quantum technologies due to the combinations of their inherent properties and the properties of the fluorescent color centers hosted in diamond. They can be employed as quantum sensing devices with spatial resolution in the range of the nanometer and capable of withstanding harsh conditions while also being biocompatible, allowing applications with sensitive biological systems; but they also find application in quantum computing and photonics fields. For all these applications the central features are the properties of the photoluminescent color centers employed, the color centers on which this thesis is focused are the Nitrogen-Vacancy (NV) and Silicon-Vacancy (SiV) centers of diamond. Both centers are of high interest due to spin dependent properties of their fluorescent emission which can be accessed at room temperature. The development of quantum technologies based on such fluorescent nanodiamonds is stifled by the the lack of production techniques that can be easily scaled to industrial levels. In fact most of the more prominent techniques found in literature exhibit drawbacks both in terms of control of particle properties and of scalability. This thesis focuses on the synthesis of nanodiamonds by Pulsed Laser Ablation in Liquid, with particular interest in the possibility of producing continuously nanodiamonds containing NV and SiV centers. For the NV center the technique of choice have been Pulsed Laser Ablation in liquid nitrogen focusing on the yield of the process as the technique has already been experimentally validated. For the SiV centers the ablation process was performed in water and the graphite precursor have been substituted for a composite graphite and silicon carbide precursor.

Ferroelectric materials are characterized by a reversible spontaneous polarization in the absence of an electric field. The characteristic polarization response of a ferroelectric material to an applied electric field enables a binary state device in the form of a thin film ferroelectric capacitor that can be used to store digital information. This provides opportunities for the development of high speed, low cost and low power, nonvolatile memory devices. The development of commercial ferroelectric memory devices has however been hampered by (a) several reliability issues including fatigue, leakage current, aging, time dependent dielectric breakdown, retention and imprint and (b) processing problems including the development of a low temperature thin film deposition process and the development of a patterning technology. Lead zirconate titanate (PZT) is now widely considered as the most promising material for ferroelectric memory applications as a result of its excellent ferroelectric properties and wide operating temperature range. However, it is commonly found that metal electroded-PZT capacitors (e.g., Pt/PZT/Pt) show a loss of switchable polarization with cumulative switching cycles. This phenomenon is known as fatigue and is the one of the critical problems affecting the lifetime of ferroelectric memories. This research is primarily focused on the problem of fatigue. On the basis of a quantitative model, various guidelines to minimize the degradation problem have been derived. The model attributes fatigue to domain pinning by space charge that is caused by defect (e.g. oxygen vacancy) entrapment at various interface sites such as electrode-ferroelectric interface, domain boundaries and grain boundaries. Two different approaches to minimize the problem have been outlined : (a) control of the defect density and (b) control of the interface state. The control of interface state was achieved by replacing the metal electrodes with conducting oxide electrodes such as RuO₂. The oxide electrode/PZT capacitors were characterized for their diffusion barrier properties, perovskite phase formation, interface nature and ferroelectric properties. The results indicate that these oxide electroded PZT films are good candidates for nonvolatile memory applications. However, the leakage current levels at the operating voltages are far higher than the metal counterparts. Simultaneous minimization of fatigue and leakage current in PZT films was achieved by using multilayer metal/conducting oxide electrodes (e.g., Pt/RuO₂). The control of defect density was attained by (a) donor doping to compensate for the oxygen vacancies (e.g, Nb doping in PZT) and (b) utilizing ferroelectric materials that have a low intrinsic defect concentration. As a result of the latter approach, novel ferroelectric materials belonging to the layer-structure family of oxides have been identified as excellent candidates for fatigue free nonvolatile memory applications. Laser ablated SrBi₂(Ta_xNb_{1 - x})₂O₉ (0<x<1) films showed very good hysteresis characteristics (remnant polarization value of 11 µC/cm², coercive field of 60 kV/cm), no fatigue was observed up to 10⁹ switching cycles and very low leakage current densities. Furthermore, the formation and properties of these films were characterized. It was found grain size and orientation played a major role in determining the properties of these films. C-axis oriented films were found to exhibit almost no polarization. An additional objective of this research was to identify an etching technology (process integration issue) for patterning of the ferroelectric capacitors. The etching process should provide high etch rates, good etch anisotropy, high etch selectivity and minimal post etch residues. It has been shown that a reactive ion etch process with CCl₂F₂/O₂ as the etch gas mixture can meet these requirements. A detailed process study has been conducted to determine the mechanism of etching. / Ph. D.

Die Synthese kolloidaler Nanopartikel ist daher eines der wichtigsten Forschungsthemen der letzten Jahre. Die gepulste Laserablation in Flüssigkeiten stellt eine Alternative zu den nasschemischen Synthesewegen dar. Merkmale der gepulsten Laserablation in Flüssigkeiten ist der geringe experimentelle Aufwand, die Vielseitigkeit und die Möglichkeit stabilisatorfreie kolloidale Nanopartikel herzustellen. Eine Weiterentwicklung ist die Verwendung von Pulversuspensionen als Ausgangsmaterial. Dies führt zu höheren Produktivitäten und neuen Materialien. Die zugrundeliegenden Prozesse sind allerdings komplex. Um diese Mechanismen aufzuklären, wurde ein chemischer Ansatz gewählt. Als Ausgangsmaterial wurden daher verschiedene Kupferverbindungen (Cu2C2, Cu5Si, Cu3N, Cu(N3)2, Cu3P, Cu2O, CuO, Cu2S, CuS und CuI) verwendet. Die hergestellten Nanopartikel wurden mit Hilfe der analytischen Transmissionselektronenmikroskopie charakterisiert. Dadurch konnten nachgewiesen werden, dass zwei Mechanismen an der Nanopartikelbildung beteiligt sind. Die Laserbestrahlung von Ausgangsmaterialien wie CuO und Cu3N führt zur Bildung von metallischen Kupfernanopartikeln. In dem dabei erzeugten Plasma nukleieren die Kupferatome zunächst zu kleinen primären Nanopartikeln. Diese Partikel koaleszieren anschließend und bilden größere sekundäre Partikel. Im Gegensatz zu dieser reduktiven Ablation, resultiert die Laserbestrahlung von CuI in der Fragmentierung des Materials. In diesem Fall wird kein Plasma erzeugt, sondern der induzierte thermische Stress führt zur Fragmentierung des Kristalls unter Beibehaltung der chemischen Zusammensetzung. Die Frage, welcher der beiden Mechanismen für ein bestimmtes Ausgangsmaterial dominiert, ist entscheidend für potentielle Anwendungen der Methode, da hiervon die chemische Zusammensetzung der erhaltenen Nanopartikel abhängt. Dies wird am Beispiel der Synthese von Bi2Te3 Nanopartikeln diskutiert, die in thermoelektrischen Elementen zur Anwendung kommen können. / The synthesis of colloidal nanoparticles has become a major topic in recent years. The pulsed laser ablation in liquids poses an alternative to the common wet-chemical approaches. Key features of the pulsed laser ablation in liquids are its simple setup, its versatility, and the possibility to generate surfactant-free colloidal nanoparticles. A further development of this technique is the use of suspended powders instead of bulk targets. This leads to higher productivities and even new materials. Although the generation of colloids by irradiating a suspension is straight forward, the underlying mechanisms of the size reduction from micrometer to nanometer sized particles appear to be quite complex. In order to reveal the mechanism a chemical approach was chosen. Hence, various copper compounds (Cu2C2, Cu5Si, Cu3N, Cu(N3)2, Cu3P, Cu2O, CuO, Cu2S, CuS and CuI) were used as a model system in order to investigate the impact of the leaving group on the ablation process. The generated nanoparticles were characterized with analytical transmission electron microscopy. These investigations clearly show that there are two distinct mechanisms involved in nanoparticle formation. The laser irradiation of precursors like CuO and Cu3N results in the formation of metallic copper nanoparticles. In the generated plasma copper atoms nucleate and form small primary particles. These particles later coalesce to larger secondary particles. In contrast to this reductive ablation, the irradiation of CuI follows a fragmentation mechanism. Here, the absorbed power of the laser beam does not produce a plasma but introduces thermal stress leading to fragmentation of the crystal while the chemical composition is preserved. The question which mechanism is predominant is of utmost importance as the chemical composition of the nanoparticles depends on the formation process. This is discussed on the example of the synthesis of Bi2Te3 nanoparticles, which can be used in thermoelectric applications.

La datation de l’âge de génération des hydrocarbures et de la déposition de la roche mère fournit des informations importantes dans la prospection pétrolière. Dans ce travail, différentes stratégies ont été étudiées pour la détermination des métaux traces, et des rapports isotopiques du plomb dans des produits pétroliers par des techniques de spectrométrie de masse. Les stratégies d’analyses développées dans ce travail ont été utilisées pour estimer l’âge de génération du pétrole, ainsi que l’âge de déposition de la roche mère âge du « New Albany shales » dans le basin d’Illinois, en utilisant les géochronomètres U-Th-Pb. Les ages déterminés par la méthode U-Th-Pb sont en très bon accord avec ceux prédits par les modèles numériques géologiques, ce qui démontre le potentiel de cette approche pour étudier l’histoire de la formation des hydrocarbures et dans la recherche de nouvelles sources d'hydrocarbures. / Timing crude oil generation and source rock deposition provides important clues in petroleum prospection. In this work, different analytical procedures were developed for trace metals and Pb isotope ratio were determination crude oils and related products. These analytical strategies were then used, for the first time, to assess the applicability of the U-Th-Pb geochronometers for timing source rock deposition age and crude oil generation in the Illinois Basin. Ages determined are in good agreement with those predicted by geological numerical models, demonstrating the potential of these geochronometers to study the history of hydrocarbons formation and to find new hydrocarbon sources.

Dans l’industrie, les sources d’expositions aux particules ultrafines (PUF) sont nombreuses et connues depuis longtemps. Ces particules quelles soient manufacturées ou non intentionnelles (générées au cours de procédés industriels) présentent des propriétés singulières qui impliquent des effets sur la santé différents de ceux induits par des particules de plus grande taille (micrométrique). L’étude spécifique des PUF nécessite donc le développement de méthodes de prélèvement et d’analyse adaptées permettant d’obtenir des informations pertinentes complémentaires à la masse totale de poussières prélevées. Cette métrique semblerait insuffisante pour caractériser correctement les effets toxiques des PUF. La thèse a donc été menée dans l’optique de disposer de méthodes dédiées à l’analyse des nanoparticules et en particulier sur la caractérisation chimique des particules en fonction de leur taille (couplage entre dispositifs de prélèvement en fonction de la taille des particules et méthode d’analyse). Les méthodes développées ont ensuite été testées sur des échantillons provenant soit de sites et/ou procédés industriels (fonderie, projection thermique) soit d’essais en laboratoire par prélèvement sur banc de génération de PUF. / Expositions to nanoparticles (NPs) are known in industrial hygiene for a long time. Either from primary or secondary sources (industrial processes), these particles have specific properties which imply different toxicities compared to larger particles (micrometric) from the same material. Therefore NPs study requires adapted sampling and analytical technique development and more specifically methods allowing to access relevant information other than total dust mass. The latter seems not be sufficient for toxic effect assessment. Thus, this work has been conducted in order to dispose of analytical methods dedicated to NPs and especially on size-dependent particle chemical analysis. Then, the developed methods have been applied on samples collected either from industrial sites and/or processes (smelter, thermal projection), either from NP generation bench.

L’engouement pour l’originalité des propriétés physiques des nanoparticules s’est accompagné d’un développement de nombreuses méthodes de synthèse depuis un demi siècle. Parmi elles, l’ablation laser en liquide permet de produire des nanoparticules avec des surfaces libres de tout contaminant et ce pour une multitude de combinaisons de matériaux et de solvants. Cependant, la simplicité apparente de cette technique dissimule la complexité des mécanismes physico-chimiques, ce qui entraîne actuellement un manque de contrôle des objets synthétisés. Tout d’abord, nous nous sommes intéressés à la cinétique des bulles pour laquelle les conditionsextrêmes d’ablation laser en liquide présentent des cas originaux de cinétique dans le domaine de la mécanique des fluides. Puis, ce travail de thèse vise à donner de plus amples perspectives quant à une meilleure maîtrise de la structure cristalline des nanoparticules et de la stabilité colloïdale. Une manière plus directe de contrôler la taille, la phase cristalline et la stabilité colloïdale des solutions contenant des nanoparticules est d’ajouter des ligands. Nous avons donc étudié les mécanismes de stabilisation de ces solutions en utilisant des ions qui se complexent aux nanoparticules d’or. Nous avons aussi réussi à synthétiser des nanoparticules de rubis (alumine dopée chrome). La stabilisation de ces nanoparticules dans une phase métastable en utilisant des ligands organiques a été expliquée par une étude théorique / Laser generation of nanoparticles in liquids : new insights on crystal structure control and colloidal stability The great interest of nanoparticles for their original physical and an chemical properties has been supported by the development of numerous methods of synthesis. In the nineties, laser generation of nanoparticles in liquids appeared, including Pulsed Laser Ablation in Liquids (PLAL). The PLAL technique enables to produce surface free particles for plenty of material and solvent combinations. However, the apparent simplicity of its implementation hides complex physico-chemical mechanisms resulting in a lack of control of the final products. We firstly investigated the dynamics of the laser-generated bubbles for which the PLAL extreme conditions present new studied cases of bubbles dynamics not encountered in the field of fluid mechanics. Then, we aim to bring new insights into better control of the nanoparticles morphology and their colloidal stability. A straight way to tune sizes, crystal structures and the colloidal stability consists in the addition of stabilizing agents. Hence, we investigated the mechanisms of stabilization of colloidal gold using complexing ions. We also succeed to synthesis nano-rubies, i.e. chromium doped corundum alumina nanoparticles, unexpected at nanoscale. The stabilization of the metastable crystal structure using ligands is explained thanks to a comprehensive theoretical approach

Recent years witnessed a vast advent of stalagmites as palaeoclimate archives. The multitude of geochemical and physical proxies and a promise of a precise and accurate age model greatly appeal to palaeoclimatologists. Although substantial progress was made in speleothem-based palaeoclimate research and despite high-resolution records from low-latitudinal regions, proving that palaeo-environmental changes can be archived on sub-annual to millennial time scales our comprehension of climate dynamics is still fragmentary. This is in particular true for the summer monsoon system on the Indian subcontinent. The Indian summer monsoon (ISM) is an integral part of the intertropical convergence zone (ITCZ). As this rainfall belt migrates northward during boreal summer, it brings monsoonal rainfall. ISM strength depends however on a variety of factors, including snow cover in Central Asia and oceanic conditions in the Indic and Pacific. Presently, many of the factors influencing the ISM are known, though their exact forcing mechanism and mutual relations remain ambiguous. Attempts to make an accurate prediction of rainfall intensity and frequency and drought recurrence, which is extremely important for South Asian countries, resemble a puzzle game; all interaction need to fall into the right place to obtain a complete picture. My thesis aims to create a faithful picture of climate change in India, covering the last 11,000 ka. NE India represents a key region for the Bay of Bengal (BoB) branch of the ISM, as it is here where the monsoon splits into a northwestward and a northeastward directed arm. The Meghalaya Plateau is the first barrier for northward moving air masses and receives excessive summer rainfall, while the winter season is very dry. The proximity of Meghalaya to the Tibetan Plateau on the one hand and the BoB on the other hand make the study area a key location for investigating the interaction between different forcings that governs the ISM. A basis for the interpretation of palaeoclimate records, and a first important outcome of my thesis is a conceptual model which explains the observed pattern of seasonal changes in stable isotopes (d18O and d2H) in rainfall. I show that although in tropical and subtropical regions the amount effect is commonly called to explain strongly depleted isotope values during enhanced rainfall, alone it cannot account for observed rainwater isotope variability in Meghalaya. Monitoring of rainwater isotopes shows no expected negative correlation between precipitation amount and d18O of rainfall. In turn I find evidence that the runoff from high elevations carries an inherited isotopic signature into the BoB, where during the ISM season the freshwater builds a strongly depleted plume on top of the marine water. The vapor originating from this plume is likely to memorize' and transmit further very negative d18O values. The lack of data does not allow for quantication of this plume effect' on isotopes in rainfall over Meghalaya but I suggest that it varies on seasonal to millennial timescales, depending on the runoff amount and source characteristics. The focal point of my thesis is the extraction of climatic signals archived in stalagmites from NE India. High uranium concentration in the stalagmites ensured excellent age control required for successful high-resolution climate reconstructions. Stable isotope (d18O and d13C) and grey-scale data allow unprecedented insights into millennial to seasonal dynamics of the summer and winter monsoon in NE India. ISM strength (i. e. rainfall amount) is recorded in changes in d18Ostalagmites. The d13C signal, reflecting drip rate changes, renders a powerful proxy for dry season conditions, and shows similarities to temperature-related changes on the Tibetan Plateau. A sub-annual grey-scale profile supports a concept of lower drip rate and slower stalagmite growth during dry conditions. During the Holocene, ISM followed a millennial-scale decrease of insolation, with decadal to centennial failures resulting from atmospheric changes. The period of maximum rainfall and enhanced seasonality corresponds to the Holocene Thermal Optimum observed in Europe. After a phase of rather stable conditions, 4.5 kyr ago, the strengthening ENSO system dominated the ISM. Strong El Nino events weakened the ISM, especially when in concert with positive Indian Ocean dipole events. The strongest droughts of the last 11 kyr are recorded during the past 2 kyr. Using the advantage of a well-dated stalagmite record at hand I tested the application of laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) to detect sub-annual to sub-decadal changes in element concentrations in stalagmites. The development of a large ablation cell allows for ablating sample slabs of up to 22 cm total length. Each analyzed element is a potential proxy for different climatic parameters. Combining my previous results with the LAICP- MS-generated data shows that element concentration depends not only on rainfall amount and associated leaching from the soil. Additional factors, like biological activity and hydrogeochemical conditions in the soil and vadose zone can eventually affect the element content in drip water and in stalagmites. I present a theoretical conceptual model for my study site to explain how climatic signals can be transmitted and archived in stalagmite carbonate. Further, I establish a first 1500 year long element record, reconstructing rainfall variability. Additionally, I hypothesize that volcanic eruptions, producing large amounts of sulfuric acid, can influence soil acidity and hence element mobilization. / Stalagmiten erfuhren in den letzten Jahren vermehrt Aufmerksamkeit als bedeutende Paläoklima- Archive. Paläoklimatologen sind beeindruckt von der grossen Zahl geochemischer und physikalischer Indikatoren (Proxies) und der Möglichkeit, präzise absolute Altersmodelle zu erstellen. Doch obwohl substantielle Fortschritte in der speleothem-basierten Klimaforschung gemacht wurden, und trotz hochaufgelöster Archive aus niederen Breiten, welche zeigen, das Umweltveränderungen auf Zeitskalen von Jahren bis Jahrtausenden archiviert und rekonstruiert werden können, bleibt unser Verständnis der Klimadynamik fragmentarisch. Ganz besonders gilt dies für den Indischen Sommermonsun (ISM) auf dem Indischen Subkontinent. Der ISM ist heute als ein integraler Bestandteil der intertropischen Konvergenzzone verstanden. Sobald dieser Regengürtel während des borealen Sommer nordwärts migriert kann der ISM seine feuchten Luftmassen auf dem Asiatischen Festland entladen. Dabei hängt die Stärke des ISM von einer Vielzahl von Faktoren ab. Zu diesen gehören die Schneedicke in Zentralasien im vorhergehenden Winter und ozeanische Bedingungen im Indischen und Pazifschen Ozean. Heute sind viele dieser Faktoren bekannt. Trotzdem bleiben deren Mechanismen und internen Verbindungen weiterhin mysteriös. Versuche, korrekte Vorhersagen zu Niederschlagsintensität und Häufigkeit oder zu Dürreereignissen zu erstellen ähneln einem Puzzle. All die verschiedenen Interaktionen müssen an die richtige Stelle gelegt werden, um ein sinnvolles Bild entstehen zu lassen. Meine Dissertation versucht, ein vertrauenswürdiges Bild des sich wandelnden Holozänen Klimas in Indien zu erstellen. NE Indien ist eine Schlüsselregion für den östlichen Arm des ISM, da sich hier der ISM in zwei Arme aufteilt, einen nordwestwärts und einen nordostwärts gerichteten. Das Meghalaya Plateau ist das erste Hindernis für die sich nordwärts bewegenden Luftmassen und erhält entsprechend exzessive Niederschläge während des Sommers. Die winterliche Jahreszeit dagegen ist sehr trocken. Die Nähe zum Tibetplateau einerseits und der Bucht von Bengalen andererseits determinieren die Schlüsselposition dieser Region für das Studium der Interaktionen der den ISM beeinflussenden Kräfte. Ein Fundament für die Interpretation der Paläoklimarecords und ein erstes wichtiges Ergebnis meiner Arbeit ist ein konzeptuelles Modell, welches die beobachteten saisonalen Veränderungen stabiler Isotope (d18O und d2H) im Niederschlag erklärt. Ich zeige, das obwohl in tropischen und subtropischen Regionen meist der amount effect zur Erklärung stark negativer Isotopenwerte während starker Niederschläge herangezogen wird, dieser allein nicht ausreicht, um die Isotopenvariabilität im Niederschlag Meghalaya's zu erklären. Die Langzeitbeobachtung der Regenwasserisotopie zeigt keine negative Korrelation zwischen Niederschlagsmenge und d18O. Es finden sich Hinweise, das der Abfluss aus den Hochgebirgsregionen Tibets und des Himalaya eine Isotopensignatur an das Oberflächenwasser der Bucht von Bengalen vererbt. Dort bildet sich aus isotopisch stark abgereicherten Wässern während des ISM eine Süsswasserlinse aus. Es ist wahrscheinlich, das Wasserdampf, der aus dieser Linse stammt, ein Isotopensignal aufgeprägt bekommt, welches abgereichertes d18O weitertransportiert. Der Mangel an Daten lässt es bisher leider nicht zu, quantitative Aussagen über den Einfluss dieses plume effect' auf Niederschläge in Meghalaya zu treffen. Es lässt sich allerdings vermuten, das dieser Einfluss auf saisonalen wie auch auf langen Zeitskalen variabel ist, abhängig vom Abfluss und der Quellencharacteristik. Der Fokus meiner Arbeit liegt in der Herauslösung klimatischer Signale aus nordostindischen Stalagmiten. Hohe Urankonzentrationen in diesen Stalagmiten erlaubt eine exzellente Alterskontrolle, die für hochauflösende Klimarekonstruktionen unerlässlich ist. Die stabilen Isotope (d18O und d13C), sowie Grauwertdaten, erlauben einmalige Einblicke in die Dynamik des Sommer und auch des Wintermonsun in NE Indien. Die ISM Stärke (d. h. Niederschlagsmenge) wird in Veränderungen in den d18Ostalagmites reflektiert. Das d13C Signal, welches Tropfratenänderungen speichert, dient als potenter Indikator für winterliche Trockenheitsbedingungen. Es zeigt Ähnlichkeit zu temperaturabhängigen Veränderungen auf dem Tibetplateau. Das sub-annuell aufgelöste Grauwertprofil stärkt das Konzept, das verminderte Tropfraten und langsameres Stalagmitenwachstum eine Folge von Trockenheit sind. Während des Holozäns folgte der ISM der jahrtausendelangen Verringerung der Insolation. Es finden sich aber ebenso rapide Anomalien, die aus atmosphärischen Veränderungen resultieren. Die Phase des höchsten Niederschlages und erhöhter Saisonalität korrespondiert mit dem Holozänen Thermalen Maximum. Nach einer Phase einigermassen stabilen Bedingungen begann vor ca. 4500 Jahren ENSO einen zunehmenden Einfluss auf den ISM auszuüben. Starke El Nino Ereignisse schwächen den ISM, besonders wenn diese zeitgleich mit positiven Indian Ocean Dipole Ereignissen auftreten. Die stärksten Dürren des gesamten Holozäns traten in den letzten 2000 Jahren auf. Um zusätzliche Informationen aus den hervorragenden Proben zu gewinnen nutzte ich die Vorteile der laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Diese erlaubt die Detektion sub-annueller bis sub-dekadischer Elementkonzentrationsveränderungen in Stalagmiten. Mittels einer neu entwickelten Ablationszelle konnten Proben von maximal 22 cm Länge untersucht werden. Jedes analysierte Element ist ein potentieller Träger einer Klimainformation. Die Kombination der früheren Ergebnisse mit denen der LA-IPC-MS zeigt, das die Elementkonzentrationen nicht nur von Niederschlagsveränderungen und assoziiertem Auswaschen aus dem Boden abhängen. Zusätzlich können auch die biologische Aktivität und hydrogeochemische Bedingungen in der vadosen Zone Einfluss auf die Elementzusammensetzung im Tropfwasser und in den Stalagmiten haben. Darum entwickelte ich ein theoretisches Modell für meinen Standort, um zu klären, wie Klimasignale von der Atmosphäre in die Höhle transportiert werden können. Ein anschliessend rekonstruierter 1500 Jahre langer Proxyrecord zeigt Niederschlagsvariabilität an. Zudem besteht die Möglichkeit, das Vulkaneruptionen, welche grosse Mengen an Schwefelsäure produzieren, eine Bodenversauerung verursachen und damit die Elementmobilisierung verstärken können.

<p>The spectroscopic, SEM and Raman measurements on carbon nanotubes under the exact conditions of which OES analysis were made showed that at<br /> a pressure of 400 Torr and a flow rate of 200 sccm, the quality and quantity of single-walled carbon nanotubes was the highest.</p>

Carbon nanotubes (CNTs), discovered by Ijima in 1991, are one of the allotropes of carbon, and can be described as cylinders of graphene sheet capped by hemifullerenes. CNTs have excellent electrical, mechanical, thermal and optical properties and very small size. Due to their unique properties and small size, CNTs have a great potential for use in electronics, medical applications, field emission devices (displays,scanning and electronprobes/microscopes) and reinforced composites. CNTs can be grown by different methods from a number of carbon sources such as graphite, CO,C2H4, CH4 and camphor. Under certain conditions, a metallic catalyst is used to initiate the growth. The three main methods used to grow CNTs are: Arc-discharge, laser ablation (LA) and chemical vapour deposition (CVD). In the present work CNTs were grown from a mixture of camphor (C10H16O) and ferrocene (C10H10Fe) using Chemical Vapour Deposition (CVD) and argon was used as a carrier gas. The iron particles from ferrocene acted as catalysts for growth. The substrates used for the growth of CNTs were crystalline Si and SiO2 (Quartz) placed in a quartz tube in a horizontal furnace. Several parameters have been found to affect the CNT growth process. The effects of three parameters: growth temperature, carrier gas (Ar) flow rate and catalyst concentration were investigated in the present work in order to optimize the growth conditions with a simple and economical CVD setup. The samples were characterized using electron microscopy (EM), thermogravimetirc analysis (TGA), Raman and FTIR spectroscopy techniques. It was found that the quality and yield of the CNTs were best at 800°C growth temperature, 80sccm flow rate and 4% catalyst concentration.