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.

In this study nano-patterning was carried out using two different nano-optic devices namely- the NSOM and Fresnel zone plate. In the first study, NSOM was used to generate nano-patterns on selected semiconducting (Si and Ge) and metallic (Cr, Cu and Ag) targets under different laser pulse durations, laser energies and number of laser pulses. Based on the experimental results, femtosecond laser pulses, provided lower pattern generation thresholds on targets but higher damage thresholds to the NSOM probes at the wavelength (~400-410 nm) studied, compared with nanosecond laser pulses. Three different mechanisms were identified as the dominant processes for pattern generation under different conditions, namely nano-scale laser ablation, nano-scale thermal oxidation and nano-scale melting/recrystallization of the targets. Furthermore, the resulting nano-patterns also showed a significant dependence on the optical properties (i.e., absorption coefficient and surface reflectivity) of the target material. By comparing the obtained experimental results, it was concluded that the optical energy transport from the NSOM probe to the target dominates the pattern generation when femtosecond laser is applied to the NSOM system. When nanosecond laser is applied, both the thermal and optical energy transported from the NSOM probe to the targets attribute to the obtained morphology of nano-patterns on different targets under the experimental conditions studied. In the second study, a traditional Fresnel zone plate with a focus length of 3 micrometres was fabricated with a novel lift-off process in e-beam lithography. The fabrication process involved, using a HSQ/PMMA bi-layer in a negative tone lift-off process with a layer of conducting polyaniline for charge dissipation. HSQ was used as the high resolution negative resist for e-beam patterning and the PMMA under-layer was used to enable a HSQ lift-off process. The fabricated Fresnel zone plate was used to generate nano-patterns on a UV sensitive photoresist using nanosecond laser light with lamda~409nm. The smallest pattern sizes generated was close to the diffraction limit. Nano-pattern sizes generated on the photoresist were comparable with a numerically calculated intensity distribution at the focus spot of the designed Fresnel zone plate obtained from Scalar Diffraction Theory.

The present study describes the growth and characterization of pulsed laser ablated Bao.sSro.sTiOs (BST) thin films. Emphasis has been laid on the study of a plausible correlation between structure and property in order to optimize the processing parameters suitably for required application. An attempt has been made to understand the basic properties such as, origin of dielectric response, charge transfer under low and high-applied electric fields across the BST capacitor and finally the dielectric breakdown process. Chapter 1 gives a brief introduction on the application of ferroelectric thin films in microelectronic industry and its growth techniques. It also addresses the present issues involved in the introduction of BST as a capacitor material for high-density dynamic random access memories. Chapter 2 outlines the motivation for the present study and briefly outlines the research work involved. Chapter 3 describes the experimental procedure involved in the growth and characterization of BST thin films using pulsed laser ablation technique. Details include the setup design for PLD growth, material synthesis for the ceramic targets, deposition conditions used for thin film growth and basic characterizations methods used for study of the grown films. Chapter 4 describes the effect of systematic variation of deposition parameters on the physical and electrical properties of the grown BST films. The variation in processing conditions has been found to directly affect the film crystallinity, structure and morphology. The change observed in these physical properties may also be correlated to the observed electrical properties. This chapter summarizes the optimal deposition conditions required for growing BST thin films using a pulsed laser ablation technique. Microstructure of BST films has been categorized into two types: (a) Type I structure, with multi-grains through the film thickness, for amorphous as-grown films after high temperature annealing (exsitu crystallized), and (b) columnar structure (Type II) films, which were as-grown well-crystallized films, deposited at high temperatures. The ac electrical properties have been reviewed in detail in Chapter 5. Type I films showed a relatively lower value of dielectric constant (e ~ 426) than Type II films with dielectric constant around 567. The dissipation factors were around 0.02 and 0.01 for Type I and Type II films respectively. The dispersion in the frequency domain characteristics has been quantitatively explained using Jonscher's theory. Complex impedance spectroscopy employed showed significant grain boundary response in the case of multi-grained Type I films while negligible contribution from grain boundaries has been obtained in the case of columnar grained Type II BST films. The average relaxation time r obtained from the complex impedance plane plots show almost three orders higher values for Type I films. The obtained results suggest that in multi-grained samples, grain boundary play a major role in electrical properties. This has been explained in accordance to a model proposed on the basis of depleted grains in the case of Type I films where the grain sizes are smaller than the grain boundary depletion width. Chapter 6 describes the dc leakage properties of the grown BST thin films and the influence of microstructure on the leakage properties. It was evident from the analysis of the graph of leakage current against measurement temperature, that, the observed leakage behavior in BST films, can not be attributed to a single charge transport mechanism. For Type I films, the Arrhenius plot of the leakage current density with 1000/T exhibits different regions with activation energy values in the range of 0.5 and 2.73 for low fields (2.5kV/cm). The activation energy changes over to 1.28 eV at high fields (170 kV/cm). The obtained values agree well with that obtained from the ac measurements, thus implying a similarity in the origin of the transport process. The activation energy value in the range of 0.5 eV is attributed to the electrode/film Schottky barrier, while the value in the range of 2.73 eV is due to deep trap levels originating from Ti+3 centers. The value in the range of 1.28 eV has been attributed to oxygen vacancy motion. Similar results have been obtained from the Arrhenius plot of the leakage current for Type II films. In this case, only two different activation energy values can be identified in the measured temperature and applied electric field range. At low fields the activation energy value was around 0.38 eV while at high fields the value was around 1.06 eV. These values have been identified to be originating from the electrode/film Schottky barrier and oxygen vacancy motion respectively. Thus a complete picture of the charge transport process in the case of BST thin film may be summarized as comprising of both electronic motion as well as contribution from oxygen vacancy motion. The effect of electrical stress on the capacitance-voltage (C-V) and the leakage current has been analyzed in Chapter 7. From the change in the zero bias capacitance after repeated electron injection through the films the values of the electronic capture cross-section and the total trap density for Type I and II films have been estimated. The results showed higher values for Type I film in comparison to Type II films. The difference has been attributed to the presence of grain boundaries and a different interface in the case of Type I films when compared to Type II films where the absence of grain boundaries is reflected in the columnar microstructure. A study of the time-dependent-dielectric-breakdown (TDDB) characteristics under high fields for Type I and Type II films showed higher endurance for Type I film. On the other hand space-charge-transient characteristics have been observed in the case of Type II films at elevated temperature of measurement. Mobility and activation energy values extracted from the transient characteristics are found to be in the range of 1 x 10~12 cm2 /V-sec and 0.73 eV respectively, suggesting a very slow charge transport process, which has been attributed to the motion of oxygen vacancies. An overall effect of electrical stress suggested that oxygen vacancy motion can be related to the observed resistance degradation and TDDB, which has been further enhanced by the combination of high temperature and high electric fields. Chapter 8 deals with the effect of intentional doping in the BST films. The doping includes Al at the Ti-site, Nb in the Ti-site and La at the Ba/Sr-site. The effect of doping was observed both on the structure and electrical properties of the BST films. Acceptor doping of 0.1 atomic 7c Al was found to decrease the dielectric constant as well as the leakage current. For higher concentration of acceptor-dopant, the leakage current was found to increase while showing space-charge-transient in the TDDB characteristics, again suggesting the effect of increased concentration of oxygen vacancies. Donor doping using 2 atomic % La and Xb significantly improved the leakage as well as the TDDB characteristics by reducing the concentration of oxygen vacancies. A further procedure using graded donor doping in the BST films exhibits even better leakage and TDDB properties. An unconventional, graded doping of donor cations has been carried out to observe the impact on leakage behavior, in particular. The leakage current measured for a graded La-doped BST film show almost six orders of lower leakage current in comparison to undoped BST films, while endurance towards breakdown has been observed to increase many-fold. Chapter 9 highlights the main findings of the work reported in this thesis and lists suggestions for future work, to explore new vistas ahead.

Die Strukturen der Erdalkalimetall-Subnitride (EA2N) von Calcium, Strontium und Barium ermöglichen mit ihrem schichtartigen Aufbau aus EA6N-Oktaedern Intercalationsreaktionen. Die Redox-Intercalation von Stickstoff in Sr2N wurde an Einkristallen untersucht. Nur durch eine drastische Erhöhung des Reaktionsgasdruckes im Vergleich zu den Reaktionen an mikrokristallinen Proben wurde die Intercalation der Diazenidionen in die Kristalle zu Sr4N3 und SrN möglich. Für eine analoge Intercalation von Wasserstoff in Sr2N konnten die Reaktionsbedingungen dahingehend optimiert werden, dass erstmals phasenreines Strontiumnitridhydrid (Sr2N)H bzw. deuterid (Sr2N)D erhalten wurde. Anhand von Intercalationsreaktionen mit Sr2N Kristallen konnte gezeigt werden, dass der Intercalationsprozess, erkennbar an der deutlichen Farbänderung von schwarz nach bersteinfarben, von außen nach innen fortschreitet. Als Methode zur räumlich aufgelösten Analyse wurde die Laserablation, in Kombination mit einem ICP - Massenspektrometer (LA-ICP-MS) verwendet. In der Literatur beschriebene Quantifizierungsstrategien wurden auf die Anwendbarkeit für die gegebene Fragestellung untersucht. Mit der ortsaufgelösten Analyse von Einkristallen konnte gezeigt werden, dass die Intercalation von Stickstoff in die Kristalle kontinuierlich von den Kanten zur Kristallmitte fortschreitet.

Τα τελευταία έτη η σύνθεση και ο χαρακτηρισμός μονοδιάστατων νανοδομών αποκτά αυξανόμενο ερευνητικό ενδιαφέρον καθώς συνδυάζουν φαινόμενα από την νάνο κλίμακα με την δυνατότητα χειρισμού τους λόγω του μεγάλου μήκους τους. Εκτός από τα καθιερωμένα υλικά με αυτήν την μορφολογία όπως είναι οι νανοσωλήνες άνθρακα, οι νανοράβδοι οξειδίου του ψευδαργύρου και τα νανοκαλώδια πυριτίου μία κατηγορία υλικών που αναπτύσσει τέτοιες νανοδομές είναι τα χαλκογενή Σελήνιο και Τελλούριο γεγονός που εξηγείται από την υψηλής ανισοτροπίας κρυσταλλική τους δομή. Στόχος αυτής της εργασίας είναι η παραγωγή, μέσω φωτοαποδόμησης, νανοσωλήνων Τελλουρίου οι οποίοι μέσω φωτοοξείδωσης μετατρέπονται σε νανοκαλώδια Οξειδίου του Τελλουρίου. Η διερεύνηση της κινητικής του φαινομένου ανάλογα με το χρησιμοποιούμενο μήκος κύματος και την ένταση της ακτινοβολίας καθώς και ο χαρακτηρισμός των παραγόμενων νανοδομών γίνεται με φασματοσκοπία Raman. Τα συμπεράσματα στα οποία καταλήγουμε ενισχύονται από μία σειρά άλλων πειραματικών μεθόδων όπως περίθλαση ακτίνων Χ (XRD) και ηλεκτρονική μικροσκοπία σάρωσης και διέλευσης (SEM, TEM). / One dimensional (1D) nanostructures of semiconducting oxides and elemental chalcogens culminate over the last decade in nanotechnology owing to their unique properties exploitable in several applications sectors. Whereas several synthetic strategies have been established for rational design of 1D materials using solution chemistry and high temperature evaporation methods, much less attention has been given to the laser-assisted growth of hybrid nanostructures. Here, we present a laser-assisted method for the controlled fabrication of Te nanotubes. A series of light-driven phase transition is employed to controllably transform Te nanotubes to core-Te/sheath-TeO2 and/or even neat TeO2 nanowires. This solid-state laser-processing of semiconducting materials apart from offering new opportunities for the fast and spatially controlled fabrication of anisotropic nanostructures, provides a means of simultaneous growing and integrating these nanostructures into an optoelectronic or photonic device.

Solar irradiation is a vast and plentiful source of energy. The use of photovoltaic (PV) devices to convert solar energy directly to electrical energy is an elegant way of sustainable power generation which can be distributed or in large PV plants based on the need. Solar cells are the small building blocks of photovoltaics and when connected together they form PV modules. Thin film solar cells require significantly less energy and raw materials to be produced, as compared to the dominant Si wafer technologies. CIGS thin film solar cells are considered to be the most promising thin film alternative due to its proven high efficiency. Most thin film PV modules utilise monolithic integration, whereby thin film patterning steps are included between film deposition steps, to create interconnection of individual cells within the layered structure. The state of the art is that CIGS thin film modules are made using one laser patterning step (P1) and two mechanical patterning steps (P2 and P3). Here we present work which successfully demonstrates the replacement of mechanical patterning by laser patterning methods. The use of laser ablation promises such advantages as increased active cell area and reduced maintenance and downtime required for regular replacement of mechanical tools. The laser tool can also be used to transform CIGS into a conducting compound along a patterned line. We have shown that this process can be performed after all semiconductor layers are deposited using a technique we call laser micro-welding. By performing patterning at the end of the process flow P2 and P3 patterning could be performed simultaneously. Such solutions will further reduce manufacturing times and may offer increased control of semiconductor interfaces. While showing promising performance on par with reference processes there are still open questions of importance for these novel techniques, particularly that of long term stability. Thin film modules are inherently sensitive to moisture and require reliable encapsulation. Before the techniques introduced here can be seen industrially they must have achieved proven stability. In this work we present a proof of existence of stable micro-welded interconnections. / Felaktigt tryckt som Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology 731