In der vorliegenden Arbeit wird die großflächige Abscheidung von organischen Leuchtdioden (OLED) für Beleuchtungsanwendungen in einer neuartigen Beschichtungsanlage vorgestellt. Ausgehend von den speziellen Anforderungen an gleichförmige Schichtdickenverteilung und hohe Abscheideraten für die organischen Schichten, sind die Verfahren der thermischen Vakuumverdampfung (VTE) und der organischen Dampfphasenabscheidung (OVPD) auf Substraten der Größe 370 x 470 mm² unter Fertigungsbedingungen kombiniert. Die Quellensysteme der Anlage wurden hinsichtlich der Verteilung des Materialauftrages und der Oberflächenrauigkeit qualifiziert. Die Kontrolle der Schichteigenschaften ist bei der organischen Dampfphasenabscheidung durch Variation der Parameter Substrattemperatur und Abscheiderate in einem weiten Bereich möglich. Die in situ Kontrolle der Schichtdicke mittels spektroskopischer Reflektometrie wird vorgestellt. Ein Messsystem ist in die Beschichtungsanlage integriert und abgeschiedene Schichten charakterisiert worden. Die Arbeit zeigt, dass die genaue Bestimmung der Dicke einzelner Schichten oder ganzer Schichtstapel mit diesem Verfahren möglich ist und zur ex situ Ellipsometrie vergleichbare Ergebnisse liefert. Um robuste OLED-Bauelemente herzustellen, wird eine organische Kurzschlussunterdrückungsschicht eingeführt, die konform mittels der OVPD-Technologie abgeschieden wird. Die strombegrenzenden Eigenschaften dieser Schicht wirken Defektströmen innerhalb der OLED entgegen. Die reproduzierbare Herstellung von 100 x 100 mm² großen, weißes Licht emittierenden OLED-Modulen mit mittleren Leistungseffizienzen von über 13 lm/W zeigt das Potential dieser Technologie. / The thesis deals with the large area deposition of organic light-emitting diodes (OLED) for lighting applications with a novel deposition tool. The special needs of film thicknesses homogeneity and high deposition rates for organic layers request the combination of thermal vacuum deposition (VTE) and organic vapour phase deposition (OVPD) processes to fabricate OLEDs on 370 x 470 mm² substrates. The deposition sources are qualified regarding layer homogeneity and morphology of the deposition processes. The layer properties are controlled in a wide range by the variation of the organic vapour phase deposition parameters: substrate temperature and deposition rate. The in situ determination of the substrate thickness is shown by the application of spectroscopic reflectometry. The thesis demonstrates the thickness analysis of single and multi-layer stacks by reflectometry. The data fit well to ex situ ellipsometry. Robust OLED devices with an additional short-circuit protection layer deposited by OVPD technology are introduced. The current limiting properties of this layer reduce the leakage currents in the OLED device. The fabrication of 100 x 100 mm² white emitting OLED modules with power efficiencies about 13 lm/W shows the great potential of the manufacturing technology.

The aim of this work is to explore the joining of inspiration, such as different garments and materials, in relation to commonly used methods in the fashion industry when it comes to joining of different trends and references such as clashing and collaging. The work proposes a new method and framework for join- ing inspiration which generates different results depending on what kind of inspiration that is put in to it. A garment can roughly be broken down to a silhouette and shape, materials and details. The material put in to the method and framework is based on information from trend seminars for SS16, because that is how many of today’s trend-oriented fashion brands get there inspiration. Trendy garment silhouettes are mixed through processes of computational morphing in Adobe Flash by a generation of spin in the mixing process were shape hints are used in a new manner. The new generated silhouettes are further developed and materialized through procedures of interpretation and figuration. Different trendy materials are melded in a direct and concrete way through mixed media techniques such as laminating, fusing and vacuum-techniques. The final steps of the method is a garment shape and material synthesis with starting point in the generated shape with the final material. The projects intention is to let the physical experimentation, interpretation and figuration play a central role in the research process for new types of methods, garments, materials and expressive pos- sibilities.

Gas-phase thermolysis is a long-known and well established method for the preparation of reactive species. It is, however, limited to relatively volatile substances, which are easily vaporised. In the present work, the solution-spray technique for preparative scale was developed. With this technique, it is possible to subject low-volatile substances, which hardly vaporise even under high-vacuum conditions, to gas-phase thermolysis. By utilising oil nozzles used in heating and burner systems, it was possible to integrate a stable solution-spray into the existing flash-vacuum-pyrolysis system. The influence of several variables, such as flow-rate, pressure, temperature and solvent was determined. The solution-spray technique was applied in [3,3]-sigmatropic rearrangements of certain propargyl thiocyanates to the corresponding allenyl isothiocyanates. Furthermore, the parent compound propa-1,2-dienyl isothiocyanate was reacted with various sterically demanding primary and secondary amines to form 2-amino-1,3-thiazoles in moderate to excellent yields. Based on this, a catalyst-free four-center three-component reaction was developed. 2-Amino-1,3-thiazoles with complex substituents in 5-position at the heterocyclic ring are formed. Reaction mechanisms are discussed to explain the occurance of a highly substituted 1,3-thiazine structure. The influence of reaction temperature, concentrations and solvent were determined and are also discussed. It was shown that 2-amino-5-methyl-1,3-thiazoles are the apparently first aromatic substance class, that readily undergoes Prins-type 1,3-dioxane ring-formation. / Die Gasphasenthermolyse ist eine lang bekannte und etablierte Methodik zur Synthese reaktiver Spezies. Sie ist allerdings auf flüchtige Substanzen mit einer guten Verdampfbarkeit beschränkt. Für schwerflüchtige Verbindungen, welche sich selbst im Hochvakuum nur mäßig oder gar nicht in die Gasphase bringen lassen, wurde in der vorliegenden Arbeit die Solution-Spray-Technik für die Anwendung im präparativen Maßstab entwickelt. Unter Verwendung von Ölzerstäuberdüsen, wie sie in der Heizungs- und Brennertechnik Anwendung finden, wurde die Erzeugung eines stabilen Lösungs-Sprays in die vorhandene Blitzvakuumpyrolyse-Technik integriert. Der Einfluss verschiedener Variablen, wie Flussrate, Druck, Temperatur und Lösungsmittel wurde untersucht. Die Solution-Spray-Technik wurde für die [3,3]-sigmatrope Umlagerung bestimmter Propargylthiocyanate zu Allenyl-isothiocyanaten angewendet. Des Weiteren wurde Propa-1,2-dienylisothiocyanat – das einfachste Allenylisothiocyanat – mit diversen sterisch anspruchsvollen primären und sekundären Aminen in mäßigen bis exzellenten Ausbeuten zu 2-Amino-1,3-thiazolen umgesetzt. Darauf aufbauend konnte eine Vier-Zentren-drei-Komponenten-Reaktion entwickelt werden. Es entstehen in hohen Ausbeuten 2-Amino-1,3-thiazole mit komplexen Substituenten an der 5-Position des Heterocyclus. Reaktionsmechanismen werden diskutiert um die alternative Bildung einer hochsubstituierten 1,3-Thiazinstruktur zu erklären. Der Einfluss von Reaktionstemperatur, Konzentration und Lösungsmittel auf das Produktverhältnis wurde ebenfalls untersucht und wird diskutiert. Es konnte gezeigt werden, dass 2-Amino-5-methyl-1,3-thiazole als offenbar erste aromatische Substanzklasse sehr gute Substrate für die Bildung von 1,3-Dioxanen nach Prins darstellen.

Today’s buildings are responsible for 40% of the world’s energy use and also a substantial share of the Global Warming Potential (GWP). In Sweden, about 21% of the energy use can be related to the heat losses through the climatic envelope. The “Million Program” (Swedish: Miljonprogrammet) is a common name for about one million housing units, erected between 1965 and 1974 and many of these buildings suffer from poor energy performance. An important aim of this study was to access the possibilities of using Vacuum Insulation Panels (VIPs) in buildings with emphasis on the use of VIPs for improving the thermal efficiency of the “Million Program” buildings. The VIPs have a thermal resistance of about 8-10 times better than conventional insulations and offer unique opportunities to reduce the thickness of the thermal insulation. This thesis is divided into three main subjects. The first subject aims to investigate new alternative VIP cores that may reduce the market price of VIPs. Three newly developed nanoporous silica were tested using different steady-state and transient methods. A new self-designed device, connected to a Transient Plane Source (TPS) instrument was used to determine the thermal conductivity of granular powders at different gaseous pressure combined with different mechanical loads. The conclusion was that the TPS technique is less suitable for conducting thermal conductivity measurements on low-density nanoporous silica powders. However, deviations in the results are minimal for densities above a limit at which the pure conduction becomes dominant compared to heat transfer by radiation. The second subject of this work was to propose a new and robust VIP mounting system, with minimized thermal bridges, for improving the thermal efficiency of the “Million Program” buildings. On the basis of the parametric analysis and dynamic simulations, a new VIP mounting system was proposed and evaluated through full scale measurements in a climatic chamber. The in situ measurements showed that the suggested new VIP technical solution, consisting of 20mm thick VIPs, can improve the thermal transmittance of the wall, up to a level of 56%. An improved thermal transmittance of the wall at centre-of-panel coordinate of 0.118 to 0.132 W m-2K-1 and a measured centre-of-panel thermal conductivity (λcentre-of-panel) of 7 mW m-1K-1 were reached. Furthermore, this thesis includes a new approach to measure the thermal bridge impacts due to the VIP joints and laminates, through conducting infrared thermography investigations. An effective thermal conductivity of 10.9 mW m-1K-1 was measured. The higher measured centre-of-panel and effective thermal conductivities than the published centre-of-panel thermal conductivity of 4.2 mW m-1K-1 from the VIP manufacturer, suggest that the real thermal performance of VIPs, when are mounted in construction, is comparatively worse than of the measured performance in the laboratory. An effective thermal conductivity of 10.9 mW m-1K-1 will, however, provide an excellent thermal performance to the construction. The third subject of this thesis aims to assess the environmental impacts of production and operation of VIP-insulated buildings, since there is a lack of life cycle analysis of whole buildings with vacuum panels. It was concluded that VIPs have a greater environmental impact than conventional insulation, in all categories except Ozone Depilation Potential. The VIPs have a measurable influence on the total Global Warming Potential and Primary Energy use of the buildings when both production and operation are taken into account. However, the environmental effect of using VIPs is positive when compared to the GWP of a standard building (a reduction of 6%) while the PE is increased by 20%. It was concluded that further promotion of VIPs will benefit from reduced energy use or alternative energy sources in the production of VIP cores while the use of alternative cores and recycling of VIP cores may also help reduce the environmental impact. Also, a sensitivity analysis of this study showed that the choice of VIPs has a significant effect on the environmental impacts, allowing for a reduction of the total PE of a building by 12% and the GWP can be reduced as much as 11% when considering both production and operation of 50 yes. Finally, it’s possible to conclude that the VIPs are very competitive alternative for insulating buildings from the Swedish “Million Program”. Nevertheless, further investigations require for minimizing the measurable environmental impacts that acquired in this LCA study for the VIP-insulated buildings. / Dagens byggnader ansvarar för omkring 40% av världens energianvändning och  står också för en väsentlig del av utsläppen av växthusgaser. I Sverige kan ca 21 % av energianvändningen relateras till förluster genom klimatskalet. Miljonprogrammet är ett namn för omkring en miljon bostäder som byggdes mellan 1965 och 1974, och många av dessa byggnader har en dålig energiprestanda efter dagens mått. Huvudsyftet med denna studie har varit att utforska möjligheterna att använda vakuumisoleringspaneler (VIP:ar) i byggnader med viss fokus på tillämpning i Miljonprogrammets byggnader. Med en värmeledningsförmåga som är ca 8 - 10 gånger bättre än för traditionell isolering erbjuder VIP:arna unika möjligheter till förbättrad termisk prestanda med minimal isolerings tjocklek. Denna avhandling hade tre huvudsyften. Det första var att undersöka nya alternativ för kärnmaterial som bland annat kan reducera kostnaden vid produktion av VIP:ar. Tre nyutvecklade nanoporösa kiselpulver har testats med olika stationära och transienta metoder. En inom projektet utvecklad testbädd som kan anslutas till TPS instrument (Transient Plane Source sensor), har använts för att mäta värmeledningsförmågan hos kärnmaterial för VIP:ar, vid varierande gastryck och olika mekaniska laster. Slutsatsen blev att transienta metoder är mindre lämpliga för utföra mätningar av värmeledningsförmåga för nanoporösa kiselpulver låg densitet. Avvikelsen i resultaten är dock minimal för densiteter ovan en gräns då värmeledningen genom fasta material blir dominerande jämfört med värmeöverföring genom strålning. Det andra syftet har varit att föreslå ett nytt monteringssystem för VIP:ar som kan användas för att förbättra energieffektiviteten i byggnader som är typiska för Miljonprogrammet. Genom parametrisk analys och dynamiska simuleringar har vi kommit fram till ett förslag på ett nytt monteringssystem för VIP:ar som har utvärderats genom fullskaleförsök i klimatkammare. Resultaten från fullskaleförsöken visar att den nya tekniska lösningen förbättrar väggens U-värde med upp till 56 %. En förbättrad värmegenomgångskoefficienten för väggen i mitten av en VIP blev mellan 0.118 till 0,132 W m-2K-1 och värmeledningstalet centre-av-panel 7 mW m-1K-1 uppnåddes. Detta arbete innehåller dessutom en ny metod för att mäta köldbryggor i anslutningar med hjälp av infraröd termografi. En effektiv värmeledningsförmåga för 10.9 mW m-1K-1 uppnåddes. Resultaten tyder även på att den verkliga termiska prestandan av VIP:ar i konstruktioner är något sämre än mätvärden för paneler i laboratorium. En effektiv värmeledningsförmåga av 10.9 mW m-1K-1 ger dock väggkonstruktionen en utmärkt termisk prestanda. Det tredje syftet har varit att bedöma miljöpåverkan av en VIP-isolerad byggnad, från produktion till drift, eftersom en livscykelanalys av hela byggnader som är isolerade med vakuumisoleringspaneler inte har gjorts tidigare. Slutsatsen var att VIP:ar har en större miljöpåverkan än traditionell isolering, i alla kategorier förutom ozonnedbrytande potential. VIP:ar har en mätbar påverkan på de totala utsläppen av växthusgaser och primärenergianvändningen i byggnader när både produktion och drift beaktas. Miljöpåverkan av de använda VIP:arna är dock positiv jämfört med GWP av en standardbyggnad (en minskning med 6 %) medan primärenergianvändningen ökade med 20 %. Slutsatsen var att ytterligare användning av VIP:ar gynnas av reducerad energiförbrukning och alternativa energikällor i produktionen av nanoporösa kiselpulver medan användningen av alternativa kärnmaterial och återvinning av VIP kärnor kan hjälpa till att minska miljöpåverkan. En känslighetsanalys visade att valet av VIP:ar har en betydande inverkan på miljöpåverkan, vilket ger möjlighet att reducera den totala användningen av primärenergi i en byggnad med 12 % och utsläppen av växthusgaser kan vara minska, så mycket som 11 % när det gäller både produktion och drift under 50 år. Avslutningsvis är det möjligt att dra slutsatsen att VIP:ar är ett mycket konkurrenskraftigt alternativ för att isolera byggnader som är typiska för Miljonprogrammet. Dock krävs ytterligare undersökningar för att minimera de mätbara miljöeffekter som förvärvats i denna LCA-studie för VIP-isolerade byggnader. / <p>QC 20151109</p> / Simulations of heat and moisture conditions in a retrofit wall construction with Vacuum Insulation Panels / Textural and thermal conductivity properties of a low density mesoporous silica material / A study of the thermal conductivity of granular silica materials for VIPs at different levels of gaseous pressure and external loads / Evaluation of the thermal conductivity of a new nanoporous silica material for VIPs – trends of thermal conductivity versus density / A comparative study of the environmental impact of Swedish residential buildings with vacuum insulation panels / ETICS with VIPs for improving buildings from the Swedish million unit program “Miljonprogrammet”

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No description available.

Organic semiconductors show promise to yield a novel class of bendable electronic devices, and much research efforts have focused on the optimization of these films for device performance. It is well known that the structure of organic films has a large influence over the electronic properties. In particular, the carrier mobility is often highly anisotropic, and domain boundaries have a detrimental effect on charge transport. Therefore the domain structure and lattice orientation are of particular interest. However, little is known about the domain structure of organic films, and techniques to study these properties have only begun to emerge in recent years. In this thesis, we apply two experimental techniques, Grazing-Incidence X-ray Diffraction (GIXD) and Lateral Force Microscopy (LFM), toward studying the lattice and domain structure of tetracene films grown on the silicon(001)-monohydride surface. We describe the necessary steps toward optimizing the sensitivity of these techniques to the domain structure. Results show that the crystalline tetracene films form a layered morphology in which the a-b plane lies parallel to the substrate surface. The film lattice structure is similar to bulk tetracene, and the lattice is confined to two orthogonal orientations, forming a partially-commensurate relationship with the substrate surface lattice along the film 'a' axis. LFM images reveal two types of polycrystalline domains. The first type ("major domains") are tens of microns in size, and are classified by their lattice orientation. They are subdivided into the second type ("sub-domains"), which range from 0.1 to 5um in size, and are argued to represent regions of uniform molecular tilt direction. The GIXD data show that the single-crystal domains which comprise these two larger domain types are anisotropic in size, being up to two times longer along the film 'b' axis than along 'a'. The single-crystal domains range from 0.05 to 0.2um in size, depending on lattice orientation and film thickness. The mathematical basis for these single-crystal domain size calculations is presented. The single-crystal domain sizes are thickness-dependent, and are two orders of magnitude smaller than a typical surface island observed in atomic-force microscopy (AFM) topographs. Substrate steps can also significantly influence the film structure by inducing boundaries in the single-crystal domains and sub-domains, but not in the major domains. This detailed knowledge of the domain structure of organic thin-films may assist in our understanding of the factors which affect charge transport in thin films, and may help to direct research efforts in optimizing the film structure for device performance. / Natural Sciences and Engineering Research Council (NSERC), Canadian Foundation for Innovation (CFI), Ontario Innovation Trust (OIT).

El propósito de este estudio es abordar el concepto de espacio y, en particular, su desocupación, a través de tres obras: Caja Vacía/Metafísica de Jorge Oteiza, Who´s afraid of red, yellow and blue de Barnett Newman y el Pabellón de Alemania de Ludwig Mies van der Rohe. El discurso se construye a través de un transitar sobre la banda de Moebius y en su vaivén y en su doblez aparecen y desparecen imágenes, ideas y textos sobre los que fluye la voluntad de construir una interpretación nueva sobre el objeto descrito. Martin Heidegger, Gilles Deleuze y Gaston Bachelard son los tres sostenes teóricos de esta estructura. Y más cerca y más lejos de este texto siempre se mantiene la difícil tarea de entender cuál es la forma de habitar y de ser (Ich bin) del hombre en la tierra. / The purpose of this study is to address the concept of space and, in particular, its disoccupation through three different pieces of work: Empty/Metaphysical Box by Jorge Oteiza, Who´s afraid of red, yellow and blue by Barnett Newman and German Pavilion by Ludwig Mies van der Rohe. The discourse is constructed through a move on the Moebius band, its swing and double apparition and disappearance of images, ideas and texts which build a new interpretation of the subject matter. Martin Heidegger, Gilles Deleuze and Gaston Bachelard are the three theorists of this structure. The difficult task of understanding what is the way of living and being of man (Ich bin) on earth always remains what is closer and further away from this text.

L'intégration de diélectriques High-k dans les empilements de grille des dispositifs MOS a fait naître de nouvelles interrogations concernant la fiabilité des futurs nœuds technologiques. La miniaturisation constante des dispositifs conduisant à l'amincissement des épaisseurs d'oxyde de grille, leur caractérisation électrique est rendue de plus en plus complexe à l'échelle du dispositif. Pour palier à ce problème, l'utilisation d'un microscope à force atomique en mode conducteur sous ultravide permet grâce à la faible surface de contact entre la pointe et l'échantillon de réduire suffisamment le courant tunnel pour pouvoir étudier la dégradation et le claquage diélectrique d'oxyde ultra fin. La comparaison systématique des résultats de fiabilité de l'empilement High-k du nœud 28nm et de la couche interfaciale seule ayant subi les mêmes étapes de développement que celles présentes dans l'empilement, obtenus par C-AFM sous ultra vide, ont permis de montrer expérimentalement que la probabilité de claquage des oxydes de grille High-k est gouvernée par la fiabilité propre des couches qui la composent, et de déduire une loi d'extrapolation de la durée de vie en tension et en surface ce qui permet de prédire la statistique de défaillance du dispositif. Les impacts d'un pré-stress en tension de l'ordre de la milliseconde sur les distributions de claquage des oxydes de grille simples et bicouches ont été rapportés. Ces résultats sont expliqués dans ce manuscrit par le déclenchement lors de l'application du stress, d'une dégradation au sein de l'oxyde, prenant naissance dans la couche interfaciale des oxydes High-k et conduisant à une réduction locale de l'épaisseur de diélectrique. Des phénomènes de résistance différentielle négative au moment de la rupture diélectrique ont été étudiés et modélisés pour différentes épaisseurs d'oxyde, par une croissance filamentaire de la dégradation. Il a été possible de donner une expression analytique reliant le temps caractéristique de croissance filamentaire et le temps moyen de claquage observé sur les distributions statistiques. Enfin, les mesures C-AFM de ce travail ont été étendues au cas des structures MIM utilisées pour le développement des futurs mémoires résistives OxRAM. Dans ce cas un effet d'auto-guérison à l'échelle nanométrique a été mis en évidence. / Integration of High-k dielectrics in gate oxides of MOS raised new issues concerning the reliability of futur technology nodes. The constant miniaturisation of devices leads to thinner gate oxides, making their electrical caracterisation more complex at the device scale. To solve this problem, an atomic force microscope in conductive mode under ultra high vacuum can be used thanks to the readuce contact area between the tip and the sample which allow a drastic decrease of the tunneling current and thus the study of the degradation and the dielectric breakdown of ultra-thin oxides. The systematic comparaison of the TDDB distributions obtained on the High-k gate oxide of the 28nm technology node on one side and obtained on the Interfacial layer alone revealed that the failure probability of High-k oxides is governed by the failure probability of each layer present in the stack. This allow to give an extrapolation law of the High-k gate oxide lifetime as a function of the applied voltage and the electrode area and to predict the failure statistic of the 28nm tehcnology node. The impact of voltage pre-stress with a microseconde range of duration on the TDDB and VBD distributions of both single layer and High-k gate oxides is given is the manuscript. The results are then interpreted by an invasive degradation nucleating from an interface during a stress and leading to a local thinned oxide. Pre-breakdown negative differential resistance have been studied and modeled for several oxide thickness, using a growing mecanism of the elctrical degradation. An analytic expression linking the growth caracteristic time of the filament and the mean time to breakdown observed on the statistical distributions has then been given. Finally, C-AFM measurements developped in this work has been extended to MIM structures used for oxide resistive random access memories (OxRAM). A self healing has been observed at the nanometric scale for these samples.

Nous avons développé un système de transfert des surfaces monocristallines préparées sous ultra-haut vide (UHV) vers un milieu électrolytique pour effectuer des mesures voltampérométriques. Ce système original très compact comprend une valise sous vide et une cellule électrochimique dédiée. Le système a été testé avec succès sur des surfaces monocristallines de platine, en particulier la surface Pt(111) très sensible à la qualité de la préparation sous UHV. Puis nous avons utilisé ce système pour caractériser les propriétés électrochimiques du système Pt/W(111) avec d'une part l'effet des contraintes élastiques pour les couches ultra-minces planaires de Pt épitaxié ainsi que la stabilité en milieu électrolytique de nano-pyramides obtenues par déstabilisation en température des surfaces Pt/W(111). Ce travail ouvre des perspectives intéressantes pour l'étude électrochimiques des surfaces modèles préparées sous UHV. / In this work, we developed a system for transferring single crystal surfaces prepared in ultra-high vacuum (UHV) to an electrolytic medium where voltammetric measurements are carried out. This unique system includes a compact vacuum chamber and its dedicated electrochemical cell. The system was successfully tested on platinum single-crystal surfaces; in particular the Pt (111) surface which is well known for it's sensitive to the quality of the preparation under UHV. Then we used this system for characterizing the electrochemical properties of the Pt / W (111) system, both the effect of elastic strain of ultrathin epitaxial planar Pt films and the stability of nano-pyramids obtained after a temperature annealing of the planar Pt / W (111) system. This work opens up interesting perspectives for the study of electrochemical model surfaces prepared in UHV.