Alloys of titanium are highly preferred materials for their excellent strength to weight ratio but the tribological issues while using them has been posing challenging issues for the tribological analyst, which are still areas of active research. Ti-6Al-4V (Ti64) is the most popular alloy of titanium and our understanding of the fundamental mechanisms of wear and friction of this alloy is still not complete. Previous investigations related to the tribology of these alloys have suggested a synergistic effect of plastic deformation and tribo-oxidation. The present investigation described in this thesis explores the existence of one more mode, namely the formation of a Mechanically Mixed Layer (MML). The thesis examines the effect of these modes one by one and analyses the synergistic effect of these mechanisms, and also the effect of heat generation during sliding. The tribological condition existing have been varied by doing wear experiments using Ti64 pins sliding against alumina and SS316L (controls MML), diameter of pin (expected to control debris entrapment and thus MML formation), tribo-system (horizontal disc Vs vertical disc, which is also expected to control debris entrapment and thus MML formation), environment (ambient and vacuum, expected to control tribo-oxidation) and sliding speed (expected to control interface temperature and thus plastic deformation mechanism and tribo-oxidations). The division of the main chapters has been so made to present the findings spread over Chapters 5-8, with each chapter dealing with specific tribological test conditions. In each chapter, results from the tribological experimentations in the form of wear and friction are presented, together with the characterization methods which throw light into the tribological mechanisms. These characterization methods include Scanning Electron Microscopy (SEM), Energy Dispersive X-ray Spectroscopy (EDAX), X-Ray Diffraction (XRD) and Electron probe micro-analyzer (EPMA). Wherever possible, the debris collected from the experiments have been subjected to morphological and detailed chemical analysis, and a feature which has not been explored much in detail by tribological investigators, but having a promising potential. Experimental results from tribological testing when Ti64 pins slides against two different materials (Alumina and SS316L) in pin-on-disc tribometers under two different environmental conditions (ambient /vacuum) are analyzed. Each set of experiments looks at two different effects - (1) the effect of sliding speed on the tribological behavior while using a pin of a fixed diameter (all other parameters remaining the same) and (2) the effect of using pins of different diameters for a given set of parameters. Three different pin-sizes were employed (2.1 mm. 4.6 mm and 6.6 mm), the normal loads on these pins were changed according to the pin-size used so that all experiments were done at the same contact pressure (2.8 MPa). By performing the experiments against the ceramic disc (alumina) under vacuum conditions, the effect of this plastic deformation is studied in isolation because the possibility of the Tribo Chemical Reaction (TCR) due to oxidation is inhibited and no MML was found to be formed due to poor compatibility of mixing between the metallic pin and the ceramic disc. For the low speeds/strain rates experiments, the effect of plastic deformation as influenced by the adiabatic shear banding is seen to influence wear which progressively changes to temperature induced plastic deformation and wear. The situation is found to be different when we change the environmental conditions from vacuum to ambient for the same tribo-combination. The tests shows a reduction in wear rate with speed, and this is due to the oxide formations due to TCR as confirmed from the SEM/EDAX characterization. In contrast to previous experiments under vacuum, these permit the effect of TCR also to influence the tribological behavior. The scenario changes when the alumina disc is replaced by a metallic one (SS316L) and tests carried out in vacuum, as the MML was found to be formed with this tribo-pair. Because of the mutual affinity of the materials in the tribo-pair, the wear damage is severe in this case and the flash temperatures crossing the phase transition temperature (~880oC) for Ti64 at high speeds. The growth of the β phase with increase in the sliding (temperature) conditions is captured from the XRD spectra of the wear debris. Synergistic effect of all these mechanisms (plastic deformation, MML, and TCR) is permitted by conducting experiments with Ti64 pin against stainless steel and in ambient conditions. A comparison of the tribological response by presenting results when experiments are run over a range of speeds while using different sized pins under ambient conditions (and compared with similar results in vacuum) while using SS316L disc serve to demarcate the differences in the wear modes which are active/inactive depending on the tribological conditions. In addition a study incorporating the effect of frictional heating and its influence on the tribological phenomena is analyzed. Main conclusions from the thesis are: The wear resistance of Ti64 alloy when sliding against SS316L is found to be influenced by Strain Rate Response (SRR), Tribo Oxidation (TO), Mechanically Mixed Layer (MML) and the prevailing heat flux conditions at the contact. The wear rates were found to decrease marginally with sliding speeds (strain rates) up to a certain speed, which is ascribed to reduction in adiabatic shear band intensity with increase in strain rate. Adiabatic Shear Band (ASB), which allows easy crack propagation, intensity reduces as temperature of deformation of Ti64 is increased. From the results it can be confirmed that the propensity for formation of MML depends on compatibility of the disc and the pin material. The contribution due to of entrapment and retention of debris in the contact zone also would influence formation of the MML. The effect of frictional heating plays an influential role as it can affect the factors (TO, ASB, MML) governing the tribological response. The sensitivity to temperature, which is a marked feature of this alloy in undergoing softening, as confirmed by previous researchers, is reflected in the experimental results. Since the main factor that triggers the micro-structural instability is the energy dissipation that accompanies deformation more fundamental research which can improve the thermal transport properties of this alloy, would be the future scope of work of this thesis. Also, the unique composition of the MML which offers high wear resistance under specific operating conditions opens up the possibility of new such alloy formulations, production routes and techniques which should improve the tribological response of this alloy.

No description available.

Dans cette thèse, nous avons abordé plusieurs thématiques liées aux modes de variabilité climatique dans l'Atlantique tropical à l'échelle interannuelle. Les analyses statistiques nous ont permis dans un premier temps de mettre en évidence les deux principaux modes dominants de cette variabilité interannuelle: un mode équatorial et un mode méridien. Le mode équatorial est responsable d'anomalies de température de surface de la mer (SST) principalement dans le Golfe de Guinée et est identifié par des variations de la pente du niveau de la mer dans la bande équatoriale. Il est dû à des rétroactions dynamiques entre le vent, le niveau de la mer et la SST. Quant au mode méridien, il se manifeste par des fluctuations inter-hémisphériques de SST et est contrôlé par des rétroactions dynamiques et thermodynamiques entre le vent, l'évaporation et la SST. L'évaluation du couplage de ces variables clés du mode méridien nous a permis de proposer un modèle conceptuel pour expliquer les principaux mécanismes responsables des oscillations du mode méridien. Le modèle a montré que le mode méridien résulte de la superposition d'un mécanisme auto-entretenu basé sur les rétroactions positives et négatives générant des oscillations régulières de haute fréquence (2-3 ans) et d'un autre mécanisme d'oscillation basse fréquence (4-9 ans) lié à l'influence d'ENSO du Pacifique Est. Comme l'évolution de ces deux modes est fortement liée au déplacement méridien de la zone de convergence intertropicale (ITCZ) qui transporte les pluies, nous avons ensuite identifié la signature de ces modes sur la salinité de la surface de la mer à l'aide observations in situ et d'une simulation numérique régionale. Les processus océaniques et/ou atmosphériques responsables de la signature de chaque mode ont été également identifiés grâce à un bilan de sel dans la couche de mélange du modèle validé. Le bilan de sel a révélé que le forçage atmosphérique, lié à la migration de l'ITCZ, contrôle la région équatoriale tandis que l'advection, due à la modulation des courants, du gradient vertical et le mélange à la base de la couche de mélange, explique les variations de SSS dans les régions sous l'influence des panaches. [...] / In this thesis, we investigate several topics related to the interannual climatic modes in the tropical Atlantic. Statistical analyses allows us to extract the two main dominant modes of interannual variability: an equatorial mode and a meridional mode. The equatorial mode is responsible for Sea Surface Temperature (SST) anomalies mainly found in the Gulf of Guinea and is linked to variations of the sea-level slope in the equatorial band. It is due to dynamic feedbacks between zonal wind, sea level and SST. The meridional mode is characterised by inter-hemispheric SST fluctuations and is controlled by dynamic and thermodynamic feedbacks between the wind, evaporation and SST. After quantifying the coupling between key variables involved in the meridional mode, we develop a conceptual model to explain the main mechanisms responsible for meridional mode oscillations. The model shows that the meridional mode results from the superposition of a self-sustaining mechanism based on positive and negative feedbacks generating regular oscillations of high frequency (2-3 years) and another low frequency oscillation mechanism (4-9 years) related to the influence of ENSO. As the evolution of these two modes is strongly linked to the meridional shift of the Intertropical Convergence Zone (ITCZ) and associated rainfall maximum, we identify the signature of these modes on Sea Surface Salinity (SSS) using in situ observations and a regional numerical simulation. Oceanic and/or atmospheric processes responsible for the signature of each mode are also identified through a mixed-layer salt budget in the validated model. The salt balance reveals that the atmospheric forcing, related to the ITCZ migration, controls the equatorial region while the advection, due to the modulation of current dynamics, the vertical gradient and mixing at the base of the mixed layer, explains SSS variations in regions under the influence of plumes. Finally, we study the Equatorial Kelvin wave characteristics and influences on the density that are involved in the meridional and equatorial mode connection processes, using a very simplified model of gravity wave propagation along the equator. After a brief description of this model, which was initially constructed to study dynamics in the equatorial Pacific, we apply it to the specific case of the equatorial Atlantic by validating its analytical and numerical solutions under adiabatic conditions. [...]

This work deals with the investigation and research on organic solar cells. In the first part of this work we focus on the spectroscopical and electrical characterization of the acceptor molecule and fullerene derivative C70. In combination with the donor molecule zinc-phthalocyanines (ZnPc) we investigate C70 in flat and bulk heterojunction solar cells and compare the results with C60 as acceptor. The stronger and spectral broader thin film absorption of C70 and thus enhanced contribution to photocurrent as well as the similar electrical properties with respect to C60 result in higher power conversion efficiencies. In the second part, modifications of the blend layer morphology of a C60:ZnPc bulk heterojunction solar cell are considered. Using substrate heating during co-deposition of acceptor and donor, the molecular arrangement is influenced. Due to the additional thermal energy at the substrate the blend layer morphology is improved and optimized for a substrate heating temperature of 110°C. With transmission electron microscopy, molecular phase separation of C60 and ZnPc and the formation of polycrystalline ZnPc domains in a lateral dimension on the order of 50 nm are detected. Mobility measurements show an increased ZnPc hole mobility in the heated blend layer. The improved charge carrier percolation and transport are confirmed by the enhanced performance of such bulk heterojunction solar cells. Furthermore, we show a strong influence of the pre-deposited p-doped hole transport layer on the molecular phase separation. In the third part, we study the dependency of the open circuit voltage on the mixing ratio of C60 and ZnPc in bulk heterojunction solar cells. For the different mixing ratios we determine the ionization potentials of C60 and ZnPc. Over the various C60:ZnPc blends from 1:3 - 6:1, the ionization potentials change linearly, but different from each other and exhibit a correlation to the change in open circuit voltage. Depending on the mixing ratio an intrinsic ZnPc layer adjacent to the blend leads to injection barriers which result in reduced open circuit voltage. We hence determine a voltage loss dependent on ZnPc layer thickness and barrier height. / Diese Arbeit beschäftigt sich mit der Untersuchung und Forschung an organischen Solarzellen und gliedert sich in drei Teile. Im ersten Teil wird auf die spektroskopische und elektrische Charakerisierung des Fullerenderivates C70 eingegangen, welches als Akzeptormolekül in Kombination mit dem Donormolekül Zink-Phthalocyanin (ZnPc) in Flach- und Mischschichtheteroübergänge organischer Solarzellen Anwendung findet. Dabei wird das Molekül mit dem bisherigen Standard Akzeptormolekül C60 verglichen. Die deutlich stärkere und spektral verbreiterte Dünnschichtabsorption von C70, sowie die vergleichbaren elektrischen Eigenschaften zu C60 führen zu einer Effizienzsteigerung in den Flach- und Mischschichtsolarzellen, welche maßgeblich durch die Erhöhung des Kurzschlussstromes erreicht wird. Im zweiten Teil widmet sich diese Arbeit der Morphologiemodifizierung des Mischschichtsystems C60:ZnPc, welche durch Heizen des Substrates während der Mischverdampfung von Akzeptor- und Donormolekülen in organischen Mischschichtsolarzellen erreicht werden kann. Es wird gezeigt, dass mit der zusätzlichen Zufuhr thermischer Energie über das Substrat die Anordnung der Moleküle in der Mischschicht beeinflusst werden kann. Unter Verwendung eines Transmissionselektronmikroskops lässt sich für die Mischschicht mit der optimalen Solarzellensubstrattemperatur von 110°C eine Phasenseparation von C60 und ZnPc unter Ausbildung von polykristallinen ZnPc Domänen in der lateralen Dimension von 50 nm nachweisen. Mit zusätzlichen Messungen der Ladungsträgerbeweglichkeiten des Mischschichtsystems kann die verbesserte Perkolation und Löcherbeweglichkeit von ZnPc für die Steigerung der Performance geheizter Solarzellen bestätigt werden. Desweiteren wird gezeigt, dass die Ausbildung einer Phasenseparation sehr stark von der darunter liegenden Molekülschicht z.B. der p-dotierte Löchertransportschicht abhängig ist. Im letzten und dritten Teil geht die Arbeit auf die Abhängigkeit der Klemmspannung von der Mischschichtkonzentration von C60 und ZnPc ein. Für die unterschiedlichen Volumenkonzentrationen von C60:ZnPc zwishen 6:1 und 1:6 kann gezeigt werden, dass sich die Ionisationspotentiale von C60 und ZnPc über einen großen Bereich linear und voneinander verschieden verändern und mit den absoluten Änderung der offenenen Klemmspannung korrelieren. Desweiteren wird gezeigt, dass sich durch eine zusätzlich an die Mischschicht angrenzende intrinsische ZnPc Schicht, abhängig von der Mischschichtkonzentration, Injektionsbarrieren ausbilden, welche nachweislich einen Spannungsverlust bedingen. Dabei kann gezeigt werden, dass der Spannungsverlust mit der ZnPc Schichtdicke und der Barrierenhöhe korreliert.

This work deals with the investigation and research on organic solar cells. In the first part of this work we focus on the spectroscopical and electrical characterization of the acceptor molecule and fullerene derivative C70. In combination with the donor molecule zinc-phthalocyanines (ZnPc) we investigate C70 in flat and bulk heterojunction solar cells and compare the results with C60 as acceptor. The stronger and spectral broader thin film absorption of C70 and thus enhanced contribution to photocurrent as well as the similar electrical properties with respect to C60 result in higher power conversion efficiencies. In the second part, modifications of the blend layer morphology of a C60:ZnPc bulk heterojunction solar cell are considered. Using substrate heating during co-deposition of acceptor and donor, the molecular arrangement is influenced. Due to the additional thermal energy at the substrate the blend layer morphology is improved and optimized for a substrate heating temperature of 110°C. With transmission electron microscopy, molecular phase separation of C60 and ZnPc and the formation of polycrystalline ZnPc domains in a lateral dimension on the order of 50 nm are detected. Mobility measurements show an increased ZnPc hole mobility in the heated blend layer. The improved charge carrier percolation and transport are confirmed by the enhanced performance of such bulk heterojunction solar cells. Furthermore, we show a strong influence of the pre-deposited p-doped hole transport layer on the molecular phase separation. In the third part, we study the dependency of the open circuit voltage on the mixing ratio of C60 and ZnPc in bulk heterojunction solar cells. For the different mixing ratios we determine the ionization potentials of C60 and ZnPc. Over the various C60:ZnPc blends from 1:3 - 6:1, the ionization potentials change linearly, but different from each other and exhibit a correlation to the change in open circuit voltage. Depending on the mixing ratio an intrinsic ZnPc layer adjacent to the blend leads to injection barriers which result in reduced open circuit voltage. We hence determine a voltage loss dependent on ZnPc layer thickness and barrier height.:Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 15 2 History, Fundamentals, and Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 2.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 2.2 Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 2.2.1 Organic semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 2.2.2 Photovoltaic principle and organic solar cells . . . . . . . . . . . . . . . . . ... . . 42 2.3 Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 61 3 Materials & Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 63 3.1 Organic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 63 3.1.1 Standard photoactive materials . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 63 3.1.2 Transport materials and dopants . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . 67 3.1.3 Material purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69 3.2 Sample preparation and vacuum tools . . . . . . . . . . . . . . . . . . . . . . . . .. . 70 3.2.1 Sample preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 70 3.2.2 Vacuum tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 70 3.2.3 Substrates and layer stacks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 73 3.3 Solar cell characterization tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 77 3.3.1 J(V)-measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 3.3.2 EQE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 3.4 Further characterization tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 79 3.4.1 UPS and XPS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 79 3.4.2 OFET . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 81 3.4.3 AFM, SEM, TEM, and WAXRD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82 3.4.4 Optical Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 3.5 Simulation and modeling software . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84 3.5.1 Optical simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84 3.5.2 Electrical simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84 4 Results: C70 as acceptor molecule for organic solar cells . . . . . . . . . . . . . . 85 4.1 Optical characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85 4.2 Mobility measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 88 4.3 Ultraviolet photoelectron spectroscopy . . . . . . . . . . . . . . . . . . . . . . .. . . 89 4.4 p-i-i flat heterojunction solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 90 4.4.1 Di-NPD/fullerene flat heterojunction solar cells . . . . . . . . . . . . . . . . . . 90 4.4.2 ZnPc/fullerene flat heterojunction solar cells . . . . . . . . . . . . . . . . . . . . 91 4.5 p-i-i bulk heterojunction solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95 4.5.1 p-i-i mixed C60:C70:ZnPc bulk heterojunction solar cell . . . . . . . . . . . 99 4.6 Outlook: fullerene C84 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 101 5 Results: Bulk heterojunction solar cells deposited on heated substrates . 103 5.1 150 nm thick C60:ZnPc blend layers in m-i-p bulk heterojunctions . . . . 103 5.2 60 nm thick C60:ZnPc blend layers in m-i-p bulk heterojunctions . . . . . 107 5.2.1 AFM and SEM measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 5.2.2 Absorption measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 5.2.3 X-Ray (WAXRD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 113 5.2.4 TEM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. .. 116 5.2.5 OFET . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. .. 119 5.2.6 C70:ZnPc m-i-p bulk-heterojunctions . . . . . . . . . . . . . . . . . . . . . . .. . 121 5.3 p-i-i bulk heterojunction solar cells deposited at 110°C . . . . . . . . . . . . 124 5.3.1 Influence of sublayer on blend layer morphology . . . . . . . . . . . . . . . . 128 6 Results: On the influence of Voc in p-i-i bulk heterojunction solar cells . . 137 6.1 Dependency of Voc on C60:ZnPc mixing ratio . . . . . . . . . . . . . . . . . . . . 137 6.2 Influence of different hole transport layers on C60:ZnPc . . . . . . . . . .. . 140 6.2.1 Red and blue illumination measurements . . . . . . . . . . . . . . . . . . . . . . 143 6.2.2 Optical characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146 6.2.3 UPS measurements for different C60:ZnPc mixing ratios . . . . . . . . .. 148 6.3 Influence of thin ZnPc and C70 interlayers on Voc . . . . . . . . . . . . . . .. . 152 6.3.1 UPS measurements of blend/ZnPc interfaces . . . . . . . . . . . . . . . . . . . 155 6.3.2 Blend/ZnPc injection barrier: experiment and simulation . . . . . . . . . . 158 7 Conclusion and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171 / Diese Arbeit beschäftigt sich mit der Untersuchung und Forschung an organischen Solarzellen und gliedert sich in drei Teile. Im ersten Teil wird auf die spektroskopische und elektrische Charakerisierung des Fullerenderivates C70 eingegangen, welches als Akzeptormolekül in Kombination mit dem Donormolekül Zink-Phthalocyanin (ZnPc) in Flach- und Mischschichtheteroübergänge organischer Solarzellen Anwendung findet. Dabei wird das Molekül mit dem bisherigen Standard Akzeptormolekül C60 verglichen. Die deutlich stärkere und spektral verbreiterte Dünnschichtabsorption von C70, sowie die vergleichbaren elektrischen Eigenschaften zu C60 führen zu einer Effizienzsteigerung in den Flach- und Mischschichtsolarzellen, welche maßgeblich durch die Erhöhung des Kurzschlussstromes erreicht wird. Im zweiten Teil widmet sich diese Arbeit der Morphologiemodifizierung des Mischschichtsystems C60:ZnPc, welche durch Heizen des Substrates während der Mischverdampfung von Akzeptor- und Donormolekülen in organischen Mischschichtsolarzellen erreicht werden kann. Es wird gezeigt, dass mit der zusätzlichen Zufuhr thermischer Energie über das Substrat die Anordnung der Moleküle in der Mischschicht beeinflusst werden kann. Unter Verwendung eines Transmissionselektronmikroskops lässt sich für die Mischschicht mit der optimalen Solarzellensubstrattemperatur von 110°C eine Phasenseparation von C60 und ZnPc unter Ausbildung von polykristallinen ZnPc Domänen in der lateralen Dimension von 50 nm nachweisen. Mit zusätzlichen Messungen der Ladungsträgerbeweglichkeiten des Mischschichtsystems kann die verbesserte Perkolation und Löcherbeweglichkeit von ZnPc für die Steigerung der Performance geheizter Solarzellen bestätigt werden. Desweiteren wird gezeigt, dass die Ausbildung einer Phasenseparation sehr stark von der darunter liegenden Molekülschicht z.B. der p-dotierte Löchertransportschicht abhängig ist. Im letzten und dritten Teil geht die Arbeit auf die Abhängigkeit der Klemmspannung von der Mischschichtkonzentration von C60 und ZnPc ein. Für die unterschiedlichen Volumenkonzentrationen von C60:ZnPc zwishen 6:1 und 1:6 kann gezeigt werden, dass sich die Ionisationspotentiale von C60 und ZnPc über einen großen Bereich linear und voneinander verschieden verändern und mit den absoluten Änderung der offenenen Klemmspannung korrelieren. Desweiteren wird gezeigt, dass sich durch eine zusätzlich an die Mischschicht angrenzende intrinsische ZnPc Schicht, abhängig von der Mischschichtkonzentration, Injektionsbarrieren ausbilden, welche nachweislich einen Spannungsverlust bedingen. Dabei kann gezeigt werden, dass der Spannungsverlust mit der ZnPc Schichtdicke und der Barrierenhöhe korreliert.:Contents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 15 2 History, Fundamentals, and Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 2.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 2.2 Fundamentals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 2.2.1 Organic semiconductors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21 2.2.2 Photovoltaic principle and organic solar cells . . . . . . . . . . . . . . . . . ... . . 42 2.3 Motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 61 3 Materials & Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 63 3.1 Organic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 63 3.1.1 Standard photoactive materials . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 63 3.1.2 Transport materials and dopants . . . . . . . . . . . . . . . . . . . . . . . . . . ... . . 67 3.1.3 Material purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69 3.2 Sample preparation and vacuum tools . . . . . . . . . . . . . . . . . . . . . . . . .. . 70 3.2.1 Sample preparation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 70 3.2.2 Vacuum tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 70 3.2.3 Substrates and layer stacks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 73 3.3 Solar cell characterization tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 77 3.3.1 J(V)-measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 3.3.2 EQE . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 3.4 Further characterization tools . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 79 3.4.1 UPS and XPS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 79 3.4.2 OFET . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 81 3.4.3 AFM, SEM, TEM, and WAXRD . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82 3.4.4 Optical Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 3.5 Simulation and modeling software . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84 3.5.1 Optical simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84 3.5.2 Electrical simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84 4 Results: C70 as acceptor molecule for organic solar cells . . . . . . . . . . . . . . 85 4.1 Optical characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85 4.2 Mobility measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 88 4.3 Ultraviolet photoelectron spectroscopy . . . . . . . . . . . . . . . . . . . . . . .. . . 89 4.4 p-i-i flat heterojunction solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 90 4.4.1 Di-NPD/fullerene flat heterojunction solar cells . . . . . . . . . . . . . . . . . . 90 4.4.2 ZnPc/fullerene flat heterojunction solar cells . . . . . . . . . . . . . . . . . . . . 91 4.5 p-i-i bulk heterojunction solar cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95 4.5.1 p-i-i mixed C60:C70:ZnPc bulk heterojunction solar cell . . . . . . . . . . . 99 4.6 Outlook: fullerene C84 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . 101 5 Results: Bulk heterojunction solar cells deposited on heated substrates . 103 5.1 150 nm thick C60:ZnPc blend layers in m-i-p bulk heterojunctions . . . . 103 5.2 60 nm thick C60:ZnPc blend layers in m-i-p bulk heterojunctions . . . . . 107 5.2.1 AFM and SEM measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 5.2.2 Absorption measurements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 5.2.3 X-Ray (WAXRD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 113 5.2.4 TEM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. .. 116 5.2.5 OFET . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. .. 119 5.2.6 C70:ZnPc m-i-p bulk-heterojunctions . . . . . . . . . . . . . . . . . . . . . . .. . 121 5.3 p-i-i bulk heterojunction solar cells deposited at 110°C . . . . . . . . . . . . 124 5.3.1 Influence of sublayer on blend layer morphology . . . . . . . . . . . . . . . . 128 6 Results: On the influence of Voc in p-i-i bulk heterojunction solar cells . . 137 6.1 Dependency of Voc on C60:ZnPc mixing ratio . . . . . . . . . . . . . . . . . . . . 137 6.2 Influence of different hole transport layers on C60:ZnPc . . . . . . . . . .. . 140 6.2.1 Red and blue illumination measurements . . . . . . . . . . . . . . . . . . . . . . 143 6.2.2 Optical characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146 6.2.3 UPS measurements for different C60:ZnPc mixing ratios . . . . . . . . .. 148 6.3 Influence of thin ZnPc and C70 interlayers on Voc . . . . . . . . . . . . . . .. . 152 6.3.1 UPS measurements of blend/ZnPc interfaces . . . . . . . . . . . . . . . . . . . 155 6.3.2 Blend/ZnPc injection barrier: experiment and simulation . . . . . . . . . . 158 7 Conclusion and Outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171

La région boréale arctique (RBA) couvre une vaste étendue qui lui confère un rôle important dans le système climatique mondial, par ses échanges d'énergie et de matière avec l'atmosphère. La température de l'air dans la région boréale arctique a augmenté à des taux disproportionnés par rapport à la moyenne mondiale, entraînant des changements dans la composition et la structure de la végétation. La RBA comprend l'écotone de la forêt boréale et de la toundra (EFT), qui s'étend sur plus de 10,000 km à travers l'hémisphère nord. La structure et la composition de la végétation varient considérablement à travers l’EFT. Du sud au nord, les arbres deviennent plus courts, plus dispersés et finalement absents. Ce gradient entraîne des variations dans la balance énergétique de surface. Ainsi, des changements dans la composition et la structure de la végétation dans l’EFT pourraient influencer le climat régional futur de ces régions. Ces changements régionaux pourraient se répercuter sur le climat mondial en interagissant avec le cycle du carbone par des changements dans les régimes de perturbations et la profondeur de la couche limite atmosphérique. L'objectif de cette étude était de développer un état des lieux de la variation latitudinale des interactions entre la surface et l’atmosphère et du climat régional à travers l’EFT dans le nord-ouest du Canada. Nous avons utilisé des mesures de covariance des turbulences provenant d’une forêt subarctique en marge de l’EFT et d’une toundra minérale caractérisant l’EFT du nord-ouest du Canada afin de quantifier les différences journalière et saisonnières des échanges d'énergie. Quatre paramètres de surface (albédo, conductance aérodynamique, conductance de surface et facteur de découplage) ont été examinés dans le but d’expliquer les différences dans la balance énergétique de surface. Des observations par radiosonde basées sur des campagnes de terrain et une expérience de modélisation de la couche limite atmosphérique ont été réalisées afin de discuter des conséquences potentielles des changements de végétation sur la dynamique de la couche limite atmosphérique (hauteur, température, humidité) et ses implications pour le climat régional. La forêt subarctique a démontré une meilleure capacité à transférer la chaleur vers l’atmosphère et une plus grande résistance à l'évapotranspiration, se traduisant par des conditions atmosphériques plus chaudes et sèches, spécialement au printemps. En été et automne, une conductance de surface plus élevée sur le site de la toundra s’est traduite par à une plus grande proportion de l'énergie utilisée pour humidifier l'atmosphère, résultant en une couche atmosphérique moins épaisse et un refroidissement régional du climat. La caractérisation des interactions entre la surface et l’atmosphère à travers l’EFT contribuera à améliorer les prédictions des effets des changements de végétation en cours sur le climat régional dans la région boréale arctique. / Considering its vast extent, the Arctic-boreal region (ABR) plays an important role in the global climate system through its exchange of energy and matter with the atmosphere. Air temperature across the ABR has been increasing at a higher rate compared to the global average and has led to changes in vegetation composition and structure across the ABR. The ABR includes the forest-tundra ecotone (FTE), spanning more than 10,000 km across the northern hemisphere. As the world’s longest transition zone, the FTE separates the boreal and Arctic biomes over a width of only a few tens to hundreds of kilometers. Vegetation composition and structure varies considerably across the FTE as trees become, from south to north, shorter and more stunted, sparser, and eventually, absent. The associated latitudinal gradient in surface properties results in corresponding latitudinal variations in the energy balance. Thus, changes in the latitudinal variation in surface properties and energy exchanges within the atmospheric boundary layer (ABL) may affect future regional climate across the FTE. The goal of this study was to develop a baseline understanding of the latitudinal variation in surface-atmosphere interactions and atmospheric boundary layer dynamics across the FTE in northwestern Canada. We used paired eddy covariance measurements of surface energy fluxes and supporting environmental measurements at a subarctic woodland (‘woodland’) and a mineral upland tundra site (‘tundra’) to quantify differences in daily and seasonal differences in woodland and tundra properties and energy exchanges. Four bulk surface parameters (albedo, aerodynamic conductance, surface conductance, and decoupling factor) were examined to explain drivers of those differences. Campaign-based radiosonde observations and numerical experiments using an ABL model were used to examine the impacts of a sparse tree cover on ABL dynamics (height, temperature, humidity) and their implications for surface climate compared to treeless tundra. The sparse tree cover at the woodland site showed an enhanced ability to transfer heat into the atmosphere and a higher resistance to evapotranspiration compared to tundra, leading to warmer and drier conditions especially in late winter and spring. In summer and fall, higher bulk surface conductance at the tundra site led to more energy being used to moisten the atmosphere, resulting in a shallower ABL and regional cooling of the atmosphere. Refined characterization of land surface-atmosphere interactions across the FTE will help to project the effect of ongoing vegetation changes on regional climate in the circumpolar Arctic-boreal region.