Charge generation, transport and recombination in organic solar cells

This thesis presents a study of the charge generation, transport, and recombination processes in organic solar cells performed with time-resolved experimental techniques. Organic solar cells based on polymers can be solution-processed on large areas and thus promise to become an inexpensive source of renewable energy. Despite significant improvements of the power conversion efficiency over the last decade, the fundamental working principles of organic solar cells are still not fully understood. It is the aim of this thesis to clarify the role of different performance limiting processes in organic solar cells and to correlate them with the molecular structure of the studied materials, i.e. poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl C61 butyric acid methyl ester (PCBM). By combining time-of-flight charge transport measurements, transient absorption spectroscopy, a newly developed experimental technique called time delayed double pulse experiment and drift-diffusion simulations a comprehensive analysis of the working principles of P3HT:PCBM solar cells could be performed. It was found that the molecular structure of P3HT (i.e. the regioregularity) has a pronounced influence on the morphology of thin films of pristine P3HT and of blends of P3HT with PCBM. This morphology in turn affected the charge transport properties as well as the charge generation and recombination kinetics. Well-ordered regioregular P3HT was found to be characterized by a high charge carrier mobility, efficient charge generation and low but field-dependent (non-geminate) recombination. Importantly, the charge generation yield was found to be independent of temperature and applied electric field as opposed to the expectations of the Onsager-Braun model that is commonly applied to describe the temperature and field dependence of charge generation in organic solar cells. These properties resulted in a reasonably good power conversion efficiency. In contrast to this, amorphous regiorandom P3HT was found to show poor charge generation, transport and recombination properties that combine to a much lower power conversion efficiency.

Entwicklung kohärenter Lichtquellen im XUV-Regime

Plasmabasierte Röntgenlaser sind aufgrund ihrer kurzen Wellenlänge und schma-rnlen spektralen Bandbreite attraktive Diagnose-Instrumente in einer Vielzahl potentieller Anwendungen, beispielsweise in den Bereichen Spektroskopie, Mikroskopie und EUV-Lithografie. Dennoch sind Röntgenlaser zum heutigen Stand noch nicht sehr weit verbreitet, was vorwiegend auf eine zu geringe Pulsenergie und für manche Anwendungen nicht hinreichende Strahlqualität zurückzuführen ist. In diesem Zusammenhang wurden in den letzten Jahren bedeutende Fortschritte erzielt. Die gleichzeitige Weiterentwicklung von Pumplasersystemen und Pumpmechanismen ermöglichte es, kompakte Röntgenlaserquellen mit bis zu 100 Hz zu betreiben. Um gleichzeitig höhere Pulsenergien, höhere Strahlqualität und volle räumliche Kohärenz zu erhalten, wurden intensive Studien theoretischer und experimenteller Natur durchgeführt. In diesem Kontext wurde in der vorliegenden Arbeit ein experimenteller Aufbau zur Kombination von zwei Röntgenlaser-Targets entwickelt, die sogenannte Butterfly-Konfiguration. Der erste Röntgenlaser wird dabei als sogenannter Seed für das zweite, als Verstärker dienende Röntgenlasermedium verwendet (injection-seeding). Aufrndiese Weise werden störende Effekte vermieden, welche beim Entstehungsprozessrndes Röntgenlasers durch die Verstärkung von spontaner Emission zustande kom-rnmen. Unter Verwendung des ebenfalls an der GSI entwickelten Double-Pulse Gra-rnzing Incidence Pumpschemas ermöglicht das hier vorgestellte Konzept, erstmaligrnbeide Röntgenlasertargets effizient und inklusive Wanderwellenanregung zu pum-rnpen.rnBei einer ersten experimentellen Umsetzung gelang die Erzeugung verstärkter Silber-Röntgenlaserpulse von 1 µJ bei 13.9 nm Wellenlänge. Anhand der gewonnenen Daten erfolgte neben dem Nachweis der Verstärkung die Bestimmung der Lebensdauer der Besetzungsinversion zu 3 ps. In einem Nachfolgeexperiment wurden die Eigenschaften eines Molybdän-Röntgenlaserplasmas näher untersucht. Neben dem bisher an der GSI angewandten Pumpschema kam in dieser Strahlzeit noch eine weitere Technik zum Einsatz, welche auf einem zusätzlichen Pumppuls basierte. In beiden Schemata gelang neben dem Nachweis der Verstärkung die zeitliche und räumliche Charakterisierung des Verstärkermediums. Röntgenlaserpulse mit bis zu 240 nJ bei einer Wellenlänge von 18.9 nm wurden nachgewiesen. Die erreichte Brillanz der verstärkten Pulse lag ca. zwei Größenordnungen über der des ursprünglichen Seeds und mehr als eine Größenordnung über der Brillanz eines Röntgenlasers, dessen Erzeugung auf der Verwendung eines einzelnen Targets basierte. Das in dieser Arbeitrnentwickelte und experimentell verifizierte Konzept birgt somit das Potential, extrem brillante plasmabasierte Röntgenlaser mit vollständiger räumlicher und zeitlicher Kohärenz zu erzeugen.rnDie in dieser Arbeit diskutierten Ergebnisse sind ein wesentlicher Beitrag zu der Entwicklung eines Röntgenlasers, der bei spektroskopischen Untersuchungen von hochgeladenen Schwerionen eingesetzt werden soll. Diese Experimente sind amrnExperimentierspeicherring der GSI und zukünftig auch am High-Energy StoragernRing der FAIR-Anlage vorgesehen.rn

Time-dependent hierarchical organization of spatial working memory: a transcranial magnetic stimulation study

The performance of memory-guided saccades with two different delays (3 and 30 s of memorization) was studied in seven healthy subjects. Double-pulse transcranial magnetic stimulation (dTMS) with an interstimulus interval of 100 ms was applied over the right dorsolateral prefrontal cortex (DLPFC) early (1 s after target presentation) and late (28 s after target presentation). Early stimulation significantly increased in both delays the percentage of error in amplitude (PEA) of contralateral memory-guided saccades compared to the control experiment without stimulation. dTMS applied late in the delay had no significant effect on PEA. Furthermore, we found a significantly smaller effect of early stimulation in the long-delay paradigm. These results suggest a time-dependent hierarchical organization of the spatial working memory with a functional dominance of DLPFC during the early memorization, independent from the memorization delay. For a long memorization delay, however, working memory seems to have an additional, DLPFC-independent component.

Hemispheric asymmetry in visuospatial attention assessed with transcranial magnetic stimulation

Transcranial magnetic stimulation (TMS) was used to study visuospatial attention processing in ten healthy volunteers. In a forced choice recognition task the subjects were confronted with two symbols simultaneously presented during 120 ms at random positions, one in the left and the other in the right visual field. The subject had to identify the presented pattern out of four possible combinations and to press the corresponding response key within 2 s. Double-pulse TMS (dTMS) with a 100-ms interstimulus interval (ISI) and an intensity of 80% of the stimulator output (corresponding to 110-120% of the motor threshold) was applied by a non-focal coil over the right or left posterior parietal cortex (PPC, corresponding to P3/P4 of the international 10-20 system) at different time intervals after onset of the visual stimulus (starting at 120 ms, 270 ms and 520 ms). Double-pulse TMS over the right PPC starting at 270 ms led to a significant increase in percentage of errors in the contralateral, left visual field (median: 23% with TMS vs 13% without TMS, P=0.0025). TMS applied earlier or later showed no effect. Furthermore, no significant increase in contra- or ipsilateral percentage of errors was found when the left parietal cortex was stimulated with the same timing. These data indicate that: (1) parietal influence on visuospatial attention is mainly controlled by the right lobe since the same stimulation over the left parietal cortex had no significant effect, and (2) there is a vulnerable time window to disturb this cortical process, since dTMS had a significant effect on the percentage of errors in the contralateral visual hemifield only when applied 270 ms after visual stimulus presentation.

Possibilities of advanced MAG-welding processes in shipbuilding

In shipbuilding industry welding of primer coated and tack welded steel products cause different issues. Primer coated steel products are commonly used at shipyards to ensure corrosion free storage of products in outdoor conditions. However usage of primer can cause imperfections to welds. To prevent porosity primed steel products are usually welded with tubular welding wires. Tack welds cause commonly interferences in mechanized welding when over welded, which increases costs related to welding due to increased need of preparing and repairing. The aim of this study is to research possibilities of advanced solid wire MAG-welding processes to deal with these two previously mentioned problems. This study concentrates to examine possibilities of MAG-welding, pulse MAG-welding, double pulse MAG-welding, RapidArc and ForceArc processes. Large amount of experiments were made to find out the produced porosity and the ability to over weld tack welds with each process in different circumstances. In welding of primed steel products porosity is caused mainly by hydrogen, CO, CO2, nitrous gases and zinc fumes. It was found in experiments that porosity of MAG-welding can be greatly decreased by using pulse MAG-welding instead. Also reduction of welding speed, usage of air gap and usage of solid wire product with higher amount of alloying elements reduces porosity. Researched advanced MAG-welding processes did not have an improvement into over welding of tack welds. With studied throat thicknesses and welding positions conventional MAG-welding managed better over welding of tack welds than the four studied advanced MAG-welding processes. Studied solid wire MAG-welding processes would be best suited at shipyard for mechanized welding in welding position PB. In welding positions PD and PG tubular welding wires are clearly more productive.

An adiabatic model for a two-stage double-inlet pulse tube refrigerator

A numerical modelling technique for predicting the detailed performance of a double-inlet type two-stage pulse tube refrigerator has been developed. The pressure variations in the compressor, pulse tube, and reservoir were derived, assuming the stroke volume variation of the compressor to be sinusoidal. The relationships of mass flowrates, volume flowrates, and temperature as a function of time and position were developed. The predicted refrigeration powers are calculated by considering the effect of void volumes and the phase shift between pressure and mass flowrate. These results are compared with the experimental results of a specific pulse tube refrigerator configuration and an existing theoretical model. The analysis shows that the theoretical predictions are in good agreement with each other.

Broadband ultrafast pulse generation with double wall carbon nanotubes

Materials with nonlinear optical properties are much sought after for ultrafast photonic applications. Mode-locked lasers can generate ultrafast pulses using saturable absorbers[1]. Currently, the dominant technology is based on semiconductor saturable absorber mirrors (SESAMs). However, narrow tuning range (tens of nm), complex fabrication and packaging limit their applications[2]. Single wall nanotubes (SWNTs) and graphene offer simpler and cost-effective solutions[1]. Broadband operation can be achieved in SWNTs using a distribution of tube diameters[1,3], or by using graphene[4-8], due to the gapless linear dispersion of Dirac electrons[8,9]. © 2011 IEEE.

Double-wall carbon nanotubes for wide-band, ultrafast pulse generation.

We demonstrate wide-band ultrafast optical pulse generation at 1, 1.5, and 2 μm using a single-polymer composite saturable absorber based on double-wall carbon nanotubes (DWNTs). The freestanding optical quality polymer composite is prepared from nanotubes dispersed in water with poly(vinyl alcohol) as the host matrix. The composite is then integrated into ytterbium-, erbium-, and thulium-doped fiber laser cavities. Using this single DWNT-polymer composite, we achieve 4.85 ps, 532 fs, and 1.6 ps mode-locked pulses at 1066, 1559, and 1883 nm, respectively, highlighting the potential of DWNTs for wide-band ultrafast photonics.

The effect of different pulse durations in the treatment of nail psoriasis with 595-nm pulsed dye laser: a randomized, double-blind, intrapatient left-to-right study

Several studies have proven the efficacy of pulsed dye laser (PDL) in the treatment of plaque type psoriasis. However, only two published studies indicate the effectiveness of PDL on nail psoriasis.

Large-Eddy Simulation of physiological pulsatile non-newtonian flow in a channel with double constriction

Physiological pulsatile flow in a 3D model of arterial double stenosis, using the modified Power-law blood viscosity model, is investigated by applying Large Eddy Simulation (LES) technique. The computational domain has been chosen is a simple channel with biological type stenoses. The physiological pulsation is generated at the inlet of the model using the first four harmonics of the Fourier series of the physiological pressure pulse. In LES, a top-hat spatial grid-filter is applied to the Navier-Stokes equations of motion to separate the large scale flows from the subgrid scale (SGS). The large scale flows are then resolved fully while the unresolved SGS motions are modelled using the localized dynamic model. The flow Reynolds numbers which are typical of those found in human large artery are chosen in the present work. Transitions to turbulent of the pulsatile non-Newtonian along with Newtonian flow in the post stenosis are examined through the mean velocity, wall shear stress, mean streamlines as well as turbulent kinetic energy and explained physically along with the relevant medical concerns.

Double star chopper cell converter for battery electric vehicles with inter-module SoC balancing and fault tolerant control

A modularized battery system with Double Star Chopper Cell (DSCC) based modular multilevel converter is proposed for a battery operated electric vehicle (EV). A design concept for the modularized battery micro-packs for DSCC is described. Multidimensional pulse width modulation (MD-PWM) with integrated inter-module SoC balancing and fault tolerant control is proposed and explained. The DSCC can be operated either as an inverter to drive the EV motor or as a synchronous rectifier connected to external three phase power supply equipment for charging the battery micro-packs. The methods of operation as inverter and synchronous rectifier with integrated inter-module SoC balancing and fault tolerant control are discussed. The proposed system operation as inverter and synchronous rectifier are verified through simulations and the results are presented.