5 search hits
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Dynamik und Energetik von Triplettexzitonen in konjugierten Polymeren und Molekülen
(2011)
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Sebastian Tim Hoffmann
- Der Markt für elektronische Bauteile wie zum Beispiel organische Leuchtdioden (OLEDs) auf Basis von organischen Halbleitern wächst stetig, daher ist es von immer größerer Bedeutung, die in diesen Materialien ablaufenden Prozesse zu verstehen. Besonders Triplettzustände spielen für OLEDs eine wichtige Rolle. Diese Arbeit beschäftigt sich zum einen mit den Eigenschaften des Transfers von Triplett-Exzitonen und zum anderen mit energetischen Prozessen von Triplettanregungen in organischen Halbleitern. Es wurde die aus der Relaxation des Triplettzustandes resultierende Phosphoreszenz untersucht, insbesondere die zeit- und temperaturabhängige Veränderung ihrer Intensität, sowie die temperaturabhängige Verschiebung der Spektren. Mittels temperaturabhängig gemessener Diffusionsraten konnte gezeigt werden, dass es einen Temperaturbereich der Diffusion gibt, der stark und einen, der kaum temperaturaktiviert ist. Die Gesamtaktivierungsenergie setzt sich dabei aus einem Beitrag der energetischen Unordnung auf Grund der zufälligen Verteilung der Energieniveaus eines Ensembles von Chromophoren und einem proportional zur Reorganisationsenergie zusammen. Letzterer dominiert beim Marcus-Modell oberhalb einer Übergangstemperatur und beschreibt die Energie, die auf Grund von Änderungen in der Elektronendichte aufgebracht werden muss, um die darauf folgende Änderung der Kernabstände zu ermöglichen. Bei tiefen Temperaturen steht nur wenig thermische Aktivierungsenergie zur Verfügung und es dominieren Tunnelprozesse. Hier spielt besonders der Beitrag der energetischen Unordnung eine Rolle. Dieser zweite Mechanismus kann durch die sogenannten Miller-Abrahams Raten beschrieben werden. Um den Einfluss von energetischer Unordnung und Reorganisationsenergie auf den Transfer von Triplettexzitonen besser untersuchen zu können wurde ein Materialsystem auf Grundlage von Poly(p-Phenylen) untersucht, in welchem beide Parameter systematisch variiert sind. Im Vergleich mit einem von Theoretikern erarbeiteten Modell ergab sich eine Abweichung der experimentell ermittelten Parameter bei tiefen Temperaturen. Durch Messungen der spektralen Diffusion der Triplettexzitonen konnte gezeigt werden, dass das im Modell vorausgesetzte Erreichen des thermischen Gleichgewichts in Abhängigkeit der energetischen Unordnung teilweise nicht mehr erfüllt ist und zu einer Frustration der spektralen Relaxation führen kann. Um die experimentellen Ergebnisse zu überprüfen wurden zusätzlich Monte-Carlo-Simulationen durchgeführt. Dabei hat sich zum einen gezeigt, dass sich die Frustration reproduzieren lässt. Zum anderen lassen sich die experimentell bestimmten Triplettdiffusionsraten mit den Miller-Abrahams-Raten im Tieftemperaturbereich und die Marcus-Raten im Hochtemperaturbereich beschreiben und damit auf den Triplett-Transfer anwenden. Im zweiten Teil der Arbeit wurde die Bedeutung von Triplettzuständen in Materialien für elektronische Bauteile untersucht. Triplettzustände spielen zum Beispiel für die in OLEDs verwendeten Wirts- und Gast-Materialien eine wichtige Rolle. Als Wirtsmaterialien wurden CBP-Derivate (4,4‘-bis(N-carbazolyl)-2,2‘-biphenyl) untersucht. Alle nichtstrahlenden Zerfälle im Wirtsmaterial führen zu einer Effizienzminderung der OLED, deshalb müssen die in den Materialien stattfindenden Prozesse besser verstanden werden. Die Triplettniveaus in den CBP-Derivaten sind normalerweise hoch genug, damit kein Energietransfer auf den Wirt stattfinden kann. Hier zeigte sich jedoch im Film eine Besonderheit. In Abhängigkeit der Substituenten konnte die Stärke der Ausbildung eines Triplett-Sandwich-Excimers variiert werden, bei dem die Carbazoleinheiten zweier Moleküle überlappen. Wegen des guten Wellenfunktionsüberlapps der Carbazoleinheiten ist bei diesem Excimer die Stabilisierungsenergie sehr hoch und kann daher durch ungewollten Energietransfer vom Gast- auf das Wirtsmaterial die Effizienz mindern. Als Beispiel für Gast-Materialien wurden zusätzlich blau emittierende Ir-Komplexe untersucht. Wegen der benötigten hohen Triplettenergien ist es eine Herausforderung, effiziente blaue Triplettemitter herzustellen. In einer Serie dieser Komplexe konnte an einem blau emittierenden aber ineffizienten Komplex durch Spektroskopie und quantenchemische Rechnungen ein intramolekularer Energietransfer auf den Hilfsliganden identifiziert und Lösungsansätze aufzeigt werden, diesen effizienzmindernden Prozess zu beheben. Zusammenfassend kann gesagt werden, dass in dieser Arbeit wesentliche und fundamentale Aspekte herausgefunden wurden, die das Verständnis des Transfers von Triplettexzitonen erweitern und als Modell für Ladungstransfer allgemein dienen können. Außerdem wurde gezeigt, wie wichtig es ist, effizienzmindernde Prozesse und Zustände, sowohl in Wirts- als auch Gast-Systemen zu verstehen, um damit Strategien zu ihrer Vermeidung entwickeln zu können.
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Active and Passive Transport at Interfaces
(2011)
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Saeedeh Aliaskarisohi
- In this thesis we studied different forms of transport at interfaces. Four different interfacial transport mechanisms have been investigated. In each of them one physical aspect of active and passive transport is discussed. The four systems are arranged and discussed in four separate chapters. In chapter 3 and 4 we study the effect of static or hydrodynamic interactions on the cross over from individual diffusion towards collective diffusion. In chapter 3 the diffusion of circular domains on a giant unilamellar vesicle is measured. By tracking the motion of hydrodynamic interacting domains on a curved membrane we determined whether it is possible to extract rheological properties of the bilayer membrane. A similar two dimensional system interacting via static dipole interactions is studied in chapter 4. A mixture of paramagnetic and nonmagnetic colloidal particles immersed into a diluted ferrofluid is self assembled into colloidal flowers. In this experiment the effect of static interactions on the modes of diffusion of the petals of the colloidal flower is investigated in a one dimensional system. The results are compared with the single file diffusion of a hard core interacting one dimensional system. In chapter 5, the effect of actively directing particles with fluctuating active forces in a symmetry broken environment is studied. We address the question how to competing symmetry breaking effects decide on the direction of motion. The system consists of paramagnetic colloidal particles placed into an aqueous solution above the liquid-solid interface of a magnetic garnet film. An external modulated field supplies the fluctuations and the symmetry is broken by tilting the external field with respect to the magnetic film and/or by a magnetic symmetry broken pattern of the magnetic film. The direction of motion of the paramagnetic colloids is measured and we give a theoretical explanation of why which symmetry breaking wins. The fluidization of a two dimensional solid to a two dimensional liquid via the yielding of the monolayer is studied in chapter 6. The monolayer is locally yielded with thermo capillary interactions by focusing a laser onto it. We investigate the yielding as a function of the chemical nature of the monolayer and determine the thermodynamic requirements necessary for thermo capillary yielding.
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Dynamics and statistics of hydrodynamically interacting particles in laminar flows
(2011)
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Jochen Bammert
- The subject of this thesis is the investigation of the dynamics and statistics of hydrodynamically interacting particles in low Reynolds number flows, which is discussed in three interrelated themes. The first theme focuses on polymer fractionation. With our basic model we explore the possibility to sort dumbbells with respect to their size using a two dimensional periodic potential. It turns out that the purely diffusive behavior of a dumbbell in this structured landscape is dominated by the ratio of two characteristic length scales, namely the wavelength of the potential l and the size of the dumbbell b. We explain why the diffusion constant in the potential plane shows a pronounced local maximum around l/b equal 3/2. Furthermore, the influence of the spring rigidity and the hydrodynamic interaction on the diffusive motion are examined as well as the dumbbell statistics. If the dumbbell is driven by an external flow through the periodic landscape two different kinds of motion occur: transport along a potential valley and a stair-like motion oblique to the trenches. In the latter case, the dumbbell jumps regularly to a neighboring valley which results in an effective deflection. The onset of the oblique movement as well as the deflection angle beta depend on the hydrodynamic interaction, on the ratio l/b, and on the Brownian motion of the beads. Especially the significant dependence of beta on l/b enables particle sorting. The results are published. The second theme deals with the Brownian dynamics in shear flows. Here, we investigate the correlations of particle fluctuations in order to characterize the direct interplay between thermal motion, hydrodynamic interactions, and non-uniform flows.With respect to the experimental implementation the particles are caught by harmonic potentials. First, we consider one trapped Brownian bead in linear shear and Poiseuille flows. The correlation functions of the particle’s position and velocity fluctuations are calculated analytically. The main result is the occurrence of shear-induced cross-correlations between orthogonal fluctuations in the shear plane which are asymmetric in time. Moreover, the positional probability distribution, P(r), of a single bead in both types of flow is determined. In Poiseuille flow, where no analytical solutions can be obtained, we use perturbation expansions to derive formulas for P(r) that are valuable for the analysis of experimental data. In the case of a linear shear flow, a connection between the static correlations and the distribution functions is derived which allows a consistency check between independent measurements. Considering a system with several Brownian particles it is obvious that hydrodynamic interactions influence the correlations. In order to investigate this effect, we calculate the positional correlation functions for a setup of two trapped Brownian beads which are exposed to a linear shear flow. As expected, the one-particle correlations change compared to the single particle case described above. They depend on the distance between the two beads. In addition, we find inter-particle correlations between orthogonal positional fluctuations of different particles. The structure of these new cross-correlations depends significantly on the relative orientation of the two beads in the shear flow. They can have zero, one, or two local extrema as a function of time. In collaboration with Prof. Wagner from Saarbrücken some of our predictions are already confirmed by experiments, where polystyrene beads are caught by optical traps and simultaneously exposed to linear shear flows in a special microfluidic device. The results are published and further investigations are in progress.The third theme concentrates on the rheology of colloidal suspensions. Our deterministic model system consists of Hookean dumbbells suspended in a confined Newtonian fluid under constant shear. We perform a numerical study using fluid particle dynamics simulations, where the effective viscosity of the suspension, eta, and the dumbbell statistics are determined. The investigations on the tumbling motion of a single dumbbell reveals that eta is influenced by three different contributions: the volume fraction occupied by the dumbbell, the hydrodynamic interaction between the beads, and elastic correlation effects. For a suspension of independent spheres we observe in our simulations that the viscosity, as a function of the volume fraction Phi, differs from the prediction of Einstein, Batchelor and Green if Phi becomes larger than 8%. Replacing the beads by dumbbells leads to an increase of eta , which depends significantly on the length of the springs connecting the two beads. The distribution function for the orientation angle of the dumbbells indicates the complex motion of the individual objects in the suspension, which may lead to the so-called elastic turbulence, as experimentally discovered by Groisman and Steinberg.
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Holographic Investigation of Azobenzene-Containing Low-Molecular-Weight Compounds
(2011)
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Hubert Audorff
- In the present thesis, holographic volume and surface relief gratings in azobenzene-containing low-molecular-weight compounds are investigated to obtain a broader understanding of this new class of material. Azobenzene chromophores undergo light-induced trans-cis-trans isomerization cycles leading to a reorientation of the long axis of the chromophores. If linearly polarized light is incident on the sample, these isomerizations result in a reorientation of this axis perpendicular to the light polarization. A holographic light grating, which can be formed by the interference of two coherent laser beams, leads to the inscription of a refractive-index modulation in the material. The azobenzene-containing low-molecular-weight compounds studied in this thesis consist of different building blocks: the core unit, the azobenzene chromophores with substituents, and the spacer and the linkage group between chromophore and core unit. These components can be used in a modular-design principle to synthesize a large library of low-molecular-weight compounds. Surprisingly, some of the investigated low-molecular-weight compounds form also a liquid-crystalline phase besides the amorphous phase as evidenced by polarized microscopy. If these liquid-crystalline compounds are prepared as solid films, however, they are quenched to an amorphous state. Upon reorientation of the azobenzene chromophores by illumination with a holographic light grating, a phase transition from the amorphous to an ordered state can be induced. This phase change in the latent liquid-crystalline low-molecular-weight compounds is very interesting for applications. The latent liquid-crystalline low-molecular-weight compounds show a post-development of the refractive-index modulation after the writing process. The holographic gratings are even stable at temperatures higher than the glass transition temperature, which further proves the light-induced formation of an ordered domain. In contrast to their polymeric counterparts, molecular materials are expected to show a faster response to light because of the absence of polymer chain entanglements. Therefore, molecular glasses can be used as blending material for photo-addressable polymers to improve the photo-sensitivity of the blend as compared to the pure polymer. The influence of the core and the substituent was investigated in low-molecular-weight compounds which do not form liquid-crystalline phases. An azobenzene-containing diblock copolymer for holographic data storage consists of an inert majority block and a minority block containing the covalently bound photo-sensitive azobenzene chromophores. Blending a few weight percent of the optimized molecular glass to the diblock copolymer leads to an increase of sensitivity with increasing content of the molecular glass, mainly because the writing time to the maximum of the refractive-index modulation decreased. The increase of the sensitivity is much larger than the observed rise of the refractive-index modulation due to the higher concentration of azobenzene chromophores. It was demonstrated that the shorter writing times are not caused by thermal effects, the molecules of the molecular glass in the inert block, or by changes of the free volume or the morphology, but that they are due to the azobenzene chromophores of the molecular glass in the minority block. They reorient faster than the chromophores attached to the polymer backbone and, thereby create free volume. Additionally, they can assist the reorientation of the azobenzene chromophores bound to the polymer by cooperative effects, i.e. dipolar and steric interactions. Both effects result in shorter writing time and higher sensitivity of the system. In a blend containing two weight percent of the molecular glass, the inscribed gratings are still long-term stable and the sensitivity increases by a factor of 1.7 as compared to the pure diblock copolymer. Upon illumination of an azobenzene-containing material with a holographic light grating, besides the volume grating, also a surface relief grating can develop. Surface modulations with heights of up to 600 nm were achieved in molecular glasses. It was found that the build-up of the surface relief grating depends on the electrical susceptibility of the material at the optical frequency of the laser and the polarization of the laser beams. These experimental findings are in agreement with the gradient force model. According to this theory, the macroscopic material transport results from the forces on the polarized material in the electrical field gradient caused by the holographic light grating. For many applications it is important that the holographically produced surface relief gratings can be transferred to polymer surfaces. Replica molding can be used to easily copy the surface modulations to e.g. polycarbonate.
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Modulation of Incommensurately Modulated Structures Studied by the Maximum Entropy Method
(2011)
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Li Liang
- In this thesis, modulated properties of incommensurately modulated crystals are studied by the Maximum Entropy Method (MEM). This was done exemplarily on the compounds Rubidium tetrachlorozincate and Chromium pyrophosphate. To do so, the MEM derived (3+1)-dimensional superspace electron density was analysed to receive information on atomic positions and their modulation, and structure refinement by the method of least-squares and interpretation of the difference-Fourier maps were performed to better describe the atomic displacement parameters (ADPs) and to improve the applied structural models. All the MEM calculations are done by the computer program BayMEM. The analysis of this MEM reconstructed density map is done by the computer program EDMA. Our results suggest that the modulation of harmonic ADPs, anharmonic ADPs and its modulation form an intrinsic part of incommensurately modulated structures. We have shown that with a data set of certain resolution and satellite reflections of higher order, the inclusion of modulation of harmonic ADPs, the anharmonic ADPs and the modulation of anharmonic ADPs can significantly improve the fit of the structure model to the diffraction data. Such model then better represents the true nature of the structure under investigation.
