Nanoscopic studies of conjugated polymer blends by (electric) scanning probe microscopy

Conjugated polymers and conjugated polymer blends have attracted great interest due to their potential applications in biosensors and organic electronics. The sub-100 nm morphology of these materials is known to heavily influence their electromechanical properties and the performance of devices they are part of. Electromechanical properties include charge injection, transport, recombination, and trapping, the phase behavior and the mechanical robustness of polymers and blends. Electrical scanning probe microscopy techniques are ideal tools to measure simultaneously electric (conductivity and surface potential) and dielectric (dielectric constant) properties, surface morphology, and mechanical properties of thin films of conjugated polymers and their blends.rnIn this thesis, I first present a combined topography, Kelvin probe force microscopy (KPFM), and scanning conductive torsion mode microscopy (SCTMM) study on a gold/polystyrene model system. This system is a mimic for conjugated polymer blends where conductive domains (gold nanoparticles) are embedded in a non-conductive matrix (polystyrene film), like for polypyrrole:polystyrene sulfonate (PPy:PSS), and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). I controlled the nanoscale morphology of the model by varying the distribution of gold nanoparticles in the polystyrene films. I studied the influence of different morphologies on the surface potential measured by KPFM and on the conductivity measured by SCTMM. By the knowledge I gained from analyzing the data of the model system I was able to predict the nanostructure of a homemade PPy:PSS blend.rnThe morphologic, electric, and dielectric properties of water based conjugated polymer blends, e.g. PPy:PSS or PEDOT:PSS, are known to be influenced by their water content. These properties also influence the macroscopic performance when the polymer blends are employed in a device. In the second part I therefore present an in situ humidity-dependence study on PPy:PSS films spin-coated and drop-coated on hydrophobic highly ordered pyrolytic graphite substrates by KPFM. I additionally used a particular KPFM mode that detects the second harmonic electrostatic force. With this, I obtained images of dielectric constants of samples. Upon increasing relative humidity, the surface morphology and composition of the films changed. I also observed that relative humidity affected thermally unannealed and annealed PPy:PSS films differently. rnThe conductivity of a conjugated polymer may change once it is embedded in a non-conductive matrix, like for PPy embedded in PSS. To measure the conductivity of single conjugated polymer particles, in the third part, I present a direct method based on microscopic four-point probes. I started with metal core-shell and metal bulk particles as models, and measured their conductivities. The study could be extended to measure conductivity of single PPy particles (core-shell and bulk) with a diameter of a few micrometers.

Intra- and interspecific competition in western barbastelle bats (Barbastella barbastellus, SCHREBER 1774)

In the present thesis I examined individual and sex-specific habitat use and site fidelity in the western barbastelle bat, Barbastella barbastellus, using data from a four-year monitoring in a Special Area of Conservation in Rhineland-Palatinate, Germany. The western barbastelle occurs in central and southern Europe from Portugal to the Caucasus, but is considered to be rare in large parts of its range. Up to now, long-term field studies to assess interannual site fidelity and the possible effects of intra- and interspecific competition have not been studied in this species. Nevertheless, such data provide important details to estimate the specific spatial requirements of its populations, which in turn can be incorporated in extended conservation actions. I used radio-telemetry, home range analyses und automated ultrasound detection to assess the relation between landscape elements and western barbastelle bats and their roosts. In addition, I estimated the degree of interspecific niche overlap with two selected forest-dwelling bat species, Bechstein's bat (Myotis bechsteinii) and the brown long-eared bat (Plecotus auritus). Intra- and interannual home range overlap analyses of female B. barbastellus revealed that fidelity to individual foraging grounds, i.e. a traditional use of particular sites, seems to effect the spatial distribution of home ranges more than intraspecific competition among communally roosting females. The results of a joint analysis of annual maternity roost selection and flight activities along commuting corridors highlight the necessity to protect roost complexes in conjunction with commuting corridors. Using radio-tracking data and an Euclidean distance approach I quantified the sex-specific and individual habitat use by female and male western barbastelle bats within their home ranges. My data indicated a partial sexual segregation in summer habitats. Females were found in deciduous forest patches and preferably foraged along linear elements within the forest. Males foraged closer to forest edges and in open habitats. Finally, I examined the resource partitioning between the western barbastelle bat and two syntopic bat species with a potential for interspecific competition due to similarities in foraging strategies, prey selection and roost preferences. Simultaneous radio-tracking of mixed-species pairs revealed a partial spatial separation of the three syntopic bat species along a gradient from the forest to edge habitats and open landscape. Long-eared bats were found close to open habitats which were avoided by the other two species. B. barbastellus preferred linear landscape elements (edge habitats) and forests, M. bechsteinii also preferred forest habitats. Only little overlap in terms of roost structure and tree species selection was found.

Ein inverses Rückstreuproblem der elektrischen Impedanztomographie

Die vorliegende Arbeit untersucht das inverse Hindernisproblem der zweidimensionalen elektrischen Impedanztomographie (EIT) mit Rückstreudaten. Wir präsentieren und analysieren das mathematische Modell für Rückstreudaten, diskutieren das inverse Problem für einen einzelnen isolierenden oder perfekt leitenden Einschluss und stellen zwei Rekonstruktionsverfahren für das inverse Hindernisproblem mit Rückstreudaten vor. Ziel des inversen Hindernisproblems der EIT ist es, Inhomogenitäten (sogenannte Einschlüsse) der elektrischen Leitfähigkeit eines Körpers aus Strom-Spannungs-Messungen an der Körperoberfläche zu identifizieren. Für die Messung von Rückstreudaten ist dafür nur ein Paar aus an der Körperoberfläche nahe zueinander angebrachten Elektroden nötig, das zur Datenerfassung auf der Oberfläche entlang bewegt wird. Wir stellen ein mathematisches Modell für Rückstreudaten vor und zeigen, dass Rückstreudaten die Randwerte einer außerhalb der Einschlüsse holomorphen Funktion sind. Auf dieser Grundlage entwickeln wir das Konzept des konvexen Rückstreuträgers: Der konvexe Rückstreuträger ist eine Teilmenge der konvexen Hülle der Einschlüsse und kann daher zu deren Auffindung dienen. Wir stellen einen Algorithmus zur Berechnung des konvexen Rückstreuträgers vor und demonstrieren ihn an numerischen Beispielen. Ferner zeigen wir, dass ein einzelner isolierender Einschluss anhand seiner Rückstreudaten eindeutig identifizierbar ist. Der Beweis dazu beruht auf dem Riemann'schen Abbildungssatz für zweifach zusammenhängende Gebiete und dient als Grundlage für einen Rekonstruktionsalgorithmus, dessen Leistungsfähigkeit wir an verschiedenen Beispielen demonstrieren. Ein perfekt leitender Einschluss ist hingegen nicht immer aus seinen Rückstreudaten rekonstruierbar. Wir diskutieren, in welchen Fällen die eindeutige Identifizierung fehlschlägt und zeigen Beispiele für unterschiedliche perfekt leitende Einschlüsse mit gleichen Rückstreudaten.