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The aim of this thesis is to achieve a deep understanding of the working mechanism of polymer based solar cells and to improve the device performance. Two types of the polymer based solar cells are studied here: all-polymer solar cells comprising macromolecular donors and acceptors based on poly(p-phenylene vinylene) and hybrid cells comprising a PPV copolymer in combination with a novel small molecule electron acceptor. To understand the interplay between morphology and photovoltaic properties in all-polymer devices, I compared the photocurrent characteristics and excited state properties of bilayer and blend devices with different nano-morphology, which was fine tuned by using solvents with different boiling points. The main conclusion from these complementary measurements was that the performance-limiting step is the field-dependent generation of free charge carriers, while bimolecular recombination and charge extraction do not compromise device performance. These findings imply that the proper design of the donor-acceptor heterojunction is of major importance towards the goal of high photovoltaic efficiencies. Regarding polymer-small molecular hybrid solar cells I combined the hole-transporting polymer M3EH-PPV with a novel Vinazene-based electron acceptor. This molecule can be either deposited from solution or by thermal evaporation, allowing for a large variety of layer architectures to be realized. I then demonstrated that the layer architecture has a large influence on the photovoltaic properties. Solar cells with very high fill factors of up to 57 % and an open circuit voltage of 1V could be achieved by realizing a sharp and well-defined donor-acceptor heterojunction. In the past, fill factors exceeding 50 % have only been observed for polymers in combination with soluble fullerene-derivatives or nanocrystalline inorganic semiconductors as the electron-accepting component. The finding that proper processing of polymer-vinazene devices leads to similar high values is a major step towards the design of efficient polymer-based solar cells.
Distributed optimality
(2001)
In this thesis I propose a synthesis (Distributed Optimality, DO) between Optimality Theory (OT, Prince & Smolensky, 1993) and a morphological framework in a genuine derivational tradition, namely Distributed Morphology (DM) as developed by Halle & Marantz (1993). By carrying over the apparatus of OT to DM, phenomena which are captured in DM by language-specific rules or features of lexical entries, are given a more principled account in the terms of ranked universal constraints. On the other hand, also the DM part makes two contributions, namely strong locality and impoverishment. The first gives rise to a simple formal interpretation of DO, while the latter is shown to be indispensable in any theoretically satisfying account of agreement morphology. The empirical basis of the work is given by the complex agreement morphology of genetically different languages. Theoretical focus is mainly on two areas: First, so-called direction marking which is shown to be preferably treated in terms of constraints on feature realization. Second, the effects of precedence constraints which are claimed to regulate the status of agreement affixes as prefixes or suffixes and their respective order. A universal typology for the order of agreement categories by means of OT-constraints is proposed.
Die vorliegende Arbeit beschäftigt sich mit der Synthese und den Eigenschaften von linearen und verzweigten amphiphilen Polypeptid-Blockcopolymeren. Die Frage nach dem Einfluss der Topologie und Konformation der Blockcopolymere auf die supramolekularen und kolloidalen Eigenschaften bildete einen wichtigen Aspekt bei den Untersuchungen. Die Blockcopolymere wurden nach einem mehrstufigen Reaktionsschema durch Kombination von anionischer und ringöffnender Polymerisation von Aminosäuren-N-Carboxyanhydriden (NCA) synthetisiert. Die Untersuchung der Polypeptid-Blockcopolymere hinsichtlich ihres Aggregationsverhaltens in fester Phase sowie in verdünnter wässriger Lösung erfolgte mittels Streumethoden (SAXS, WAXS, DLS) sowie abbildender Methoden (TEM). Durch Einsatz der Blockcopolymere als polymere Stabilisatoren in der Emulsionspolymerisation wurden Oberflächen funktionalisierte Latizes erhalten. Als Beispiel für eine pharmazeutische Anwendung wurden bioverträgliche Polypeptid-Blockcopolymere als Wirkstoff-Trägersysteme in der Krebstherapie eingesetzt.