Charge generation and recombination in hybrid organic,inorganic solar cells

This thesis deals with the investigation of exciton and charge dynamics in hybrid solar cells by time-resolved optical spectroscopy. Quasi-steady-state and transient absorption spectroscopy, as well as time-resolved photoluminescence spectroscopy, were employed to study charge generation and recombination in solid-state organic dye-sensitized solar cells, where the commonly used liquid electrolyte is replaced by an organic solid hole transporter, namely 2,2′7,7′-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9′-spirobifluorene (spiro-MeOTAD), and polymer-metal oxide bulk heterojunction solar cells, where the commonly used fullerene acceptor [6,6]-phenyl C61 butyric acid methyl ester (PCBM) is replaced by zinc oxide (ZnO) nanoparticles. By correlating the spectroscopic results with the photovoltaic performance, efficiency-limiting processes and processes leading to photocurrent generation in the investigated systems are revealed. rnIt is shown that the charge generation from several all-organic donor-π-bridge-acceptor dyes, specifically perylene monoimide derivatives, employed in solid-state dye-sensitized solar cells, is strongly dependent on the presence of a commonly used additive lithium bis(trifluoromethanesulphonyl)imide salt (Li-TFSI) at the interface. rnMoreover, it is shown that charges can not only be generated by electron injection from the excited dye into the TiO2 acceptor and subsequent regeneration of the dye cation by the hole transporter, but also by an alternative mechanism, called preceding hole transfer (or reductive quenching). Here, the excited dye is first reduced by the hole transporter and the thereby formed anion subsequently injects an electron into the titania. This additional charge generation process, which is only possible for solid hole transporters, helps to overcome injection problems. rnHowever, a severe disadvantage of solid-state dye-sensitized solar cells is re-vealed by monitoring the transient Stark effect on dye molecules at the inter-face induced by the electric field between electrons and holes. The attraction between the negative image charge present in TiO2, which is induced by the positive charge carrier in the hole transporter due to the dielectric contrast between the organic spiro-MeOTAD and inorganic titania, is sufficient to at-tract the hole back to the interface, thereby increasing recombination and suppressing the extraction of free charges.rnBy investigating the effect of different dye structures and physical properties on charge generation and recombination, design rules and guidelines for the further advancement of solid-state dye-sensitized solar cells are proposed.rnFinally, a spectroscopic study on polymer:ZnO bulk heterojunction hybrid solar cells, employing different surfactants attached to the metal oxide nanoparticles, was performed to understand the effect of surfactants upon photovoltaic behavior. By applying a parallel pool analysis on the transient absorption data, it is shown that suppressing fast recombination while simultaneously maintaining the exciton splitting efficiency by the right choice of surfactants leads to better photovoltaic performances. Suppressing the fast recombination completely, whilst maintaining the exciton splitting, could lead to a doubling of the power conversion efficiency of this type of solar cell.

Abflussverhalten kleiner, forstlich genutzter Bacheinzugsgebiete am Beispiel des Einzugsgebietes des Oberen Gräfenbaches im Soonwald/Hunsrück

Die vorliegende Arbeit sollte weitere Erkenntnisse zum Abflussverhalten forstlich genutzter Standorte im Einzugsgebiet der Nahe liefern. Zu diesem Zweck wurde das 12,73 km² umfassenden Einzugsgebietes des Oberen Gräfenbaches als Untersuchungsgebiet ausgewählt, das im fast ausschließlich waldbestandenen Soonwald lokalisiert ist. Das Einzugsgebiet wurde ab 1999 mit einem hydrometeorologischen Messnetz ausgestattet. Zusammen mit Geländebeobachtungen des Abflussgeschehens und einer Aufnahme der physiogeographischen Gebietseigenschaften wurde eine Analyse des Abflussverhaltens möglich. Die Analysen umfassten die grundlegende quantitative Auswertung der erhobenen Zeitreihen mit Hilfe statistisch-mathematischer Verfahren und die Nachbildung der hydrologischen Prozesse mit Hilfe des Modells MMS/PRMS. Die räumliche Diskretisierung des Gebietes erfolgte dabei durch Ausweisung von Hydrological Response Units (HRUs). Die Nachbildung des Ist-Zustandes wurde durch Rechnung mehrerer Landnutzungsszenarien ergänzt. Die Untersuchungen zeigten die enorme Variabilität der Gebietsabflüsse bei insgesamt hohen Jahresabflussvolumina auf. Zwischen den einzelnen Hangbereichen bestehen dabei grundlegende Unterschiede, die sowohl die Abflussbildungsprozesse als auch den Abflussgang betreffen. Im Rahmen der Landnutzungsszenarien wurde aufbauend deutlich, dass sich eine Veränderung der forstlichen Bestandeszusammensetzung nur nachrangig auf die Abflussentstehung auswirkt.

Context-dependent interpretation of the conjunction 'und' in different age-groups

In contrast to formal semantics, the conjunction and is nonsymmetrical in pragmatics. The events in Marc went to bed and fell asleep seem to have occurred chronologically although no explicit time reference is given. As the temporal interpretation appears to be weaker in Mia ate chocolate and drank milk, it seems that the kind and nature of events presented in a context influences the interpretation of the conjunction. This work focuses on contextual influences on the interpretation of the German conjunction und (‘and’). A variety of theoretic approaches are concerned with whether and contributes to the establishment of discourse coherence via pragmatic processes or whether the conjunction has complex semantic meaning. These approaches are discussed with respect to how they explain the temporal and additive interpretation of the conjunction and the role of context in the interpre-tation process. It turned out that most theoretic approaches do not consider the importance of different kinds of context in the interpretation process.rnIn experimental pragmatics there are currently only very few studies that investigate the inter-pretation of the conjunction. As there are no studies that investigate contextual influences on the interpretation of und systematically or investigate preschoolers interpretation of the con-junction, research questions such as How do (preschool) children interpret ‘und’? and Does the kind of events conjoined influence children’s and adults’ interpretation? are yet to be answered. Therefore, this dissertation systematically investigates how different types of context influence children’s interpretation of und. Three auditory comprehension studies were conducted in German. Of special interest was whether and how the order of events introduced in a context contributes to the temporal read-ing of the conjunction und. Results indicate that the interpretation of und is – at least in Ger-man – context-dependent: The conjunction is interpreted temporally more often when events that typical occur in a certain order are connected (typical contexts) compared to events with-out typical event order (neutral contexts). This suggests that the type of events conjoined in-fluences the interpretation process. Moreover, older children and adults interpret the conjunc-tion temporally more often than the younger cohorts if the conjoined events typically occur in a certain order. In neutral contexts, additive interpretations increase with age. 5-year-olds reject reversed order statements more often in typical contexts compared to neutral contexts. However, they have more difficulties with reversed order statements in typical contexts where they perform at chance level. This suggests that not only the type of event but also other age-dependent factors such as knowledge about scripts influence children’s performance. The type of event conjoined influences children’s and adults’ interpretation of the conjunction. There-fore, the influence of different event types and script knowledge on the interpretation process does not only have to be considered in future experimental studies on language acquisition and pragmatics but also in experimental pragmatics in general. In linguistic theories, context has to be given a central role and a commonly agreed definition of context that considers the consequences arising from different event types has to be agreed upon.