a trimolecular composition

Photochemical upconversion based on triplet–triplet annihilation (TTA-UC) is employed to enhance the short-circuit currents generated by two varieties of thin-film solar cells, a hydrogenated amorphous silicon (a-Si:H) solar cell and a dye-sensitized solar cell (DSC). TTA-UC is exploited to harvest transmitted sub-bandgap photons, combine their energies and re-radiate upconverted photons back towards the solar cells. In the present study we employ a dual-emitter TTA-UC system which allows for significantly improved UC quantum yields as compared to the previously used single-emitter TTA systems. In doing so we achieve record photo-current enhancement values for both the a-Si:H device and the DSC, surpassing 10−3 mA cm−2 sun−2 for the first time for a TTA-UC system and marking a record for upconversion-enhanced solar cells in general. We discuss pertinent challenges of the TTA-UC technology which need to be addressed in order to achieve its viable device application

Increased upconversion performance for thin film solar cells: A trimolecular composition

Photochemical upconversion based on triplet-triplet annihilation (TTA-UC) is employed to enhance the short-circuit currents generated by two varieties of thin-film solar cells, a hydrogenated amorphous silicon (a-Si:H) solar cell and a dye-sensitized solar cell (DSC). TTA-UC is exploited to harvest transmitted sub-bandgap photons, combine their energies and re-radiate upconverted photons back towards the solar cells. In the present study we employ a dual-emitter TTA-UC system which allows for significantly improved UC quantum yields as compared to the previously used single-emitter TTA systems. In doing so we achieve record photo-current enhancement values for both the a-Si:H device and the DSC, surpassing 10-3 mA cm-2 sun-2 for the first time for a TTA-UC system and marking a record for upconversion-enhanced solar cells in general. We discuss pertinent challenges of the TTA-UC technology which need to be addressed in order to achieve its viable device application

Improving the light-harvesting of amorphous silicon solar cells with photochemical upconversion

Single-threshold solar cells are fundamentally limited by their ability to harvest only those photons above a certain energy. Harvesting below-threshold photons and re-radiating this energy at a shorter wavelength would thus boost the efficiency of such devices. We report an increase in light harvesting efficiency of a hydrogenated amorphous silicon (a-Si:H) thin-film solar cell due to a rear upconvertor based on sensitized triplet–triplet-annihilation in organic molecules. Low energy light in the range 600–750 nm is converted to 550–600 nm light due to the incoherent photochemical process. A peak efficiency enhancement of (1.0 ± 0.2)% at 720 nm is measured under irradiation equivalent to (48 ± 3) suns (AM1.5). We discuss the pathways to be explored in adapting photochemical UC for application in various single threshold devices

Improving the light-harvesting of second generation solar cells with photochemical upconversion

Photovoltaics (PV) offer a solution for the development of sustainable energy sources, relying on the sheer abundance of sunlight: More sunlight falls on the Earth’s surface in one hour than is required by its inhabitants in a year. However, it is imperative to manage the wide distribution of photon energies available in order to generate more cost efficient PV devices because single threshold PV devices are fundamentally limited to a maximum conversion efficiency, the Shockley-Queisser (SQ) limit. Recent progress has enabled the production of c-Si cells with efficiencies as high as 25%,1 close to the limiting efficiency of ∼30%. But these cells are rather expensive, and ultimately the cost of energy is determined by the ratio of system cost and efficiency of the PV device. A strategy to radically decrease this ratio is to circumvent the SQ limit in cheaper, second generation PV devices. One promising approach is the use of hydrogenated amorphous silicon (a-Si:H), where film thicknesses on the order of several 100nm are sufficient. Unfortunately, the optical threshold of a-Si:H is rather high (1.7-1.8 eV) and the material suffers from light-induced degradation. Thinner absorber layers in a-Si:H devices are generally more stable than thicker films due to the better charge carrier extraction, but at the expense of reduced conversion efficiencies, especially in the red part of the solar spectrum (absorption losses). Hence for higher bandgap materials, which includes a-Si as well as organic and dye-sensitized cells, the major loss mechanism is the inability to harvest low energy photons

Effect of a back reflector

Photochemical upconversion is applied to a hydrogenated amorphous silicon solar cell in the presence of a back-scattering layer. A custom-synthesized porphyrin was utilized as the sensitizer species, with rubrene as the emitter. Under a bias of 24 suns, a peak external quantum efficiency (EQE) enhancement of ~2 % was observed at a wavelength of 720 nm. Without the scattering layer, the EQE enhancement was half this value, indicating that the effect of the back-scatterer is to double the efficacy of the upconverting device. The results represent an upconversion figure of merit of 3.5 × 10–4 mA cm–2 sun–2, which is the highest reported to date

Measuring non-radiative relaxation time of fluorophores with biomedical applications by intensity-modulated laser-induced photoacoustic effect

Modulated tone-burst light was employed to measure non-radiative relaxation time of fluorophores with biomedical importance through photoacoustic effect. Non-radiative relaxation time was estimated through the frequency dependence of photoacoustic signal amplitude. Experiments were performed on solutions of new indocyanine green (IR-820), which is a near infrared dye and has biomedical applications, in two different solvents (water and dimethyl sulfoxide (DMSO)). A 1.5 times slower non-radiative relaxation for the solution of dye in DMSO was observed comparing with the aqueous solution. This result agrees well with general finding that non-radiative relaxation of molecules in triplet state depends on viscosity of solvents in which they are dissolved. Measurements of the non-radiative relaxation time can be used as a new source of contrast mechanism in photoacoustic imaging technique. The proposed method has potential applications such as imaging tissue oxygenation and mapping of other chemophysical differences in microenvironment of exogenous biomarkers

Einzelmolekülspektroskopische und quantenchemische Untersuchungen zum elektronischen Energietransfer

In der vorliegenden Arbeit wurden Untersuchungen zum Mechanismus, der Dynamik und der Kontrolle des elektronischen Energietransfers in multichromophoren Modellsystemen durchgeführt. Als Untersuchungsmethoden wurden hauptsächlich die konfokale Einzelmolekülspektroskopie und die Quantenchemie eingesetzt. Der Aufbau des Einzelmolekülmikroskops wurde bezüglich der Anregungs- und Detektionskomponenten variiert, um die unterschiedlichen Experimente durchzuführen. Die quantenchemischen Rechnungen wurden auf Dichtefunktional- und Coupled-Cluster-Niveau durchgeführt. Die aus den Rechnungen erhaltenen zusätzlichen Informationen über experimentell zum Teil schwer zugängliche Eigenschaften der Farbstoffe unterstützten die Interpretation der experimentellen Befunde. rnIn früheren Untersuchungen der AG Basché wurden die Energietransfer-Raten von Donor-Akzeptor-Systemen gemessen, die erhebliche Abweichungen von nach der Förster-Theorie berechneten Raten zeigten. Daher war ein Ziel der vorliegenden Arbeit, diese Abweichungen zu erklären. Zu diesem Zweck wurde die Geometrie der Diaden experimentell untersucht, sowie die elektronische Kopplung zwischen den Chromophoren quantenchemisch berechnet. Die relative Orientierung der Chromophore in den Diaden wurde in einem Einzelmolekül-Experiment mit rotierender Anregungspolarisation abgefragt. Die erhaltenen Winkelverteilungen konnten schließlich eindeutig auf die Flexibilität der die Chromophore verbrückenden Oligophenyl-Einheiten zurückgeführt werden. Die Unterschiede der gemessenen Energietransfer-Raten zu den nach der Förster-Theorie ermittelten Werten konnten jedoch nicht über die molekulare Flexibilität der Systeme erklärt werden. Aufklärung über die Diskrepanzen zur Förster-Theorie ergaben die quantenchemischen Rechnungen. In Rahmen dieser Arbeit wurde zum ersten Mal die Coupled-Cluster-Theorie zur Berechnung der elektronischen Kopplung eingesetzt. Die Betrachtung der isolierten Chromophore reichte aber nicht aus, um die gemessenen Abweichungen von der Förster-Theorie zu erklären. Erst über die Berücksichtigung der molekularen Brücke konnten die gefunden Abweichungen erklärt werden. Die deutliche Verstärkung der elektronischen Kopplung ist auf die Polarisierbarkeit der Brücke zurückzuführen.rnNach diesen Betrachtungen stand die Kontrolle des Energietransfers im Fokus der weiteren Untersuchungen. In den durchgeführten Einzelmolekülexperimenten wurden die Chromophore der Donor-Akzeptor-Systeme selektiv mit zwei Laserpulsen unterschiedlicher Wellenlänge angeregt. Beim gleichzeitigen Anregen beider Chromophore wurde Singulett-Singulett-Annihilation (SSA) induziert, ein Energietransferprozess, bei dem die Anregungsenergie vom vorigen Akzeptor zum vorigen Donor übertragen wird. Da über SSA Fluoreszenzphotonen gelöscht wurden, konnte über den Abstand der Laserpulse die Fluoreszenzintensität des einzelnen Moleküls moduliert werden. Konzeptionell verwandte Einzelmolekülexperimente wurden an einem weiteren molekularen System durchgeführt, das aus einem Kern und einer Peripherie bestand. Fluoreszenzauszeiten des Gesamtsystems bei selektiver Anregung des Kerns wurden auf die Population eines Triplett-Zustandes zurückgeführt, der die Fluoreszenz der Peripherie löschte. rnAbschließend wurde der SSA-Prozess zwischen zwei gleichartigen Chromophoren untersucht. Es wurde eine Methode entwickelt, die es zum ersten Mal erlaubte, die SSA-Zeitkonstante individueller Moleküle zu bestimmen. Hierfür wurden die Daten der gemessenen Photonen-Koinzidenzhistogramme mittels eines im Rahmen dieser Arbeit hergeleiteten analytischen Zusammenhangs ausgewertet, der über Monte-Carlo-Simulationen bestätigt wurde.The aim of the present work was the investigation of the mechanism, the dynamics and the control of electronic energy transfer processes in multichromophoric model systems. To reach these goals, confocal single molecule spectroscopy at room temperature as well as quantum chemical calculations were utilized. The excitation and detection pathways of the confocal microscope were varied to carry out the different experiments. For the quantum chemical calculations coupled-cluster and density functional theory were used. The results of the calculations supported and complemented the experimental findings. rnExperiments on single donor-acceptor dyads preceding this work showed that the measured energy transfer rates deviate substantially from rates calculated via Förster’s theory of energy transfer. Thus one goal of the present dissertation was to investigate these deviations. For this purpose the molecular geometry and the electronic coupling in the dyads were investigated. The relative orientation of the chromophores was studied by single molecule experiments with rotating excitation polarisation. Eventually the resulting distributions of angles unambiguously could be ascribed to the flexibility of the oligophenylene bridges connecting the chromophores. The deviations of the measured energy transfer rates from Förster theory, however, could not be explained with the molecular flexibility. The quantum chemical calculations clarified this point. Here, for the first time coupled-cluster theory was used to calculate the electronic coupling between two chromophores. Taking into account the isolated chromophores only, however, could not explain the measured deviations from Förster theory. Consideration of the influence of the molecular bridge on the electronic coupling strength explained the discrepancies of measured rates and Förster theory. The drastic enhancement of the electronic coupling is attributed to the polarizability of the molecular bridge.rnThe next step was the control of the energy transfer process. The chromophores of the investigated individual dyad molecules were selectively excited by two laser pulses of different wavelengths. Simultaneous excitation of both chromophores induced singlet-singlet annihilation (SSA), an electronic energy transfer process whereby the energy was transferred from the former acceptor to the former donor chromophore. Since the SSA process quenched fluorescence, the fluorescence intensity of the single molecule could be modulated by changing the time delay between the two pulses. Related experiments were carried out on a molecular system that consisted of a core and a periphery. Fluorescence off-times of the molecule upon selective excitation of the core were ascribed to formation of a core triplet state which quenches the fluorescence of the periphery.rnThe last experiment investigated the SSA process between two chemically identical chromophores. A method was derived to quantify the SSA time constants of individual molecules. The recorded photon coincidence histograms were evaluated with an analytical expression. The method was validated via Monte Carlo simulations

Wählen im räumlichen Kontext : eine empirische Untersuchung zum Einfluss der sozialen Komposition des Wahlkreises auf die individuelle Wahlentscheidung bei der Bundestagswahl 2009

Die meisten Studien der empirischen Wahlforschung führen das Wählverhalten bei deutschen Bundestagswahlen gemäß den bewährten Erklärungsansätzen (Columbia School, Cleavage-Theorie, Michigan School, …) auf Faktoren der Individualebene zurück. Nur wenige analysieren darüber hinaus den Einfluss räumlicher Kontextmerkmale. Diese Beiträge gelangen zudem zu widersprüchlichen Befunden, z.B. darüber, welcher Anteil der Gesamtvarianz überhaupt durch Kontextfaktoren erklärt werden kann. Daher will die vorliegende Arbeit klären, inwiefern die soziale Komposition des räumlichen Kontexts über individuelle Merkmale der Wähler hinaus ihre individuelle Wahlentscheidung bei der Bundestagswahl 2009 beeinflusst hat. Dazu wird zunächst ein räumliches Mehrebenen-Modell des individuellen Wahlverhaltens entwickelt, das den Einfluss von Kontextmerkmalen u.a. auf soziale Interaktionsmechanismen innerhalb der Kontexteinheiten zurückführt. Zudem werden die zentralen individuellen Erklärungsfaktoren der oben genannten Theorien (Parteiidentifikation, Kandidaten-, Sachfragen-Orientierung, soziale Gruppenzugehörigkeit) in das Modell integriert. Auf Grundlage von Daten der German Longitudinal Election Study werden anschließend logistische Mehrebenen-Modelle für die alten und erstmals auch für die neuen Bundesländer und Deutschland geschätzt. Erstmals werden zudem Wahlkreise als relevante Kontexteinheiten untersucht. Es zeigt sich, dass ein kleiner Teil der Varianz der individuellen Wahlentscheidung allein auf Merkmale des Wahlkreises zurückgeführt werden kann. Es treten sowohl direkte Kontexteffekte als auch Mehrebenen-Interaktionseffekte auf, die sich jedoch in ihrer Wirkung zwischen den Regionen und auch zwischen den Parteien erheblich unterscheiden.Most empirical studies of voting behavior explain vote choice at German federal elections using individual level variables referring on established theories of voting behavior (Columbia School, Cleavage Theory, Michigan School, ...). Only a few analyze in addition to them specific effects of the geographical context that surrounds the voters. On top of that these studies produce contradictory results, e.g. about how much of the total variance can be explained by contextual factors. That is why this study seeks to analyze if the social composition of the geographical context of voters had a particular effect on their vote choice in addition to their most important individual characteristics at the German federal election 2009. For that purpose first of all a geographical multilevel-model of vote choice is generated that explains contextual effects among other mechanisms by social interactions among the voters inside the contextual units controlling for the most important individual level factors mentioned by the theories above (party identification, candidate-, issue-orientation, social group membership). Using data of the German Longitudinal Election Study logistic multilevel-models for West- and for the first time for East-Germany and Germany are estimated. Equally for the first time electoral districts are analyzed as the relevant units of the context level. The results show that a small part of the variance of individual vote choice can be explained particularly by characteristics of the electoral districts. Not only direct context effects but also cross-level- interactions can be found. But their strength of influence differs as well between the analyzed regions as between the analyzed parties

The spectroscopy and thermochemistry of phenylallyl radical chromophores

The resonant two-color two-photon ionization and laser induced fluorescence excitation spectra of the 1-phenylallyl (cinnamyl) and inden-2-ylmethyl radicals are reported. The 1-phenylallyl radical is found to fluoresce with low yield, permitting only a coarse dispersed fluorescence spectrum, while the inden-2-ylmethyl radical yields sufficient fluorescence to obtain ground-state vibrational frequencies and two-dimensional fluorescence spectra. Computed ionization energies and thermochemical properties including radical stabilization energies are reported for a range of resonance-stabilized radicals, including the phenylpropargyl, vinylpropargyl and phenylallyl radicals