TY - JOUR A1 - Cherstvy, Andrey G. T1 - Electrostatics and charge regulation in polyelectrolyte multi layered assembly JF - The journal of physical chemistry : B, Condensed matter, materials, surfaces, interfaces & biophysical chemistry N2 - We examine the implications of electrostatic interactions on formation of polyelectrolyte multilayers, in application to field-effect based biosensors for label-free detection of charged macromolecules. We present a quantitative model to describe the experimental potentiometric observations and discuss its possibilities and limitations for detection of polyelectrolyte adsorption. We examine the influence of the ionic strength and pH on the sensor response upon polyelectrolyte layer-by-layer formation. The magnitude of potential oscillations on the sensor-electrolyte interface predicted upon repetitive adsorption charge-alternating polymers agrees satisfactorily with experimental results. The model accounts for different screening by mobile ions in electrolyte and inside tightly interdigitated multilayered structure. In particular, we show that sensors' potential oscillations are larger and more persistent at lower salt conditions, while they decay faster with the number of layers at higher salt conditions, in agreement with experiments. The effects of polyelectrolyte layer thickness, substrate potential, and charge regulation on the sensor surface triggered by layer-by-layer deposition are also analyzed. Y1 - 2014 U6 - https://doi.org/10.1021/jp502460v SN - 1520-6106 VL - 118 IS - 17 SP - 4552 EP - 4560 PB - American Chemical Society CY - Washington ER - TY - THES A1 - Schubert, Marcel T1 - Elementary processes in layers of electron transporting Donor-acceptor copolymers : investigation of charge transport and application to organic solar cells T1 - Elementare Prozesse in Schichten elektronen-transportierender Donator-Akzeptor-Copolymere : Untersuchung des Ladungstransports und Anwendung in Organischen Solarzellen N2 - Donor-acceptor (D-A) copolymers have revolutionized the field of organic electronics over the last decade. Comprised of a electron rich and an electron deficient molecular unit, these copolymers facilitate the systematic modification of the material's optoelectronic properties. The ability to tune the optical band gap and to optimize the molecular frontier orbitals as well as the manifold of structural sites that enable chemical modifications has created a tremendous variety of copolymer structures. Today, these materials reach or even exceed the performance of amorphous inorganic semiconductors. Most impressively, the charge carrier mobility of D-A copolymers has been pushed to the technologically important value of 10 cm^{2}V^{-1}s^{-1}. Furthermore, owed to their enormous variability they are the material of choice for the donor component in organic solar cells, which have recently surpassed the efficiency threshold of 10%. Because of the great number of available D-A copolymers and due to their fast chemical evolution, there is a significant lack of understanding of the fundamental physical properties of these materials. Furthermore, the complex chemical and electronic structure of D-A copolymers in combination with their semi-crystalline morphology impede a straightforward identification of the microscopic origin of their superior performance. In this thesis, two aspects of prototype D-A copolymers were analysed. These are the investigation of electron transport in several copolymers and the application of low band gap copolymers as acceptor component in organic solar cells. In the first part, the investigation of a series of chemically modified fluorene-based copolymers is presented. The charge carrier mobility varies strongly between the different derivatives, although only moderate structural changes on the copolymers structure were made. Furthermore, rather unusual photocurrent transients were observed for one of the copolymers. Numerical simulations of the experimental results reveal that this behavior arises from a severe trapping of electrons in an exponential distribution of trap states. Based on the comparison of simulation and experiment, the general impact of charge carrier trapping on the shape of photo-CELIV and time-of-flight transients is discussed. In addition, the high performance naphthalenediimide (NDI)-based copolymer P(NDI2OD-T2) was characterized. It is shown that the copolymer posses one of the highest electron mobilities reported so far, which makes it attractive to be used as the electron accepting component in organic photovoltaic cells.\par Solar cells were prepared from two NDI-containing copolymers, blended with the hole transporting polymer P3HT. I demonstrate that the use of appropriate, high boiling point solvents can significantly increase the power conversion efficiency of these devices. Spectroscopic studies reveal that the pre-aggregation of the copolymers is suppressed in these solvents, which has a strong impact on the blend morphology. Finally, a systematic study of P3HT:P(NDI2OD-T2) blends is presented, which quantifies the processes that limit the efficiency of devices. The major loss channel for excited states was determined by transient and steady state spectroscopic investigations: the majority of initially generated electron-hole pairs is annihilated by an ultrafast geminate recombination process. Furthermore, exciton self-trapping in P(NDI2OD-T2) domains account for an additional reduction of the efficiency. The correlation of the photocurrent to microscopic morphology parameters was used to disclose the factors that limit the charge generation efficiency. Our results suggest that the orientation of the donor and acceptor crystallites relative to each other represents the main factor that determines the free charge carrier yield in this material system. This provides an explanation for the overall low efficiencies that are generally observed in all-polymer solar cells. N2 - Donator-Akzeptor (D-A) Copolymere haben das Feld der organischen Elektronik revolutioniert. Bestehend aus einer elektronen-reichen und einer elektronen-armen molekularen Einheit,ermöglichen diese Polymere die systematische Anpassung ihrer optischen und elektronischen Eigenschaften. Zu diesen zählen insbesondere die optische Bandlücke und die Lage der Energiezustände. Dabei lassen sie sich sehr vielseitig chemisch modifizieren, was zu einer imensen Anzahl an unterschiedlichen Polymerstrukturen geführt hat. Dies hat entscheidend dazu beigetragen, dass D-A-Copolymere heute in Bezug auf ihren Ladungstransport die Effizienz von anorganischen Halbleitern erreichen oder bereits übetreffen. Des Weiteren lassen sich diese Materialien auch hervorragend in Organischen Solarzellen verwenden, welche jüngst eine Effizienz von über 10% überschritten haben. Als Folge der beträchtlichen Anzahl an unterschiedlichen D-A-Copolymeren konnte das physikalische Verständnis ihrer Eigenschaften bisher nicht mit dieser rasanten Entwicklung Schritt halten. Dies liegt nicht zuletzt an der komplexen chemischen und mikroskopischen Struktur im Film, in welchem die Polymere in einem teil-kristallinen Zustand vorliegen. Um ein besseres Verständnis der grundlegenden Funktionsweise zu erlangen, habe ich in meiner Arbeit sowohl den Ladungstransport als auch die photovoltaischen Eigenschaften einer Reihe von prototypischen, elektronen-transportierenden D-A Copolymeren beleuchtet. Im ersten Teil wurden Copolymere mit geringfügigen chemischen Variationen untersucht. Diese Variationen führen zu einer starken Änderung des Ladungstransportverhaltens. Besonders auffällig waren hier die Ergebnisse eines Polymers, welches sehr ungewöhnliche transiente Strom-Charakteristiken zeigte. Die nähere Untersuchung ergab, dass in diesem Material elektrisch aktive Fallenzustände existieren. Dieser Effekt wurde dann benutzt um den Einfluss solcher Fallen auf transiente Messung im Allgemeinen zu beschreiben. Zusätzlich wurde der Elektronentransport in einem neuartigen Copolymer untersucht, welche die bis dato größte gemesse Elektronenmobilität für konjugierte Polymere zeigte. Darauf basierend wurde versucht, die neuartigen Copolymere als Akzeptoren in Organischen Solarzellen zu implementieren. Die Optimierung dieser Zellen erwies sich jedoch als schwierig, konnte aber erreicht werden, indem die Lösungseigenschaften der Copolymere untersucht und systematisch gesteuert wurden. Im Weiteren werden umfangreiche Untersuchungen zu den relevanten Verlustprozessen gezeigt. Besonders hervorzuheben ist hier die Beobachtung, dass hohe Effizienzen nur bei einer coplanaren Packung der Donator/Akzeptor-Kristalle erreicht werden können. Diese Struktureigenschaft wird hier zum ersten Mal beschrieben und stellt einen wichtigen Erkenntnisgewinn zum Verständnis von Polymersolarzellen dar. KW - Organische Solarzellen KW - Ladungstransport KW - Donator-Akzeptor-Copolymere KW - Alternative Akzeptorpolymere KW - Polymer-Kristalle KW - organic solar cells KW - charge transport KW - Donor-acceptor copolymers KW - alternative electron acceptors KW - polymer crystal orientation Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus-70791 ER - TY - THES A1 - Lange, Ilja T1 - Energetische Struktur von Schichten organischer Halbleiter und ihr fundamentaler Einfluss auf die physikalischen Eigenschaften organischer elektronischer Bauteile Y1 - 2014 ER - TY - JOUR A1 - Fang, X. A1 - Guerrero, Martín A. A1 - Marquez-Lugo, R. A. A1 - Toala, Jesús Alberto A1 - Arthur, S. J. A1 - Chu, Y.-H. A1 - Blair, William P. A1 - Gruendl, R. A. A1 - Hamann, Wolf-Rainer A1 - Oskinova, Lidia M. A1 - Todt, Helge Tobias T1 - Expansion of hydrogen-poor knots in the born-again planetary nebulae A30 and A78 JF - The astrophysical journal : an international review of spectroscopy and astronomical physics N2 - We analyze the expansion of hydrogen-poor knots and filaments in the born-again planetary nebulae A30 and A78 based on Hubble Space Telescope ( HST) images obtained almost 20 yr apart. The proper motion of these features generally increases with distance to the central star, but the fractional expansion decreases, i.e., the expansion is not homologous. As a result, there is not a unique expansion age, which is estimated to be 610-950 yr for A30 and 600-1140 yr for A78. The knots and filaments have experienced complex dynamical processes: the current fast stellar wind is mass loaded by the material ablated from the inner knots; the ablated material is then swept up until it shocks the inner edges of the outer, hydrogen-rich nebula. The angular expansion of the outer filaments shows a clear dependence on position angle, indicating that the interaction of the stellar wind with the innermost knots channels the wind along preferred directions. The apparent angular expansion of the innermost knots seems to be dominated by the rocket effect of evaporating gas and by the propagation of the ionization front inside them. Radiation-hydrodynamical simulations show that a single ejection of material followed by a rapid onset of the stellar wind and ionizing flux can reproduce the variety of clumps and filaments at different distances from the central star found in A30 and A78. KW - ISM: kinematics and dynamics KW - planetary nebulae: individual (A30 and A78) Y1 - 2014 U6 - https://doi.org/10.1088/0004-637X/797/2/100 SN - 0004-637X SN - 1538-4357 VL - 797 IS - 2 PB - IOP Publ. Ltd. CY - Bristol ER - TY - JOUR A1 - Chu, X. -L. A1 - Brenner, Thomas J. K. A1 - Chen, X. -W. A1 - Ghosh, Y. A1 - Hollingsworth, J. A. A1 - Sandoghdar, Vahid A1 - Goetzinger, S. T1 - Experimental realization of an optical antenna designed for collecting 99% of photons from a quantum emitter JF - Optica N2 - A light source that emits single photons at well-defined times and into a well-defined mode would be a decisive asset for quantum information processing, quantum metrology, and sub-shot-noise detection of absorption. One of the central challenges in the realization of such a deterministic device based on a single quantum emitter concerns the collection of the photons, which are radiated into a 4 pi solid angle. Here, we present the fabrication and characterization of an optical antenna designed to convert the dipolar radiation of an arbitrarily oriented quantum emitter to a directional beam with more than 99% efficiency. Our approach is extremely versatile and can be used for more efficient detection of nanoscopic emitters ranging from semiconductor quantum dots to dye molecules, color centers, or rare-earth ions in various environments. Having addressed the issue of collection efficiency, we also discuss the photophysical limitations of the existing quantum emitters for the realization of a deterministic single-photon source. (C) 2014 Optical Society of America Y1 - 2014 U6 - https://doi.org/10.1364/OPTICA.1.000203 SN - 2334-2536 VL - 1 IS - 4 SP - 203 EP - 208 PB - Optical Society of America CY - Washington ER - TY - JOUR A1 - Cui, Qianling A1 - Shen, Guizhi A1 - Yan, Xuehai A1 - Li, Lidong A1 - Moehwald, Helmuth A1 - Bargheer, Matias T1 - Fabrication of Au@Pt multibranched nanoparticles and their application to in situ SERS monitoring JF - ACS applied materials & interfaces N2 - Here, we present an Au@Pt core-shell multibranched nanoparticle as a new substrate capable of in situ surface-enhanced Raman scattering (SERS), thereby enabling monitoring of the catalytic reaction on the active surface. By careful control of the amount of Pt deposited bimetallic Au@Pt, nanoparticles with moderate performance both for SERS and catalytic activity were obtained. The Pt-catalyzed reduction of 4-nitrothiophenol by borohydride was chosen as the model reaction. The intermediate during the reaction was captured and clearly identified via SERS spectroscopy. We established in situ SERS spectroscopy as a promising and powerful technique to investigate in situ reactions taking place in heterogeneous catalysis. KW - nanoparticles KW - gold KW - core-shell nanostructure KW - surface-enhanced Raman scattering KW - heterogeneous catalysis KW - bimetallic nanoparticles Y1 - 2014 U6 - https://doi.org/10.1021/am504709a SN - 1944-8244 VL - 6 IS - 19 SP - 17075 EP - 17081 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Cui, Qianling A1 - Yashchenok, Alexey A1 - Zhang, Lu A1 - Li, Lidong A1 - Masic, Admir A1 - Wienskol, Gabriele A1 - Moehwald, Helmuth A1 - Bargheer, Matias T1 - Fabrication of Bifunctional Gold/Gelatin Hybrid Nanocomposites and Their Application JF - ACS applied materials & interfaces N2 - Herein, a facile method is presented to integrate large gold nanoflowers (similar to 80 nm) and small gold nanoparticles (2-4 nm) into a single entity, exhibiting both surface-enhanced Raman scattering (SERS) and catalytic activity. The as-prepared gold nanoflowers were coated by a gelatin layer, in which the gold precursor was adsorbed and in situ reduced into small gold nanoparticles. The thickness of the gelatin shell is controlled to less than 10 nm, ensuring that the small gold nanoparticles are still in a SERS-active range of the inner Au core. Therefore, the reaction catalyzed by these nanocomposites can be monitored in situ using label-free SERS spectroscopy. In addition, these bifunctional nanocomposites are also attractive candidates for application in SERS monitoring of bioreactions because of their excellent biocompatibility. KW - core-shell nanostructure KW - gold KW - hybrid material KW - gelatin KW - nanoparticles KW - surface-enhanced Raman scattering Y1 - 2014 U6 - https://doi.org/10.1021/am5000068 SN - 1944-8244 VL - 6 IS - 3 SP - 1999 EP - 2002 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Krüsemann, Henning A1 - Godec, Aljaz A1 - Metzler, Ralf T1 - First-passage statistics for aging diffusion in systems with annealed and quenched disorder JF - Physical review : E, Statistical, nonlinear and soft matter physics N2 - Aging, the dependence of the dynamics of a physical process on the time t(a) since its original preparation, is observed in systems ranging from the motion of charge carriers in amorphous semiconductors over the blinking dynamics of quantum dots to the tracer dispersion in living biological cells. Here we study the effects of aging on one of the most fundamental properties of a stochastic process, the first-passage dynamics. We find that for an aging continuous time random walk process, the scaling exponent of the density of first-passage times changes twice as the aging progresses and reveals an intermediate scaling regime. The first-passage dynamics depends on t(a) differently for intermediate and strong aging. Similar crossovers are obtained for the first-passage dynamics for a confined and driven particle. Comparison to the motion of an aged particle in the quenched trap model with a bias shows excellent agreement with our analytical findings. Our results demonstrate how first-passage measurements can be used to unravel the age t(a) of a physical system. Y1 - 2014 U6 - https://doi.org/10.1103/PhysRevE.89.040101 SN - 1539-3755 SN - 1550-2376 VL - 89 IS - 4 PB - American Physical Society CY - College Park ER - TY - JOUR A1 - Abramowski, Attila A1 - Aharonian, Felix A. A1 - Benkhali, Faical Ait A1 - Akhperjanian, A. G. A1 - Angüner, Ekrem Oǧuzhan A1 - Anton, Gisela A1 - Balenderan, Shangkari A1 - Balzer, Arnim A1 - Barnacka, Anna A1 - Becherini, Yvonne A1 - Tjus, J. Becker A1 - Bernlöhr, K. A1 - Birsin, E. A1 - Bissaldi, E. A1 - Biteau, Jonathan A1 - Boettcher, Markus A1 - Boisson, Catherine A1 - Bolmont, J. A1 - Bordas, Pol A1 - Brucker, J. A1 - Brun, Francois A1 - Brun, Pierre A1 - Bulik, Tomasz A1 - Carrigan, Svenja A1 - Casanova, Sabrina A1 - Cerruti, M. A1 - Chadwick, Paula M. A1 - Chalme-Calvet, R. A1 - Chaves, Ryan C. G. A1 - Cheesebrough, A. A1 - Chretien, M. A1 - Colafrancesco, Sergio A1 - Cologna, Gabriele A1 - Conrad, Jan A1 - Couturier, C. A1 - Cui, Y. A1 - Dalton, M. A1 - Daniel, M. K. A1 - Davids, I. D. A1 - Degrange, B. A1 - Deil, C. A1 - dewilt, P. A1 - Dicldnson, H. J. A1 - Djannati-Ataï, A. A1 - Domainko, W. A1 - Dubus, G. A1 - Dutson, K. A1 - Dyks, J. A1 - Dyrda, M. A1 - Edwards, T. A1 - Egberts, Kathrin A1 - Eger, P. A1 - Espigat, P. A1 - Farnier, C. A1 - Fegan, S. A1 - Feinstein, F. A1 - Fernandes, M. V. A1 - Fernandez, D. A1 - Fiasson, A. A1 - Fontaine, G. A1 - Foerster, A. A1 - Fuessling, M. A1 - Gajdus, M. A1 - Gallant, Y. A. A1 - Garrigoux, T. A1 - Giavitto, G. A1 - Giebels, B. A1 - Glicenstein, J. F. A1 - Grondin, M. -H. A1 - Grudzinska, M. A1 - Haeffner, S. A1 - Hahn, J. A1 - Harris, J. A1 - Heinzelmann, G. A1 - Henri, G. A1 - Hermann, G. A1 - Hervet, O. A1 - Hillert, A. A1 - Hinton, James Anthony A1 - Hofmann, W. A1 - Hofverberg, P. A1 - Holler, M. A1 - Horns, D. A1 - Jacholkowska, A. A1 - Jahn, C. A1 - Jamrozy, M. A1 - Janiak, M. A1 - Jankowsky, F. A1 - Jung, I. A1 - Kastendieck, M. A. A1 - Katarzynski, K. A1 - Katz, U. A1 - Kaufmann, S. A1 - Khelifi, B. A1 - Kieffer, M. A1 - Klepser, S. A1 - Klochkov, D. A1 - Kluzniak, W. A1 - Kneiske, T. A1 - Kolitzus, D. A1 - Komin, Nu. A1 - Kosack, K. A1 - Krakau, S. A1 - Krayzel, F. A1 - Krueger, P. P. A1 - Laffon, H. A1 - Lamanna, G. A1 - Lefaucheur, J. A1 - Lemiere, A. A1 - Lemoine-Goumard, M. A1 - Lenain, J. -P. A1 - Lennarz, D. A1 - Lohse, T. A1 - Lopatin, A. A1 - Lu, C. -C. A1 - Marandon, V. A1 - Marcowith, Alexandre A1 - Marx, R. A1 - Maurin, G. A1 - Maxted, N. A1 - Mayer, M. A1 - McComb, T. J. L. A1 - Mehault, J. A1 - Meintjes, P. J. A1 - Menzler, U. A1 - Meyer, M. A1 - Moderski, R. A1 - Mohamed, M. A1 - Moulin, Emmanuel A1 - Murach, T. A1 - Naumann, C. L. A1 - de Naurois, M. A1 - Niemiec, J. A1 - Nolan, S. J. A1 - Oakes, L. A1 - Ohm, S. A1 - Wilhelmi, E. de Ona A1 - Opitz, B. A1 - Ostrowski, M. A1 - Oya, I. A1 - Panter, M. A1 - Parsons, R. D. A1 - Arribas, M. Paz A1 - Pekeur, N. W. A1 - Pelletier, G. A1 - Perez, J. A1 - Petrucci, P. -O. A1 - Peyaud, B. A1 - Pita, S. A1 - Poon, H. A1 - Puehlhofer, G. A1 - Punch, M. A1 - Quirrenbach, A. A1 - Raab, S. A1 - Raue, M. A1 - Reimer, A. A1 - Reimer, O. A1 - Renaud, M. A1 - Reyes, R. de Los A1 - Rieger, F. A1 - Rob, L. A1 - Romoli, C. A1 - Rosier-Lees, S. A1 - Rowell, G. A1 - Rudak, B. A1 - Rulten, C. B. A1 - Sahakian, V. A1 - Sanchez, David M. A1 - Santangelo, Andrea A1 - Schlickeiser, R. A1 - Schuessler, F. A1 - Schulz, A. A1 - Schwanke, U. A1 - Schwarzburg, S. A1 - Schwemmer, S. A1 - Sol, H. A1 - Spengler, G. A1 - Spies, F. A1 - Stawarz, L. A1 - Steenkamp, R. A1 - Stegmann, Christian A1 - Stinzing, F. A1 - Stycz, K. A1 - Sushch, Iurii A1 - Szostek, A. A1 - Tavernet, J. -P. A1 - Tavernier, T. A1 - Taylor, A. M. A1 - Terrier, R. A1 - Tluczykont, M. A1 - Trichard, C. A1 - Valerius, K. A1 - van Eldik, C. A1 - van Soelen, B. A1 - Vasileiadis, G. A1 - Venter, C. A1 - Viana, A. A1 - Vincent, P. A1 - Voelk, H. J. A1 - Volpe, F. A1 - Vorster, M. A1 - Vuillaume, T. A1 - Wagner, S. J. A1 - Wagner, P. A1 - Ward, M. A1 - Weidinger, M. A1 - Weitzel, Q. A1 - White, R. A1 - Wierzcholska, A. A1 - Willmann, P. A1 - Woernlein, A. A1 - Wouters, D. A1 - Zabalza, V. A1 - Zacharias, M. A1 - Zajczyk, A. A1 - Zdziarski, A. A. A1 - Zech, Alraune A1 - Zechlin, H. -S. T1 - Flux upper limits for 47 AGN observed with HESS in 2004-2011 JF - Astronomy and astrophysics : an international weekly journal N2 - Context. About 40% of the observation time of the High Energy Stereoscopic System (H.E.S.S.) is dedicated to studying active galactic nuclei (AGN), with the aim of increasing the sample of known extragalactic very-high-energy (VHE, E > 100 GeV) sources and constraining the physical processes at play in potential emitters. Aims. H.E.S.S. observations of AGN, spanning a period from April 2004 to December 2011, are investigated to constrain their gamma-ray fluxes. Only the 47 sources without significant excess detected at the position of the targets are presented. Methods. Upper limits on VHE fluxes of the targets were computed and a search for variability was performed on the nightly time scale. Results. For 41 objects, the flux upper limits we derived are the most constraining reported to date. These constraints at VHE are compared with the flux level expected from extrapolations of Fermi-LAT measurements in the two-year catalog of AGN. The H.E.S.S. upper limits are at least a factor of two lower than the extrapolated Fermi-LAT fluxes for 11 objects Taking into account the attenuation by the extragalactic background light reduces the tension for all but two of them, suggesting intrinsic curvature in the high-energy spectra of these two AGN. Conclusions. Compilation efforts led by current VHE instruments are of critical importance for target-selection strategies before the advent of the Cherenkov Telescope Array (CTA). KW - gamma rays: galaxies KW - galaxies: active Y1 - 2014 U6 - https://doi.org/10.1051/0004-6361/201322897 SN - 0004-6361 SN - 1432-0746 VL - 564 PB - EDP Sciences CY - Les Ulis ER - TY - THES A1 - Faber, Michael T1 - Folding dynamics of RNA secondary structures BT - a structure based approach Y1 - 2014 ER -