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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.
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.
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.
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
Fabrication of Au@Pt multibranched nanoparticles and their application to in situ SERS monitoring
(2014)
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.
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.
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.
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).