Self assembled materials for solar cell application

In der vorliegenden Arbeit wurden Materialien und Aufbauten für Hybrid Solarzellen entwickelt und erforscht. rnDer Vergleich zweier bekannter Lochleitermaterialien für Solarzellen in einfachen Blend-Systemen brachte sowohl Einsicht zur unterschiedlichen Eignung der Materialien für optoelektronische Bauelemente als auch neue Erkenntnisse in Bereichen der Langzeitstabilität und Luftempfindlichkeit beider Materialien.rnWeiterhin wurde eine Methode entwickelt, um Hybrid Solarzelle auf möglichst unkomplizierte Weise aus kostengünstigen Materialien darzustellen. Die „Eintopf“-Synthese ermöglicht die unkomplizierte Darstellung eines funktionalen Hybridmaterials für die optoelektronische Anwendung. Mithilfe eines neu entwickelten amphiphilen Blockcopolymers, das als funktionelles Templat eingesetzt wurde, konnten mit einem TiO2-Precursor in einem Sol-Gel Ansatz verschiedene selbstorganisierte Morphologien des Hybridmaterials erhalten werden. Verschiedene Morphologien wurden auf ihre Eignung in Hybrid Solarzellen untersucht. Ob und warum die Morphologie des Hybridsystems die Effizienz der Solarzelle beeinflusst, konnte verdeutlicht werden. Mit der Weiterentwicklung der „Eintopf“-Synthese, durch den Austausch des TiO2-Precursors, konnte die Solarzelleneffizienz von 0.15 auf 0.4 % gesteigert werden. Weiterhin konnte die Übertragbarkeit des Systems durch den erfolgreichen Austausch des Halbleiters TiO¬2 mit ZnO bewiesen werden.rnNew materials and assemblies were designed and tested for hybrid solar cell application. A simple blending approach was used to prepare hybrid solar cells in a convenient, cheap and fast method. Nano crystalline TiO2 rods were blended with different hole conducting materials and tested in solar cell devices. Comparing their performance in photovoltaic devices, while experimental conditions are kept identical, showed that the choice of solvent and photovoltaic characterization conducted in inert atmosphere is of different influence for different hole conducting materials. External influences as long term stability were investigated.rnIn comparison to the blend approach a new one-pot approach was invented to prepare a nanostructured, multi-functional material with orthogonal properties. It consists of TiO2 as a functional metal oxide and a new amphiphilic block-copolymer poly(ethyleneoxide)-b-poly(triphenylamine) (PEO-b-PTPA) that was synthesized. The hybrid material was obtained within a single step via self assembly in solution. Therefore a method had to be found to obtain crystalline TiO2 under mild conditions. Within the materials synthesis the block-copolymer not only acts as a templating agent but also adds an electronic functionality to the resulting hybrid material. During the synthesis a variety of self assembled morphologies ranging from spheres to wires were created in a controlled fashion. The obtained morphology depends on the weight fraction of the polymer, solvent, TiO2 precursor and acid. Studying films on silicon wafers with scanning electron microscopy (SEM) and transmission electron microscopy (TEM) a ternary phase diagram could be mapped whereas the crystallinity of TiO2 could be proved by high resolution-TEM. Different morphologies of this self assembled hybrid material were tested for solar cell application. Even for devices with layer thicknesses of the active material below 10 nm power conversion efficiencies up to 0.15 % at 1 sun and 1.5 AM were observed. The solar cell efficiency was increased with further development of the one-pot approach by changing the precursor. A polyethyleneglycole modified titanate was used as precursor in combination with the functional block copolymer PEO-b-PTPA. Again self-assembled network morphologies were obtained and tested in solar cell devices. While the formation of percolating networks is of general importance the solar cell performance was found to depend on the morphological design of the hybrid material. With the aid of conductive scanning force microscopy, it was proven to preserve a percolating network despite an increase of the active layer thickness. In combination with a special functionalized Ti-precursor hybrid bulk heterojunction solar cells having a maximum power conversion efficiency of 0.4 % at 1 sun and 1.5 AM were obtained.r

Relationship between tectonic overpressure, deviatoric stress, driving force, isostasy and gravitational potential energy

We present analytical derivations and 2-D numerical simulations that quantify magnitudes of deviatoric stress and tectonic overpressure (i.e. difference between the pressure, or mean stress, and the lithostatic pressure) by relating them to lateral variations in the gravitational potential energy (GPE). These predictions of tectonic overpressure and deviatoric stress associated with GPE differences are independent of rock rheology (e.g. viscous or elastic) and rock strength. We consider a simple situation with lowlands and mountains (plateau). We use a numerical two-layer model consisting of a crust with higher Newtonian viscosity than that in the mantle, and also a three-layer model in which the two-layer lithosphere overlies a much less viscous asthenosphere. Our results (1) explain why estimates for the magnitude of stresses in Tibet, previously published by different authors, vary by a factor of two, (2) are applied to test the validity of the thin sheet approximation, (3) show that the magnitude of the depth-integrated tectonic overpressure is equal to the magnitude of the depth-integrated deviatoric stress if depth-integrated shear stresses on vertical and horizontal planes within the lithosphere are negligible (the thin sheet approximation) and (4) show that under thin sheet approximation tectonic overpressure is required to build and support continental plateaus, such as in Tibet or in the Andes, even if the topography and the crustal root are in isostatic equilibrium. Under thin sheet approximation, the magnitude of the depth-integrated tectonic overpressure is equal to the depth-integrated horizontal deviatoric stress, and both are approximately 3.5 × 1012 N m−1 for Tibet. The horizontal driving force per unit length related to lateral GPE variations around Tibet is composed of the sum of both tectonic overpressure and deviatoric stress, and is approximately 7 × 1012 N m−1. This magnitude exceeds previously published estimates for the force per unit length required to fold the Indo-Australian Plate south of India, and hence the uplift of the Tibetan plateau could have folded the Indian Plate. We also discuss the mechanical conditions that are necessary to achieve isostasy, for which the lithostatic pressure is constant at a certain depth. The results show that tectonic overpressure can exist at a certain depth even if all deviatoric stresses are zero at this depth, because this tectonic overpressure is related to horizontal gradients of vertical shear stresses integrated across the entire depth of the lithosphere. The magnitude of the depth-integrated tectonic overpressure of 3.5 × 1012 N m−1 implies that the pressure estimated from observed mineral assemblages in crustal rocks is likely significantly different from the lithostatic pressure, and pressure recorded by crustal rocks is not directly related to depth. In case of significant weakening of the entire lithosphere by any mechanism our analytical and numerical studies provide a simple estimation of tectonic overpressure via variations in GP

Comparing thin-sheet models with 3-D multilayer models for continental collision

Various models have been proposed to explain tectonic deformations during continent collision. A frequently applied model is the thin viscous sheet model which is however not fully 3-D and assumes a priori diffuse thickening as the dominant deformation style. We compare a fully 3-D multilayer numerical model with a corresponding thin viscous sheet numerical model for the scenario of continent indentation. In our comparison we focus on the three basic viscous deformation styles thickening, buckling (folding) and lateral crustal flow. Both numerical models are based on the finite element method (FEM) and employ either a linear or power-law viscous rheology. The 3-D model consists of four layers representing a simplified continental lithosphere: strong upper crust, weak lower crust, strong upper mantle and weak lower mantle. The effective viscosity depth-profile in the 3-D model is used to calculate the depth-averaged effective viscosity used in the thin-sheet model allowing a direct comparison of both models. We quantify the differences in the strain rate and velocity fields, and investigate the evolution of crustal thickening, buckling and crustal flow resulting from the two models for two different phases of deformation: (1) indentation with a constant velocity and (2) gravitational collapse after a decrease of the indenting velocity by a factor of 5. The results indicate that thin-sheet models approximate well the overall large-scale lithospheric deformation, especially during indentation and for a linear viscous rheology. However, in the 3-D model, additional processes such as multilayer buckling and lower crustal flow emerge, which are ignored in the thin-sheet model but dominate the deformation style in the 3-D model within a range of a few hundreds of kilometres around the collision zone and indenter corner. Differences between the 3-D and thin-sheet model are considerably larger for a power-law viscous than for a linear viscous rheology. Buckling and lower crustal flow are significant in the 3-D model with power-law viscous rheology. For example, fibre strain rates due to buckling can be several hundred per cent different to the depth-averaged strain rate and the lateral mass flow of lower crustal material can be up to six times more than the flow of upper crustal material. Our results also show that the horizontal velocity fields of the upper crust and upper mantle remain nearly identical in the 3-D model during indentation despite their mechanical decoupling due to an intermediate weak lower crust. This result questions the validity of using similarities between velocities from the surface global positioning system (GPS) and mantle shear wave splitting data as evidence for a mechanically coupled lithosphere. 3-D multilayer models provide a more complete picture of continental collision than thin-sheet models as they enable studying the timing, locality and relative importance of different processes simultaneously which is especially important for the hundreds of kilometre scale around the collision zone and indenter corners. 3-D models are, however, still computationally challenging and we, therefore, also present results of a computational performance test of several solution algorithm

All-inorganic core-shell silica-titania mesoporous colloidal nanoparticles showing orthogonal functionality

Colloidal mesoporous silica (CMS) nanoparticles with a thin titania-enriched outer shell showing a spatially resolved functionality were synthesized by a delayed co-condensation approach. The titaniashell can serve as a selective nucleation site for the growth of nanocrystalline anatase clusters. These fully inorganic pure silica-core titania-enriched shell mesoporous nanoparticles show orthogonal functionality, demonstrated through the selective adsorption of a carboxylate-containing ruthenium N3-dye. UV-Vis and fluorescence spectroscopy indicate the strong interaction of the N3-dye with the titania-phase at the outer shell of the CMS nanoparticles. In particular, this interaction and thus the selective functionalization are greatly enhanced when anatase nanocrystallites are nucleated at the titania-enriched shell surface

Linking Alpine deformation in the Aar Massif basement and its cover units – the case of the Jungfrau–Eiger mountains (Central Alps, Switzerland)

The northwest (NW) rim of the external Aar Massif was exhumed from  ∼ 10&thinsp;km depth to its present position at 4&thinsp;km elevation above sea level during several Alpine deformation stages. Different models have been proposed for the timing and nature of these stages. Recently proposed exhumation models for the central, internal Aar Massif differ from the ones established in the covering Helvetic sedimentary units. By updating pre-existing maps and collecting structural data, a structural map and tectonic section were reconstructed. Those were interpreted together with microstructural data and peak metamorphic temperature estimates from collected samples to establish a framework suitable for both basement and cover. Deformation temperatures range between 250 and 330&thinsp;°C, allowing for semi-brittle deformation in the basement rocks, while the calcite-dominated sedimentary rocks deform in a ductile manner at these conditions. Although field data allow to distinguish multiple deformation stages before and during Aar Massif's exhumation, all related structures formed under similar P, T conditions at the investigated NW rim. In particular, we find that the exhumation occurred during two stages of shearing in Aar Massif's basement, which induced in the sedimentary rocks first a phase of folding and then a period of thrusting, accompanied by the formation of a new foliation.</p

Glycoform-resolved pharmacokinetic studies in a rat model employing glycoengineered variants of a therapeutic monoclonal antibody

Good pharmacokinetic (PK) behavior is a key prerequisite for sufficient efficacy of therapeutic monoclonal antibodies (mAbs). Fc glycosylation is a critical quality attribute (CQA) of mAbs, due to its impact on stability and effector functions. However, the effects of various IgG Fc glycoforms on antibody PK remain unclear. We used a combination of glycoengineering and glycoform-resolved PK measurements by mass spectrometry (MS) to assess glycoform effects on PK. Four differently glycoengineered mAbs, each still containing multiple glycoforms, were separately injected into rats. Rat models have been shown to be predictive of human PK. At different time points, blood was taken, from which the mAbs were purified and analyzed with a liquid chromatography-MS-based bottom-up glycoproteomics approach. This allowed us to follow changes in the glycosylation profiles of each glycoengineered mAb over time. Enzyme-linked immunosorbent assay measurements provided an absolute concentration in the form of a sum value for all glycoforms. Information from both readouts was then combined to calculate PK parameters per glycoform. Thereby, multiple glycoform kinetics were resolved within one mAb preparation. We confirmed increased clearance of high-mannose (Man5) and hybrid-type (Man5G0) glycoforms. Specifically, Man5 showed a 1.8 to 2.6-fold higher clearance than agalactosylated, complex glycans (G0F). Unexpectedly, clearance was even higher (4.7-fold) for the hybrid-type glycan Man5G0. In contrast, clearance of agalactosylated, monoantennary glycoforms (G0F-N) was only slightly increased over G0F (1.2 to 1.4-fold). Thus, monoantennary, hybrid-type and high-mannose glycoforms should be distinguished in CQA assessments. Strikingly, alpha 2,3-linked sialylation did not affect clearance, contradicting the involvement of the asialoglycoprotein receptor in mAb clearance.Proteomic

Bedrock sculpting under an active alpine glacier revealed from cosmic-ray muon radiography.

Mountain glaciers form landscapes with U-shaped valleys, roche moutonées and overdeepenings through bedrock erosion. However, little evidence for active glacial carving has been provided particularly for areas above the Equilibrium Line Altitude (ELA) where glaciers originate. This is mainly due to our lack of information about the shape of the bedrock underneath active glaciers in highly elevated areas. In the past years, the bedrock morphology underneath active glaciers has been studied by geophysical methods in order to infer the subglacial mechanisms of bedrock erosion. However, these comprise surveys on the glaciers' surface, from where it has been difficult to investigate the lateral boundary between the ice and the bedrock with sufficient resolution. Here we perform a muon-radiographic inspection of the Eiger glacier (Switzerland, European Alps) with the aid of cosmic-ray muon attenuation. We find a reach (600 × 300 m) within the accumulation area where strong lateral glacial erosion has cut nearly vertically into the underlying bedrock. This suggests that the Eiger glacier has profoundly sculpted its bedrock in its accumulation area. This also reveals that the cosmic-ray muon radiography is an ideal technology to reconstruct the shape of the bedrock underneath an active glacier

CD83 Modulates B Cell Function In Vitro: Increased IL-10 and Reduced Ig Secretion by CD83Tg B Cells

The murine transmembrane glycoprotein CD83 is an important regulator for both thymic T cell maturation and peripheral T cell responses. Recently, we reported that CD83 also has a function on B cells: Ubiquitous transgenic (Tg) expression of CD83 interfered with the immunoglobulin (Ig) response to infectious agents and to T cell dependent as well as T cell independent model antigen immunization. Here we compare the function of CD83Tg B cells that overexpress CD83 and CD83 mutant (CD83mu) B cells that display a drastically reduced CD83 expression. Correlating with CD83 expression, the basic as well as the lipopolysaccharide (LPS) induced expression of the activation markers CD86 and MHC-II are significantly increased in CD83Tg B cells and reciprocally decreased in CD83mu B cells. Wild-type B cells rapidly upregulate CD83 within three hours post BCR or TLR engagement by de novo protein synthesis. The forced premature overexpression of CD83 on the CD83Tg B cells results in reduced calcium signaling, reduced Ig secretion and a reciprocally increased IL-10 production upon in vitro activation. This altered phenotype is mediated by CD83 expressed on the B cells themselves, since it is observed in the absence of accessory cells. In line with this finding, purified CD83mu B cells displayed a reduced IL-10 production and slightly increased Ig secretion upon LPS stimulation in vitro. Taken together, our data strongly suggest that CD83 is expressed by B cells upon activation and contributes to the regulation of B cell function

Altered maturation of peripheral blood dendritic cells in patients with breast cancer

Tumours have at least two mechanisms that can alter dendritic cell (DC) maturation and function. The first affects the ability of haematopoietic progenitors to differentiate into functional DCs; the second affects their differentiation from CD14+ monocytes, promoting an early but dysfunctional maturation. The aim of this study was to evaluate the in vivo relevance of these pathways in breast cancer patients. For this purpose, 53 patients with invasive breast cancer were compared to 68 healthy controls. To avoid isolation or culture procedures for enrichment of DCs, analyses were directly performed by flow cytometry on whole-blood samples. The expression of surface antigens and intracellular accumulation of regulatory cytokines upon LPS stimulation were evaluated. The number of DCs, and in particular of the myeloid subpopulation, was markedly reduced in cancer patients (P < 0.001). Patient DCs were characterized by a more mature phenotype compared with controls (P = 0.016), and had impaired production of IL-12 (P < 0.001), These alterations were reverted by surgical resection of the tumour. To investigate the possible role of some tumour-related immunoactive soluble factors, we measured the plasmatic levels of vascular endothelial growth factor, IL-10 and spermine. A significant inverse correlation between spermine concentration and the percentage of DCs expressing IL-12 was found. Evidence was also obtained that in vitro exposure of monocyte-derived DCs to spermine promoted their activation and maturation, and impaired their function. Taken together, our results suggest that both the above-described mechanisms could concomitantly act in breast cancer to affect DC differentiation, and that spermine could be a mediator of dysfunctional maturation of DCs