Thin membranes with dense periodic arrays of nanoscopic voids were fabricated using the principles of supramolecular assembly and self-organization in polymers. Such nanoporous membranes can be used as templates for synthesis and patterning of various organic and inorganic materials. In this thesis 4-vinylpyridine fragments of polystyrene-block-poly(4-vinylpyridine) (PS-PVP) were associated with the molecules of two different low molar mass additives, 2-(4'-hydroxybenzeneazo)benzoic acid (HABA) and 3-n-pentadecyl phenol (PDP), via hydrogen bonds. The choice of an additive and a solvent is a key factor which influences the morphologies of the PS-PVP+HABA associates (supramolecular assemblies) in thin films. The reversible association via hydrogen bonds allows the amphiphilic molecules of PDP to phase segregate on the free air interface. Unlike, the molecules of HABA remain associated within cylindrical and lamellar domains formed by the PVP block. A solvent used for film deposition influences the orientation of PVP+HABA domains with respect to the confining interfaces. The films deposited from 1,4-dioxane – a good solvent for PS and a bad one for PVP+HABA – demonstrated the perpendicular orientation of PVP+HABA domains. Meanwhile, the preparation of films from a chloroform solution – a good solvent for both PS and PVP+HABA – led to the parallel alignment. The orientation was independent on the film thickness (within the studied range of 20–100 nm) and insensitive to the chemical nature of a substrate. The orientation of the domains was shown to switch upon exposure to vapors of the above mentioned solvents from the parallel to perpendicular orientation and vice versa. Moreover, the swelling of the films in solvent vapors resulted in the significant improvement of the domain ordering. Extraction of HABA with selective solvent transformed of PVP+HABA domains into channels with reactive PVP chains on the walls. The resulted membranes with the perpendicular oriented channels (the diameter about 8 nm, the inter-channel distance 24 nm) were used as a template for the creation of ordered arrays of nanodots from nickel, chromium and gold.

Visualization and study of reconformation of polyelectrolytes (PEs) of different architecture is of great fundamental and practical interest. Verification of theoretical predictions with experiment is of essential importance. On the other hand, a wide range of bottom-up techniques based on patterning of matter on the length scale of a few nanometers have been recently developed. Particularly interesting is the possibility of using self-assembled single molecule structures as templates for the deposition of inorganic matter, in particular metals. Synthetic "normal-sized" polymers of various architecture, like poly-2-vinylpyridine (P2VP) or polystyrene-poly(2-vynil pyridine) P2VP7-PS7 star-like block copolymer, adsorbed on solid substrates have been visualized for the first time with molecular resolution by AFM in different conformation. This finding allowed us to study largely discussed problem, a coil-to-globule transition of PEs. It was found that PE molecules undergo conformational transitions from stretched worm-like coil to compact globule via set of necklace-like globules, as the fraction of charged monomers decreases with an increase of pH and ionic strength. These results are in good agreement with recently developed DRO theory for weakly charged flexible PEs in poor solvent. The size of the deposited single molecules correlates very well with molecular dimensions in solution obtained in light scattering experiments. PE single molecules of various architectures was mineralized in different conformations that constitutes the route to nanoparticles with desired shape (including wire-shape and star-shaped), size, and composition (including metallic, magnetic and semiconductive nanoparticles). It was shown that molecular details of the adsorbed linear flexible PE molecules determine the dimensions of the nanostructures after metallization and that observed sizes are consistent with the decoration of single molecules with nanoclusters. Thus those metallized nanoparticles (cluster assembles) reflect the conformation of original adsorbed PE molecules. The dimensions of the obtained nanowires are significantly smaller than those previously reported. All of these features are of the potential benefit in applications for nanodevices. Metallization of the PS7-P2VP7 improves AFM resolution due to the selective deposition of Pd clusters along the P2VP chains. For the first time, the number of the P2VP second generation arms of the heteroarm block-copolymer was directly counted in the single molecule AFM experiment. Simple contrasting procedure was developed to improve AFM visualization of positively charged polymer chains deposited on the substrates of relatively high roughness. This method allows increasing the thickness of the resulting structures up to 10 nm, and, consequently, provide visualization of polymer chains on rough surfaces. This innovation is important for the development of single molecule experiments with polymer chains. The reaction of HCF-anion could be used for recognition of polycation molecules, when polycations, polyanions and neutral molecules coexist on the surface. Recently, the study was strongly restricted to atomically smooth surfaces. The contrasting procedure extends the range of substrates (Si-wafers, chemically modified or patterned Si-wafers, polished glasses, polymer films, etc) appropriate for the experiments. Thus, polymer single molecules can be considered not only as representative of the ensemble molecules, but also as individual nanoscale objects which can be used for future nanotechnology for the fabrication of single molecule electronic devices. Also these findings are important from fundamental point of view, since developed approach can be successfully applied for investigation of various "classical" problems in polymer science, such as polymer reconformation, interpolyelectrolyte complex formation, polymer diffusion, adsorption, etc.

Im Rahmen der vorliegenden Arbeit sind die Struktur und die Wasserstoffsorptionseigenschaften neuer nanokristalliner, hydridbildender magnesiumbasierter Legierungen, die mittels Rascherstarrung (Melt-Spinning Verfahren) hergestellt wurden, untersucht worden. Der Schwerpunkt der Arbeit bestand in der Erforschung der Vorgänge während der Aktivierung und der zyklischen Hydrierung/Dehydrierung der rascherstarrten Mg-Legierungen. Zusätzlich wurde das Gefüge, das sich nach der Kristallisation, Aktivierung bzw. Hydrierung einstellt, seine Erhaltung und Auswirkung auf das H2-Speicherverhalten (Struktur-Eigenschafts-Beziehungen) untersucht. Die für die Verbesserung der Kinetik des H2-Speicherverhaltens angestrebte Nanostruktur konnte nach der Hydrierung der rascherstarrten Legierungen erreicht werden. Die REM-, TEM- sowie EFTEM (EELS)-Untersuchungen zeigten, dass ein Y-Zusatz zu Mg-basierten Legierungen zu einer sehr feinen (ca. 50 nm) und homogenen Verteilung von Y-Hydriden im Gefüge der rascherstarrten Bänder führt. Mg2Ni-Hydride bilden dagegen größere Körner im Größenbereich von 2-3 µm. Bei den Cu-haltigen Legierungen wurde eine Koexistenz von Mg2NiH4 und MgCu2 in direkter Nachbarschaft nachgewiesen. Detaillierte Untersuchungen der Wasserstoffabsorption haben gezeigt, dass die Chemisorption während des linearen Anfangsbereiches des Hydrierungsverlaufes geschwindigkeitsbestimmend ist. Nach dem linearen Hydrierungsverlauf ist die Hydrierungskinetik von der Wasserstoffdiffusion durch eine geschlossene Hydridschicht beeinflusst. Mit dem breiten Spektrum der Untersuchungen (REM, EELS, TEM, HP-TGA, DSC, in situ-Synchrotron-XRD) als auch durch gezielte Variation der Zusammensetzungen wurden neue und grundlegende Erkenntnisse zum H2-Speicherverhalten der rascherstarrten Mg-basierten Legierungssysteme gewonnen. Besondere Beachtung verdient die Mg90Ni8Y1,6SE0,4-Legierung. Durch die Möglichkeit einer einfachen Herstellung, ihre schnelle Reaktionskinetik, ihren hohen Wasserstoffgehalt (bis zu 5,6 Gew.%) und ihre gute Zyklenstabilität eignet sich diese Legierung zur sicheren, volumeneffizienten sowie leichtgewichtigen Speicherung von Wasserstoff. Damit kann Wasserstoff gespeichert, transportiert und als CO2-freier Sekundärenergieträger in stationären und mobilen Anwendungen eingesetzt werden.

Visualization and study of reconformation of polyelectrolytes (PEs) of different architecture is of great fundamental and practical interest. Verification of theoretical predictions with experiment is of essential importance. On the other hand, a wide range of bottom-up techniques based on patterning of matter on the length scale of a few nanometers have been recently developed. Particularly interesting is the possibility of using self-assembled single molecule structures as templates for the deposition of inorganic matter, in particular metals. Synthetic "normal-sized" polymers of various architecture, like poly-2-vinylpyridine (P2VP) or polystyrene-poly(2-vynil pyridine) P2VP7-PS7 star-like block copolymer, adsorbed on solid substrates have been visualized for the first time with molecular resolution by AFM in different conformation. This finding allowed us to study largely discussed problem, a coil-to-globule transition of PEs. It was found that PE molecules undergo conformational transitions from stretched worm-like coil to compact globule via set of necklace-like globules, as the fraction of charged monomers decreases with an increase of pH and ionic strength. These results are in good agreement with recently developed DRO theory for weakly charged flexible PEs in poor solvent. The size of the deposited single molecules correlates very well with molecular dimensions in solution obtained in light scattering experiments. PE single molecules of various architectures was mineralized in different conformations that constitutes the route to nanoparticles with desired shape (including wire-shape and star-shaped), size, and composition (including metallic, magnetic and semiconductive nanoparticles). It was shown that molecular details of the adsorbed linear flexible PE molecules determine the dimensions of the nanostructures after metallization and that observed sizes are consistent with the decoration of single molecules with nanoclusters. Thus those metallized nanoparticles (cluster assembles) reflect the conformation of original adsorbed PE molecules. The dimensions of the obtained nanowires are significantly smaller than those previously reported. All of these features are of the potential benefit in applications for nanodevices. Metallization of the PS7-P2VP7 improves AFM resolution due to the selective deposition of Pd clusters along the P2VP chains. For the first time, the number of the P2VP second generation arms of the heteroarm block-copolymer was directly counted in the single molecule AFM experiment. Simple contrasting procedure was developed to improve AFM visualization of positively charged polymer chains deposited on the substrates of relatively high roughness. This method allows increasing the thickness of the resulting structures up to 10 nm, and, consequently, provide visualization of polymer chains on rough surfaces. This innovation is important for the development of single molecule experiments with polymer chains. The reaction of HCF-anion could be used for recognition of polycation molecules, when polycations, polyanions and neutral molecules coexist on the surface. Recently, the study was strongly restricted to atomically smooth surfaces. The contrasting procedure extends the range of substrates (Si-wafers, chemically modified or patterned Si-wafers, polished glasses, polymer films, etc) appropriate for the experiments. Thus, polymer single molecules can be considered not only as representative of the ensemble molecules, but also as individual nanoscale objects which can be used for future nanotechnology for the fabrication of single molecule electronic devices. Also these findings are important from fundamental point of view, since developed approach can be successfully applied for investigation of various "classical" problems in polymer science, such as polymer reconformation, interpolyelectrolyte complex formation, polymer diffusion, adsorption, etc.

We report the possibility to control the tilting of nanoneedles and nanowires by using structured sapphire substrates. The advantage of the reported strategy is to obtain well oriented growth along a single direction tilted with respect to the surface normal, whereas the growth in other directions is suppressed. In our particular case, the nanostructures are tilted with respect to the surface normal by an angle of 58°. Moreover, we demonstrate that variation of the nanostructures shape from nanoneedles to cylindrical nanowires by using SiO2 layer is observed.

Over millions of years evolution has optimized the properties of materials via natural selection for many specific purposes. Indeed, natural materials have unique properties which come very close to perfection. Cells, for instance, are able to carry out intricate sequences of chemical reactions that are difficult or impossible to carry out ex vivo, cell membranes are the most complex selective and responsive semipermeable membranes that exist, and animal shells exhibit a clever nanostructure that renders them hard and tough at the same time. In short, materials scientists can learn a lot from nature’s materials. The perfection and performance of nature’s materials not only spark fascination, but also trigger the question as to why certain structures or surfaces exhibit outstanding properties and inspire research towards new materials. While the materials of living nature impressively serve dedicated purposes, they are formed under restricted conditions. For instance, they have to be designed to function under a narrowly defined set of physiological conditions, and can only be composed of building blocks an organism has available. Without these restrictions, material scientists can design entirely new materials or surfaces.

Block copolymer/inorganic nanoparticle hybrids draw great attention of scientists from various areas for their potential applications in diverse fields such as microelectronics, sensors, and solar cells. Inorganic nanoparticles (NPs) can be expected to be incorporated into block copolymers with order and selectivity by self-assembly of NPs and/or by synergistic self-assembly between NPs and block copolymers. The morphology and nanostructure order of block copolymers can be also adjusted and directed by incorporation of NPs. In this study, the effect of the size and modification of AuNPs on the morphology and nanostructure orientation of block copolymer PPMA-b-PMMA thin films were systematically investigated. The lateral BCP structure in thin films was improved by adding AuNPs. The controlled location of AuNPs in the BCP thin films depended on the particle size and stabilizing species. The re-orientation of cylindrical domains depended on the modification of AuNPs. PPMA-coated AuNPs, corresponding to the lower surface energy component of BCP, were powerful in directing the cylinders from parallel to perpendicular to the substrate. These results provide a general guide for other BCP/inorganic NP hybrid systems for desired morphology and nanostructure orientation.

Thin membranes with dense periodic arrays of nanoscopic voids were fabricated using the principles of supramolecular assembly and self-organization in polymers. Such nanoporous membranes can be used as templates for synthesis and patterning of various organic and inorganic materials. In this thesis 4-vinylpyridine fragments of polystyrene-block-poly(4-vinylpyridine) (PS-PVP) were associated with the molecules of two different low molar mass additives, 2-(4'-hydroxybenzeneazo)benzoic acid (HABA) and 3-n-pentadecyl phenol (PDP), via hydrogen bonds. The choice of an additive and a solvent is a key factor which influences the morphologies of the PS-PVP+HABA associates (supramolecular assemblies) in thin films. The reversible association via hydrogen bonds allows the amphiphilic molecules of PDP to phase segregate on the free air interface. Unlike, the molecules of HABA remain associated within cylindrical and lamellar domains formed by the PVP block. A solvent used for film deposition influences the orientation of PVP+HABA domains with respect to the confining interfaces. The films deposited from 1,4-dioxane – a good solvent for PS and a bad one for PVP+HABA – demonstrated the perpendicular orientation of PVP+HABA domains. Meanwhile, the preparation of films from a chloroform solution – a good solvent for both PS and PVP+HABA – led to the parallel alignment. The orientation was independent on the film thickness (within the studied range of 20–100 nm) and insensitive to the chemical nature of a substrate. The orientation of the domains was shown to switch upon exposure to vapors of the above mentioned solvents from the parallel to perpendicular orientation and vice versa. Moreover, the swelling of the films in solvent vapors resulted in the significant improvement of the domain ordering. Extraction of HABA with selective solvent transformed of PVP+HABA domains into channels with reactive PVP chains on the walls. The resulted membranes with the perpendicular oriented channels (the diameter about 8 nm, the inter-channel distance 24 nm) were used as a template for the creation of ordered arrays of nanodots from nickel, chromium and gold.

Im Rahmen der vorliegenden Arbeit werden ab initio Berechnungen des Restwiderstandes von metallischen Nanostrukturen vorgestellt. Die elektronische Struktur der idealen Systeme wird mit Hilfe einer Screened KKR Greenschen Funktionsmethode im Rahmen der Vielfachstreutheorie auf der Grundlage der Dichtefunktionaltheorie berechnet. Die Potentiale von Punktdefekten werden selbstkonsistent mit Hilfe einer Dyson-Gleichung für die Greensche Funktion des gestörten Systems berechnet. Unter Nutzung der ab initio Ubergangswahrscheinlichkeiten wird der Restwiderstand durch Lösung der quasi-klassischen Boltzmann-Gleichung bestimmt. Ergebnisse für ultradünne Cu-Filme und die Leitfähigkeitsanomalie während des Wachstums von Co/Cu-Vielfachschichten werden vorgestellt. Der Einfluss von Oberflächen, geordneten und ungeordneten Grenzflächenlegierungen und von Defekten an verschiedenen Positionen in der Vielfachschicht auf den Effekt des Giant Magnetoresistance wird untersucht. Die selbstkonsistente Berechnung der Streueigenschaften und die verbesserte Lösung der Boltzmann-Transportgleichung unter Einbeziehung der Vertex-Korrekturen stellen ein leistungsfähiges Werkzeug zur umfassenden theoretischen Beschreibung dar. Sie verhelfen zu nützlichen Einsichten in die mikroskopischen Prozesse, die die Transporteigenschaften von nanostrukturierten Materialen bestimmen. / A powerful formalism for the calculation of the residual resistivity of metallic nanostructured materials without adjustable parameters is presented. The electronic structure of the unperturbed system is calculated using a screended KKR multiple scattering Green's function formalism in the framework of density functional theory. The scattering potential of point defects is calculated self-consistently by solving a Dyson equation for the Green's function of the perturbed system. Using the ab initio scattering probabilities the residual resistivity was calculated solving the quasiclassical Boltzmann equation. Examples are given for the resistivity of ultrathin Cu films and the conductance anomaly during the growth of a Co/Cu multilayer. Furthermore, the influence of surfaces, ordered and disordered interface alloys and defects at different positions in the multilayer on the effect of Giant Magnetoresistance is investigated. The self-consistent calculation of the scattering properties and the improved treatment of the Boltzmann transport equation including vertex corrections provide a powerful tool for a comprehensive theoretical description and a helpful insight into the microscopic processes determining the transport properties of magnetic nanostructured materials.

Plasmons, i.e. collective oscillations of conduction electrons, have a strong influence on the optical properties of metal micro- and nanostructures and are of great interest for novel photonic devices. Here, plasmons on metal-dielectric interfaces are investigated using near-field optical microscopy and differential angular reflectance spectroscopy. Emphasis is placed on the study of plasmon interaction with individual nanostructures and on the nonlinear process of surface plasmon amplification. Specifically, plasmon transmission across single grooves in thin silver films is investigated with the help of a near-field optical microscope. It is found that plasmon transmittance as a function of groove width shows a non-monotonic behavior, exhibiting certain favorable groove widths with strongly decreased transmittance values. Additionally, evidence of groove-mediated plasmon mode coupling is observed. Spatial beating due to different plasmon wave vectors produces distinct interference features in near-field optical images. A theoretical approach explains these observations and gives estimated coupling effciencies deduced from visibility considerations. Furthermore, stimulated emission of surface plasmons induced by optical pumping using an organic dye solution is demonstrated for the first time. For this a novel twin-attenuated-total-reflection scheme is introduced. The experiment is described by a theoretical model which exhibits very good agreement. Together they provide clear evidence of the claimed process.