Since its inception a quarter of a century ago, Kelvin probe force microscopy (KPFM) has enabled studying contact potential differences (CPDs) on the nanometre scale. However, current KPFM investigations are limited by the bandwidth of its constituent electronic loops to the millisecond regime. To overcome this limitation, pump-probe-driven Kelvin probe force microscopy (pp-KPFM) is introduced that exploits the non-linear electric interaction between tip and sample. The time resolution surpasses the electronic bandwidth and is limited by the length of the probe pulse. In this work, probe pulse lengths as small as 4.5 ns have been realized. These probe pulses can be synchronized to any kind of pump pulses. The first system investigated with pp-KPFM is an electrically-driven organic field-effect transistor (OFET). Here, charge carrier propagation in the OFET channel upon switching the drain-source voltage is directly observed and compared to simulations based on a transmission line model. Varying the charge carrier density reveals the impeding influence of Schottky barriers on the maximum switching frequency. The second system is an optically-modulated silicon homojunction. Here, the speed of surface photovoltage (SPV) build-up is accessed and compared to timeaveraged results. Due to slow trap states, the time-averaged method is found to lack comprehensiveness. In contrast, pp-KPFM exposes two intensity-dependent recombination times on the same timescale — high-level Shockley-Read-Hall recombination in the bulk and heat-dominated recombination in the surface layer — and a delay of the SPV decay with rising frequency, which is attributed to charge carrier retention at nanocrystals. The third system is a DCV5T-Me:C60 bulk heterojunction. The SPV dynamics is probed and compared to measurements via open-circuit corrected transient charge carrier extraction by linearly increasing voltage. Both methods reveal an exponential onset of the band bending reduction that is attributed to the charge carrier diffusion time in DCV5T-Me, and a double exponential decay, hinting at different recombination paths in the studied organic solar cell. The above-mentioned experiments demonstrate that pp-KPFM surpasses conventional KPFM when it comes to extracting dynamic device parameters such as charge carrier retention and recombination times, and prove that pp-KPFM is a versatile and reliable tool for studying electrodynamics on nanosurfaces.

The cellular membrane is a complex biological entity, far from being an inert assembly of protein and lipids which separates cells from the surrounding environment. A multitude of biological processes, ranging from active transport of ions into and out of the cell, to the immune response, are regulated at the level of the plasma membrane. The understanding of their molecular basis is among the central goals of modern biological research. In order to dissect the complexity of actual cell membranes, which involves a very complex network of intermolecular interactions, a “divide and conquer” strategy proves very useful. To this end, researchers try to isolate molecules from complex biological contexts to understand their function in simple model systems under controlled conditions. A variety of model membranes have thus been developed in order to gain insight into membrane processes. This approach has resulted in a deeper knowledge on how lipids and proteins interact and how these interactions govern the function of cellular membranes. In the recent past in fact, a connection has been established between the lateral structure of the plasma membrane and its biological function. Furthermore, a large range of biophysical techniques have been used to characterize protein-lipid microdomains. For example, atomic force microscopy (AFM) is a powerful technique which allows a highly detailed topographical characterization of lipid domains in physiological conditions. While AFM imaging offers an extremely high spatial resolution, up to the nanometer scale, the limited image acquisition speed (minutes) can pose a severe drawback in adequately studying fast dynamic processes. On the other hand, fluorescence based imaging techniques are much faster (10-3-100 s), but certainly lack the high spatial resolution that AFM offers. FCS in particular can also provide information about dynamic processes, like diffusion of fluorescent membrane components. For these reasons, implementing a combination of the above mentioned techniques on the same sample (e.g. cell membrane models) would prove extremely beneficial in the complete dynamic and structural characterization of molecular interactions. . The work described in this thesis can be summarized in two main points: i) the development of a novel combined approach of atomic force microscopy (AFM), laser scanning imaging (LSM), and fluorescence correlation spectroscopy (FCS) and ii) the study of the effects of ceramide in the lateral organization of model plasma membranes. We described one of the first simultaneous applications of AFM and FCS on biologically relevant systems. More specifically, model membranes showing complex phase separation were investigated with a combined approach of AFM, confocal fluorescence imaging, force measurements and FCS, based on commercially available instruments. AFM conveys information about the structural and mechanical properties of the different lipid phases. Different membrane domains can be distinguished based on height difference, elastic properties and line tension as measured by the AFM tip. Simultaneous optical measurements offer the correlation of these data in real time with the partition behavior and diffusion of fluorescent lipids and proteins. We established a clear link between the local membrane viscosity, probed by FCS, and the lipid-lipid interactions involved in line tension, probed by AFM force measurements. An example of a significant drawback circumvented by the AFM-FCS approach involves the use of AFM micromanipulation to eliminate unwanted interactions between lipid particles — similar to intra-cellular vesicles found in vivo experiments — and the membrane, which usually result in distorted FCS autocorrelation curves. Finally, the combined application of AFM and FCS on membrane-anchored proteins reconstituted in lipid bilayers has been instrumental in clarifying inconsistencies that arose in work that focused solely on either AFM or fluorescence techniques. We have shown that, in the case of proteins diffusing in the plane of the membrane, AFM can unambiguously detect only a small immobile fraction. Furthermore, since AFM detection of proteins might be facilitated by high local membrane viscosity (e.g. in ordered lipid phases), the measurement of protein partition between disordered and ordered membrane domains might be biased toward the latter. In this case, the use of FCS as a complementary technique allows a more thorough investigation and deeper understanding of the system of interest. The second part of this thesis dealt with the study of complex lipid mixtures which are used to model the putative lipid/proteins domains in cells, called “rafts”. Firstly, we proved how the combined fluorescence imaging/AFM approach is useful in general for studying supported lipid membranes and the role of lipid domains in biological contexts. We investigated the effect of environmental stress on biological membranes and the protective effects of several substances. Our experimental approach was shown to be a new valuable method to visualize the dehydration damage and its effects on the lateral organization of lipid domains. Our results demonstrated that disaccharides like trehalose or sucrose are effective in protecting lipid membranes, not only on a macroscopic scale — preserving the overall integrity of the bilayer — but also on a microscopic scale, preventing the clustering of microdomains. These phenomena are interesting in the context of biological damage to living cells which need to be stored for long time, like organs to be transplanted or blood platelets. Finally, a large section of this thesis focused on the effects of a specific lipid called “ceramide” on the lateral organization of proteins and lipids in the plasma membrane. Ceramide is produced by cells in several situations, like bacterial infections or apoptosis. As consequence of ceramide production in vivo, the local concentration and the dynamic behavior of lipids and membrane receptors are supposed to exhibit strong variations. In order to understand the molecular mechanisms responsible for these effects, we applied a combination of AFM, FCS and fluorescence imaging on simple model membranes containing ceramide. We could show for the first time that, in presence of raft-like Lo/Ld phase separation, physiological quantities of ceramide induced the formation of a highly ordered gel phase, constituted of ceramide and sphingomyelin. The enzymatic production of ceramide was monitored both in supported and in free-standing bilayers. In the second case, ceramide production was connected to selective vesicle budding from the raft-like phase. Since short-chain analogues are often used in both medical applications and biochemical research to mimic the effect of long-chain ceramides, we investigated the effect of chain-length on ceramide-induced membrane reorganization. We could show that only long-chain ceramides (C18 and C16) form highly ordered domains. Interestingly, FCS measurements indicated that the physical properties of the Lo raft-like domains are hardly affected by the presence of ceramide domains. Furthermore, the increased thickness of the Ld phase — as measured by AFM — and its higher viscosity — as measured by FCS — strongly support the hypothesis of ceramide-induced cholesterol displacement from rafts. On the other hand, short-chain ceramides showed completely different biophysical properties that lead to a destabilization of the raft domains, possibly acting as surfactants between the different lipid phases. Our findings contribute to the explanation of in vivo experiments where short-chain ceramides inhibit cell signaling by disrupting the lipid order in the plasma membrane. We have so far demonstrated that ceramide plays a fundamental role in lipid-lipid interactions. In a physiological context, it is also known to produce dramatic effects in living cells. Since a majority of the processes in vivo are thought to be governed by the activity of proteins, it is highly likely that ceramide not only affects lipid organization but also modifies protein-protein and protein-lipid interactions to produce its effects. To test this hypothesis, we reconstituted several membrane proteins in lipid bilayers containing Ld, Lo, and ceramide-rich domains. We were able to show that some membrane proteins are sorted into ceramide-rich domains. More specifically, the raft-associated proteins we tested were enriched in the highly ordered ceramide-rich domains, while the Ld-associated components were excluded from them. Furthermore, the inclusion of any membrane component in ceramide-rich domains is directly connected to a dramatic reduction of its in-plane diffusion. In an in vivo context, such a reorganization of membrane receptors might be used by the cell to alter the signaling process, for example, by i) separating raft receptors from inhibitors with lower raft affinity, ii) bringing both raft-associated receptors and raft-associated signaling molecules into contact, or iii) stabilizing the interactions between a receptor and its ligand by decreasing their diffusion coefficients. In conclusion, this thesis describes a novel combination of AFM, LSM, and FCS for the investigation of the lateral organization of biological membranes. Our results show that this approach applied on model membranes of increasing complexity is an effective tool for understanding the molecular mechanisms behind the organization of biological membranes. This report opens up new possibilities for further investigation in living cell membranes using the same methodology we have described.

Magnetic force microscopy (MFM) is a widely-used technique for measuring the local magnetic properties of a variety of materials. This method covers a large fi eld of applications ranging from fundamental research of micro-magnetic phenomena to industrial applications in the development of magnetic recording components. The image formation in MFM measurements is based on the magneto-static interaction of a sharp magnetic tip with the probed sample. Despite the fact that MFM is quite easy to perform, image interpretation remains challenging. This is due to the accurate characterization of the probing tip that is needed for a quantitative interpretation of the MFM data in terms of the local magnetic properties of the sample. This thesis examines the fabrication and utilization of special MFM probes based on single ferromagnetic nanoparticles as the magnetically interacting element. A magnetic probe that consists of a very small magnetic single-domain particle can be accurately described by a magnetic point dipole. Such a probe potentially yields an improved lateral resolution and a simplifi ed quantitative interpretation of MFM images compared to a standard thin-fi lm coated MFM tip. First of all, one part of this thesis examines the fabrication of suitable single-domain particles. In particular, this part is focussed on experiments concerning the protection of these particles from oxidation in ambient conditions. To this end, these ferromagnetic particles were coated with gold using the light-induced deposition of gold in a photoactive metal-salt solution. The chemical surface passivation of the particles by the gold coating was verifi ed using diff erent techniques (SQUID, MFM). In the next step, these particles were mechanically affi xed to a standard silicon tip of atomic force microscopy (AFM). The controlled attachment of a single particle, as well as the attachment of multiple particles to such a Si-AFM tip was demonstrated. Another part of the thesis examines the magnetic imaging with particle based probes in MFM experiments. A minimum of four cobalt particles affi xed to the tip was determined as the threshold for obtaining a reasonable MFM signal. It was possible to image the magnetic domain structure of a hard disk drive sample with these particle probes. Using a simulation of the MFM data, the orientation and the position of the e ffective tip dipole were determined. The e ffective dipole moment of the tip is found by a calibration experiment assuming a magnetic dipole-dipole interaction between the tip and another magnetic particle.

This thesis presents investigations on hydrogenated graphene by scanning tunneling microscopy and spectroscopy (STM/STS) as well as the implementation of spin-polarized STM. Preparation processes for a magnetic standard sample and spin-sensitive chromium tips are developed. The measurements on graphene reveal specific hydrogen adsorption sites in low coverage and the formation of a pattern at higher coverage. Both is found to be in agreement with previous predictions and calculations. Upon hydrogenation, an impurity midgap state emerges in the density of states which is measured directly for the first time. Complementing angle resolved photoemission experiments confirm that this state is dispersionless over the whole Brillouin zone. A routine is developed to prepare the standard sample system of ultra-thin iron films on tungsten (Fe/W(110)). Investigations on this system confirm the magnetic properties known from literature, including the presence of a spin spiral, and prove that it is well suited for the characterization of spin-polarized tips. Different approaches for the preparation of tips from the antiferromagnetic material chromium are tested. Among these, a promising new method is presented: The coating of crystalline chromium tips with fresh chromium material suggests reproducibility of the tip characteristics. The performance of the produced tips in STM measurements is excellent in regard to a fixed spin-polarization, high resolution and stability. Especially, a recovery of the tip magnetization direction proposed in this thesis makes this new preparation method superior to all processes yielding antiferromagnetic tips reported so far. / Inhalt der vorliegenden Arbeit sind Untersuchungen von hydogeniertem Graphen mittels Rastertunnelmikroskopie und -spektroskopie (RTM/RTS) sowie die Einführung spin-polarisierter RTM. Im Rahmen dessen wurden Präparationsprozesse für magnetische Standardproben und spin-sensitive Chrom-Spitzen entwickelt. Die Messungen an Graphen zeigen spezifische Wasserstoff-Adsorptionsstellen bei geringer Bedeckung und die Ausbildung eines Musters bei höherer Bedeckung, jeweils in Übereinstimmung mit Vorhersagen und Berechnungen. Der durch Hydrogenierung entstehende Störstellenzustand in der Bandlücke der Zustandsdichte wurde zum ersten Mal direkt gemessen. Ergänzende winkelaufgelöste Photoelektronenspektroskopieexperimente bestätigen, dass dieser Zustand in der gesamten Brillouinzone dispersionsfrei ist. Ein Verfahren zur Herstellung magnetischer Standardproben aus ultradünnen Eisenfilmen auf Wolfram (Fe/W(110)) wurde entwickelt. RTM-Untersuchungen an diesem System bestätigen die bereits aus der Literatur bekannten magnetischen Eigenschaften, insbesondere das Vorhandensein einer Spinspirale. Damit ist Fe/W(110) hervorragend geeignet für die Charakterisierung spin-polarisierter Spitzen. Verschiedene Ansätze, die zur Herstellung von Spitzen aus dem antiferromagnetischen Material Chrom verfolgt wurden, werden präsentiert, darunter auch eine vielversprechende neue Methode: Das Aufwachsen eines frischen Chromfilms auf kristalline Spitzen desselben Materials verspricht eine Reproduzierbarkeit von Spitzeneigenschaften. Der Einsatz von so hergestellten Spitzen in RTMMessungen ist geprägt von einer festgelegten Spin-Polarisation, hohem Auflösungsvermögen und Stabilität. Insbesondere die mögliche Reproduzierbarkeit der Magnetisierungsrichtung, die in dieser Arbeit diskutiert wird, macht diese Methode allen bisher berichteten Herstellungprozessen antiferromagnetischer Spitzen überlegen.

Gegenstand dieser Dissertation ist die experimentelle Untersuchung von Schwere-Fermionen-Systemen mittels Rastertunnelmikroskopie und –spektroskopie (RTM/S). In diesen Materialien führen starke elektronische Korrelationen zur Ausbildung einer besonderen Art von \"schweren\" Ladungsträgern, deren Natur bislang nicht abschließend aufgeklärt werden konnte. Einige grundlegende Aspekte der Physik der Schwere-Fermionen-Systeme werden eingangs der Arbeit dargestellt. Im Anschluss daran werden die experimentellen Methoden der RTM und RTS eingeführt sowie die verwendeten Messaufbauten vorgestellt. Dies geschieht mit Hinblick auf die experimentellen Voraussetzungen für die RTS an Schwere-Fermionen-Systemen, insbesondere auf das spektrale Auflösungsvermögen. Die Präparation geeigneter Probenoberflächen von Schwere-Fermionen-Materialien und deren Auswirkung auf RTM-Experimente nehmen eine zentrale Stellung dieser Arbeit ein und werden daher gesondert behandelt. Vorrangig wurde dabei das Spalten einkristalliner Proben untersucht. In RTS-Untersuchungen des Schwere-Fermionen-Supraleiters CeCoIn5 ist es gelungen, die für einen Supraleiter typische Energielücke im Anregungsspektrum zu messen. Die Daten können über einen weiten Temperaturbereich mit theoretischen Voraussagen für die unkonventionelle Supraleitung in diesem Material verglichen werden. Die Resultate sind im Einklang mit früheren experimentellen Befunden, welche auf einen der Supraleitung vorausgehenden sog. „Precursor“-Zustand hindeuten. Allerdings gibt es, wie auch in anderen untersuchten Schwere-Fermionen-Supraleitern, Hinweise auf Inhomogenitäten der Probenoberfläche. Im Fall des nicht-supraleitenden Kondogitter-Systems YbRh2Si2 konnte durch Spalten von Einkristallen bei tiefen Temperaturen großflächig atomar geordnete Oberflächen erzeugt werden. Es zeigen sich starke Indikationen darauf, dass die Spektroskopie-Daten die Volumeneigenschaften des Materials reflektieren. Ein Vergleich mit theoretischen Rechnungen deutet darauf hin, dass der Kondoeffekt der magnetischen Yb3+-Ionen sich in der Tunnelleitfähigkeit widerspiegelt - bis hin zum Einfluss der sich ausbildenden räumlichen Kohärenz des Kondogitters bei tiefen Temperaturen. Diese Ergebnisse gewähren wichtige Einblicke in die thermische Entwicklung der elektronischen Korrelationen in Kondogitter-Systemen, und demonstrieren somit das große Potential der Rastertunnel-Spektroskopie für die weitere Erforschung der Schwere-Fermionen-Systeme. Die im Abschnitt 6.3 'Tunnelspektroskopie-Resultate an YbRh2Si2' dargestellten Ergebnisse sind in ähnlicher Form auch veröffentlicht in Nature Vol. 474 (2011), Seiten 362-366.

Multiferroika, also Materialien, die gleichzeitig ferroelektrische und ferromagnetische Eigenschaften besitzen, sind sowohl für die Forschung um das Verständnis dieser Eigenschaften als auch für potentielle Anwendungen in neuartigen Speichern von großem Interesse. Die Rasterkraftmikroskopie spielt hierbei eine entscheidende Rolle, da mit ihrer Hilfe die Eigenschaften solcher Probensysteme auf der Nanometerlängenskala untersucht werden können. In der vorliegenden Arbeit werden drei unterschiedliche multiferroische Systeme auf ihre ferroelektrischen und ferromagnetischen Eigenschaften sowie auf deren Kopplung hin mit Hilfe verschiedener Methoden der Rasterkraftmikroskopie untersucht. Im Grundlagenteil dieser Arbeit wird dazu zunächst eine Methode vorgestellt, mit der magnetische Spitzen für die Rasterkraftmikroskopie charakterisiert werden können, so dass in experimentellen Untersuchungen die Wechselwirkung zwischen der untersuchenden Spitze und der untersuchten Probe besser abgeschätzt werden kann. Des Weiteren wird eine Möglichkeit vorgestellt, Kelvin-Sonden-Rasterkraftmikroskopie mit der magnetischen Rasterkraftmikroskopie zu kombinieren, um elektrostatische Artefakte bei den Untersuchungen der magnetischen Eigenschaften auszuschließen. Im experimentellen Teil der Arbeit werden zuerst die beiden einphasigen Multiferroika BiFeO3 und BiCrO3 untersucht. Es kann experimentell gezeigt werden, dass für die Untersuchung der ferromagnetischen Eigenschaften von Multiferroika die Kombination aus Kelvin-Sonden-Rasterkraftmikroskopie und magnetischer Rasterkraftmikroskopie notwendig ist und mit dieser Technik die magnetischen und elektrostatischen Kräfte ohne Übersprechen voneinander getrennt werden können. Mit Hilfe der Piezoantwort-Rasterkraftmikroskopie werden die ferroelektrischen Domänen dieser Systeme untersucht und lokal die Polarisationsrichtung in den einzelnen Domänen bestimmt. Weiterhin wird an einem Schichtsystem, bestehend aus einem Nickelfilm, der auf BaTiO3 aufgebracht ist, die magnetoelektrische Kopplung analysiert. Hierbei wird vor allem der Einfluss einer elektrischen Spannung auf die leichte magnetische Achse des Nickelfilms studiert, sowie die Veränderung der magnetischen Domänenstruktur in Abhängigkeit der angelegten elektrischen Spannung.

Aufgrund einer komplexen Wechselwirkung mit Proteinen ist das Genom in einer Zelle ständig mechanischer Spannung und Torsion ausgesetzt. Daher ist es wichtig die Mechanik und die Dynamik von verdrillter DNA unter Spannung zu verstehen. Diese Situation wurde experimentell mittels einer sog. magnetischen Pinzette nachgestellt, indem sowohl Kraft als auch Drehmoment auf ein einzelnes DNA Molekül ausgeübt und gleichzeitig die mechanische Antwort des Polymers aufgezeichnet wurde. Als erstes Beispiel wurde der Übergang von linearer zu sog. plectonemischer DNA untersucht, d.h. die Absorption eines Teils der induzierten Verdrillung in einer superhelikalen Struktur. Eine abrupte Längenänderung am Anfang dieses Übergangs wurde bereits im Vorfeld publiziert. In der vorliegenden Arbeit wird gezeigt, dass diese abrupte DNA Verkürzung insbesondere von der Länge der DNA und der Ionenkonzentration der Lösung abhängt. Dieses Verhalten kann mittels eines Modells verstanden werden, in dem die Energie pro Verwringung der ersten Schlinge innerhalb der Superhelix größer ist als die aller nachfolgenden. Des Weiteren wurden DNA-DNA Wechselwirkungen in der Umgebung monovalenter Ionen durch die Analyse des Superspiralisierungsverhaltens einzelner DNA Moleküle bei konstanter Kraft charakterisiert. Solche Wechselwirkungen sind für die Kompaktierung des Genoms und die Regulation der Transkription wichtig. Oft wird DNA als gleichmäßig geladener Zylinder modelliert und ihre elektrostatischen Wechselwirkungen im Rahmen der Poisson-Boltzmann-Gleichung mit einem Ladungsanpassungsfaktor berechnet. Trotz erheblicher Anstrengung ist eine präzise Bestimmung dieses Parameters bisher nicht gelungen. Ein theoretisches Modell dieses Prozesses zeigte nun eine erstaunlich kleine effektive DNA Ladung von ~40% der nominalen Ladungsdichte. Abgesehen von Gleichgewichtsprozessen wurde auch die Dynamik eines Faltungsvorgangs von DNA untersucht. Spontane Branch Migration einer homologen Holliday-Struktur wurde genutzt, um die intramolekulare Reibung der DNA zu erforschen. Mittels einer magnetischen Pinzette wurde eine torsionslimitierte Holliday-Struktur gestreckt während die Längenfluktuationen der Zweige mit schneller Videomikroskopie bei ~3 kHz aufgezeichnet wurden. Einzelne diffusive Schritte der Basenpaare sollten auf einer sub-Millisekunden Zeitskala auftreten und viel kleiner als die Gesamtfluktuationen der DNA sein. Eine Analyse der spektralen Leistungsdichte der Längenfluktuationen ermöglicht eine eindeutige Beschreibung der Dynamik der Branch Migration. Die Holliday-Struktur wurde außerdem als nanomechanischer Linearversteller eingesetzt, um einen einzelnen fluoreszierenden Quantenpunkt durch ein exponentiell abfallendes evaneszentes Feld zu bewegen. Durch die Aufzeichnung der Emission des Quantenpunkts sowohl in dem evaneszenten Feld als auch unter gleichmäßiger Beleuchtung kann die Intensitätsverteilung des Anregungsfelds ohne weitere Dekonvolution bestimmt werden. Diese neue Technik ist von besonderem wissenschaftlichen Interesse, weil die Beschreibung dreidimensionaler inhomogener Beleuchtungsfelder eine große Herausforderung in der modernen Mikroskopie darstellt. Die Ergebnisse dieser Arbeit werden dem besseren Verständnis einer Vielzahl biologischer Prozesse, die in Verbindung mit DNA Superspiralisierung stehen, dienen und weitere technische Anwendungen des DNA-basierten Linearverstellers hervorbringen. / The genome inside the cell is continuously subjected to tension and torsion primarily due to a complex interplay with a large variety of proteins. To gain insight into these processes it is crucial to understand the mechanics and dynamics of twisted DNA under tension. Here, this situation is mimicked experimentally by applying force and torque to a single DNA molecule with so called magnetic tweezers and measuring its mechanical response. As a first example a transition from a linear to a plectonemic DNA configuration is studied, i.e. the absorption of part of the applied twist in a superhelical structure. Recent experiments revealed the occurrence of an abrupt extension change at the onset of this transition. Here, it is found that this abrupt DNA shortening strongly depends on the length of the DNA molecule and the ionic strength of the solution. This behavior can be well understood in the framework of a model in which the energy per writhe for the initial plectonemic loop is larger than for subsequent turns of the superhelix. Furthermore DNA-DNA interactions in the presence of monovalent ions were comprehensively characterized by analyzing the supercoiling behavior of single DNA molecules held under constant tension. These interactions are important for genome compaction and transcription regulation. So far DNA is often modeled as a homogeneously charged cylinder and its electrostatic interactions are calculated within the framework of the Poisson-Boltzmann equation including a charge adaptation factor. Despite considerable efforts, until now a rigorous quantitative assessment of this parameter has been lacking. A theoretical model of this process revealed a surprisingly small effective DNA charge of ~40% of the nominal charge density. Besides describing equilibrium processes, also the dynamics during refolding of nucleic acids is investigated. Spontaneous branch migration of a homologous Holliday junction serves as an ideal system where the friction within the biomolecule can be studied. This is realized by stretching a torsionally constrained Holliday junction using magnetic tweezers and recording the length fluctuations of the arms with high-speed videomicroscopy at ~3 kHz. Single base pair diffusive steps are expected to occur on a sub-millisecond time scale and to be much smaller than the overall DNA length fluctuations. Power-spectral-density analysis of the length fluctuations is able to clearly resolve the overall dynamics of the branch migration process. Apart from studying intramolecular friction, the four-arm DNA junction was also used as a nanomechanical translation stage to move a single fluorescent quantum dot through an exponentially decaying evanescent field. Recording the emission of the quantum dot within the evanescent field as well as under homogeneous illumination allows to directly obtain the intensity distribution of the excitation field without additional deconvolution. This new technique is of particular scientific interest because the characterization of three-dimensional inhomogeneous illumination fields is a challenge in modern microscopy. The results presented in this work will help to better understand a large variety of biological processes related to DNA supercoiling and inspire further technical applications of the nanomechanical DNA gear.

In this thesis, the electronic properties in superconducting LiFeAs single crystal are investigated using low temperature scanning tunneling microscopy and spectroscopy (STM/S) at various temperatures. For this purpose, the differential conductance (dI/dV) measured by STS which is directly proportional to the local density of states (LDOS) of the sample to the sub-atomic precision, is used together with the topography information. The dI/dV spectra within the ±1 V energy range reveal a characteristic feature at around -350 mV to -400 mV in stoichiometric LiFeAs. This feature seems to be a universal property among all the Fe-based high temperature superconductors, because it is also found in Fe0.965Se1.035 and NaFe0.975Co0.025As single crystals at the energy of -210 mV and -200 mV, respectively. The temperature dependent spectroscopy data averaged over a spatially fixed clean area of 2 nm × 2 nm are successfully executed between 5 K and 20 K. The two distinct superconducting phases with critical temperatures Tc = 16 K and 18 K are observed. In addition, the distance between the dip position outside the superconducting gap and the superconducting coherence peak in the spectra remains temperature independent which confirms that it is not connected to an antiferromagnetic (AFM) spin resonance. The temperature dependent spectra have been measured between 5 K and 61 K within the energy range of ±100 mV as well. The hump structure at 42 mV tends to disappear around 60 K from unknown origin. The temperature dependent quasiparticle interference (QPI) has been studied within the temperature range between 6.7 K and 25 K and analyzed by the Fourier transformation of the measured spectroscopic maps. The dispersion plots in momentum space as a function of temperature show an enhancement of QPI intensity (±5.5 mV) within the superconducting gap at the Fermi level at 6.7 K near q ~ 0. This is interpreted on the basis of Andreev bound state. In both polarities outside of this, a depletion of QPI intensity is noticed between 5.5 mV and around 9 mV. At positive energies, the QPI intensity becomes very rich above 9 mV. The size of the enhanced QPI intensity near the Fermi level, and the edge of the rich QPI intensity beyond 9 mV are found to behave like superconducting order parameter with rising of temperature. Furthermore, an energy mode peaked at around 14 mV appears in the integrated QPI intensity below superconducting Tc (6.7 K). This is consistent with the observed peak at 1st derivative of the dI/dV spectra. In both of these cases, such 14 mV peak is suppressed at normal state (25 K). This mode is therefore directly related to superconductivity in LiFeAs. The off-stoichiometric LiFeAs single crystal with superconducting Tc of 6.5 K has a 10 mV rigid band shift of the Fermi level towards electron doping. The absence of the rich QPI intensity between 9 mV and 17 mV is found compared to the stoichiometric LiFeAs, and hence the 14 mV mode is absent here. This brings us to conclude once more time that such 14 mV energy mode is relevant for superconductivity in LiFeAs.

Diese Arbeit präsentiert die Ergebnisse einer Rastertunnelmikroskopiestudie an dem stöchiometrischen Supraleiter Lithium-Eisenarsenid (LiFeAs). Topographie- sowie Spektroskopieuntersuchungen an defektfreien Bereichen der Oberfläche zeigen eine Variation der Atompositionen in Abhängigkeit von der Tunnelspannung. Weiterhin wurde die Temperaturabhängigkeit der supraleitenden Energielücke untersucht. Dabei konnte die Signatur einer bosonischen Mode und damit eine Kopplung von Quasiteilchen beobachtet werden. Neben der Untersuchung defektfreier Oberflächen wurden auch Defekte und deren Einfluss auf die supraleitenden Eigenschaften analysiert. Es wurde dabei festgestellt, dass Defekte die supraleitende Energielücke ortsabhängig verändern. Die Defekte lassen sich aufgrund ihrer Symmetrie einer möglichen Gitterposition zuordnen. Eine detaillierte spektroskopische Untersuchung verschiedener Defekte zeigt deren Einfluss auf die Zustandsdichte der supraleitenden Quasiteilchen. Dabei stellt sich heraus, dass As-Defekte die supraleitende Energielücke erheblich beeinflussen. Fe-Defekte zeigen hingegen nur einen geringen Effekt. Für die Bestimmung der Ginzburg-Landau-Kohärenzlänge wurden Messungen im Magnetfeld durchgeführt. Hierfür wird in dieser Arbeit eine geeignete Näherungsfunktion hergeleitet. Die Näherung der differentiellen Leitfähigkeit bei U=0 V in einem Flussschlauch erlaubt die Bestimmung einer Kohärenzlänge von 3,9 nm. Dies entspricht einem oberen kritischen Feld von 21 Tesla. Neben der Bestimmung der Ginzburg-Landau-Kohärenzlänge wird auch eine Analyse des Flussschlauch-Gitters durchgeführt. Dabei zeigt sich, dass der Flussschlauch-Gitterabstand dem eines tetragonalen Gitters entspricht. Allerdings zeigt sich für Magnetfelder größer als 6 Tesla eine zunehmende Unordnung des Flussschlauch-Gitters, was auf eine stärker werdende Flussschlauch-Flussschlauch-Wechselwirkung hindeutet. / This work presents scanning tunneling microscopy and spectroscopy investigations on the stoichiometric superconductor lithium iron arsenide (LiFeAs). To reveal the electronic properties, measurements on defect-free surfaces as well as near defects have been performed. The former shows a shift of atomic position with respect to the applied bias voltage. Furthermore, temperature dependent spectroscopic measurements indicate the coupling of quasiparticles in the vicinity of the superconducting coherence peaks. LiFeAs surfaces influenced by atomic defects show a spacial variation of the superconducting gap. The defects can be characterized by their symmetry and thus can be assigned to a position in the atomic lattice. Detailed spectroscopic investigations of defects reveal their influence on the quasiparticle density of states. In particular, Fe-defects show a small effect on the superconductivity while As-defects strongly disturb the superconducting gap. Measurements in magnetic field have been performed for the determination of the Ginzburg-Landau coherence length . For this purpose, a suitable fit-function has been developed in this work. This function allows to fit the differential conductance of a magnetic vortex at U=0 V. The fit results in a coherence length of 3,9 nm which corresponds to an upper critical field of 21 Tesla. Besides measurements on a single vortex, investigation on the vortex lattice have been performed. The vortex lattice constant follows thereby the predicted behavior of a trigonal vortex lattice. However, for magnetic fields larger than 6 Tesla an increasing lattice disorder sets in, presumably due to vortex-vortex-interactions.

For the past decades, Kelvin probe force microscopy (KPFM) developed from a sidebranch of atomic force microscopy to a widely used standard technique. It allows to measure electrostatic potentials on any type of sample material with an unprecedented spatial resolution. While the technical aspects of the method are well understood, the interpretation of measured data remains object of intense research. This thesis intends to prove an advanced view on how sample systems which are typical for ultrahigh resolution imaging, such as organic molecular submonolayers on metals, can be quantitavily analysed with the differential charge density model. In the first part a brief introduction into the Kelvin probe experiment and atomic force microscopy is given. A short review of the theoretical background of the technique is presented. Following, the differential charge density model is introduced, which is used to further explain the origin of contrast in Kelvin probe force microscopy. Physical effects, which cause the occurence of local differential charge densities, are reviewed for several sample systems that are of interest in high resolution atomic force microscopy. Experimental evidence for these effects is presented in the second part. Atomic force microscopy was used for in situ studies of a variety of sample systems ranging from pristine metal surfaces over monolayer organic adsorbates on metals to ferroelectric substrates both, with and without organic thin film coverage. As the result from these studies, it is shown that the differential charge density model accurately describes the experimentally observed potential contrasts. This implies an inherent disparity of the measurement results between the different Kelvin probe force microscopy techniques; a point which had been overseen so far in the discussion of experimental data. Especially for the case of laterally strong confined differential charge densities, the results show the opportunity as well as the necessity to explain experimental data with a combination of ab initio calculations of the differential charge density and an electrostatic model of the tip-sample interaction.