This thesis addresses the metal nanocluster growth process on prepatterned substrates, the development of atomistic simulation method with respect to an acceleration of the atomistic transition states, and the continuum model of the ion-beam inducing semiconductor surface pattern formation mechanism. Experimentally, highly ordered Ag nanocluster structures have been grown on pre-patterned amorphous SiO2 surfaces by oblique angle physical vapor deposition at room temperature. Despite the small undulation of the rippled surface, the stripe-like Ag nanoclusters are very pronounced, reproducible and well-separated. The first topic is the investigation of this growth process with a continuum theoretical approach to the surface gas condensation as well as an atomistic cluster growth model. The atomistic simulation model is a lattice-based kinetic Monte-Carlo (KMC) method using a combination of a simplified inter-atomic potential and experimental transition barriers taken from the literature. An effective transition event classification method is introduced which allows a boost factor of several thousand compared to a traditional KMC approach, thus allowing experimental time scales to be modeled. The simulation predicts a low sticking probability for the arriving atoms, millisecond order lifetimes for single Ag monomers and about 1 nm square surface migration ranges of Ag monomers. The simulations give excellent reproduction of the experimentally observed nanocluster growth patterns. The second topic specifies the acceleration scheme utilized in the metallic cluster growth model. Concerning the atomistic movements, a classical harmonic transition state theory is considered and applied in discrete lattice cells with hierarchical transition levels. The model results in an effective reduction of KMC simulation steps by utilizing a classification scheme of transition levels for thermally activated atomistic diffusion processes. Thermally activated atomistic movements are considered as local transition events constrained in potential energy wells over certain local time periods. These processes are represented by Markov chains of multi-dimensional Boolean valued functions in three dimensional lattice space. The events inhibited by the barriers under a certain level are regarded as thermal fluctuations of the canonical ensemble and accepted freely. Consequently, the fluctuating system evolution process is implemented as a Markov chain of equivalence class objects. It is shown that the process can be characterized by the acceptance of metastable local transitions. The method is applied to a problem of Au and Ag cluster growth on a rippled surface. The simulation predicts the existence of a morphology dependent transition time limit from a local metastable to stable state for subsequent cluster growth by accretion. The third topic is the formation of ripple structures on ion bombarded semiconductor surfaces treated in the first topic as the prepatterned substrate of the metallic deposition. This intriguing phenomenon has been known since the 1960s and various theoretical approaches have been explored. These previous models are discussed and a new non-linear model is formulated, based on the local atomic flow and associated density change in the near surface region. Within this framework ripple structures are shown to form without the necessity to invoke surface diffusion or large sputtering as important mechanisms. The model can also be extended to the case where sputtering is important and it is shown that in this case, certain "magic" angles can occur at which the ripple patterns are most clearly defined. The results including some analytic solutions of the nonlinear equation of motions are in very good agreement with experimental observation.

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.

Organic solar cells offer attractive properties for novel applications and continuous advances in material and concept development have led to significant improvements in device performance. To exploit their full potential (roll-to-roll production of flexible and top-illuminated devices, using e.g. opaque metal foil or textile as substrate), highly transparent, conductive, mechanically flexible, and cost-efficient top electrodes are of great importance. The current standard material indium tin oxide (ITO) is rigid, expensive and requires a high energy / high temperature deposition process, limiting ITO (and other transparent conductive oxides) to bottom electrode applications. This work presents fundamental investigations to understand and control the properties of transparent conductors and documents four different approaches to prepare transparent electrodes on top of efficient small molecule organic solar cells, with the aim to replace ITO. Fullerene C60 layers are investigated as completely carbon-based electrodes. For an optimized doping concentration, sheet resistance and transmittance are improved and efficient solar cells are realized. Since the lateral charge transport is still limited, a combination with a microstructured conductor is suggested. Pulsed laser deposition allows for the first time a damage-free preparation of gallium doped zinc oxide (ZnO:Ga) layers on top of organic devices by careful optimization of the deposition atmosphere. ZnO:Ga electrodes with a transmittance of Tvis = 82.7 % and sheet resistance Rs = 83 Ohm/sq are obtained. The formation of local shunts due to ZnO:Ga droplets is identified and then prevented by a shadow mask between the target and the sample, enabling solar cells with similar efficiency (2.9 %) compared to a reference device using a state-of-the-art metal top contact. Another very promising alternative are intrinsically flexible, ultra-thin silver layers. By introducing an oxide interlayer, the adverse interpenetration of silver and organic materials is prevented and the charge extraction from the solar cells is improved. With a second oxide layer on top, the silver electrode is significantly stabilized, leading to an increased solar cell lifetime of 4500 h (factor of 107). Scanning electron micrographs of Ag thin films reveal a poor wetting on organic and oxide substrates, which strongly limits the electrode performance. However, it is significantly improved by a 1 nm thin seed layer. An optimized Au/Ag film reaches Tvis = 78.1 % and Rs = 19 Ohm/sq, superior to ITO. Finally, silver electrodes blended with calcium show a unique microstructure which enables unusually high transmittance (84.3 % at 27.3 Ohm/sq) even above the expectations from bulk material properties and thin film optics. Such values have not been reached for transparent electrodes on top of organic material so far. Solar cells with a Ca:Ag top electrode achieve an efficiency of 7.2 %, which exceeds the 6.9 % of bottom-illuminated reference cells with conventional ITO electrodes and defines a new world record for top-illuminated organic solar cells. With these electrodes, semi-transparent and large-area devices, as well as devices on opaque and flexible substrates are successfully prepared. In summary, it is shown that ZnO:Ga and thin metal electrodes can replace ITO and fill the lack of high performance top electrodes. Moreover, the introduced concepts are not restricted to specific solar cell architectures or organic compounds but are widely applicable for a variety of organic devices.

This thesis addresses the metal nanocluster growth process on prepatterned substrates, the development of atomistic simulation method with respect to an acceleration of the atomistic transition states, and the continuum model of the ion-beam inducing semiconductor surface pattern formation mechanism. Experimentally, highly ordered Ag nanocluster structures have been grown on pre-patterned amorphous SiO2 surfaces by oblique angle physical vapor deposition at room temperature. Despite the small undulation of the rippled surface, the stripe-like Ag nanoclusters are very pronounced, reproducible and well-separated. The first topic is the investigation of this growth process with a continuum theoretical approach to the surface gas condensation as well as an atomistic cluster growth model. The atomistic simulation model is a lattice-based kinetic Monte-Carlo (KMC) method using a combination of a simplified inter-atomic potential and experimental transition barriers taken from the literature. An effective transition event classification method is introduced which allows a boost factor of several thousand compared to a traditional KMC approach, thus allowing experimental time scales to be modeled. The simulation predicts a low sticking probability for the arriving atoms, millisecond order lifetimes for single Ag monomers and about 1 nm square surface migration ranges of Ag monomers. The simulations give excellent reproduction of the experimentally observed nanocluster growth patterns. The second topic specifies the acceleration scheme utilized in the metallic cluster growth model. Concerning the atomistic movements, a classical harmonic transition state theory is considered and applied in discrete lattice cells with hierarchical transition levels. The model results in an effective reduction of KMC simulation steps by utilizing a classification scheme of transition levels for thermally activated atomistic diffusion processes. Thermally activated atomistic movements are considered as local transition events constrained in potential energy wells over certain local time periods. These processes are represented by Markov chains of multi-dimensional Boolean valued functions in three dimensional lattice space. The events inhibited by the barriers under a certain level are regarded as thermal fluctuations of the canonical ensemble and accepted freely. Consequently, the fluctuating system evolution process is implemented as a Markov chain of equivalence class objects. It is shown that the process can be characterized by the acceptance of metastable local transitions. The method is applied to a problem of Au and Ag cluster growth on a rippled surface. The simulation predicts the existence of a morphology dependent transition time limit from a local metastable to stable state for subsequent cluster growth by accretion. The third topic is the formation of ripple structures on ion bombarded semiconductor surfaces treated in the first topic as the prepatterned substrate of the metallic deposition. This intriguing phenomenon has been known since the 1960s and various theoretical approaches have been explored. These previous models are discussed and a new non-linear model is formulated, based on the local atomic flow and associated density change in the near surface region. Within this framework ripple structures are shown to form without the necessity to invoke surface diffusion or large sputtering as important mechanisms. The model can also be extended to the case where sputtering is important and it is shown that in this case, certain "magic" angles can occur at which the ripple patterns are most clearly defined. The results including some analytic solutions of the nonlinear equation of motions are in very good agreement with experimental observation.:1 Introduction: Atomistic Models 1 1.1 Density Functional Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 1.1.1 Schroedinger equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2 1.1.2 Density functional theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 1.2 Molecular Dynamics Simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6 1.2.1 Lagrangian mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 1.2.2 MD algorithms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9 1.3 Lattice Monte Carlo simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12 1.3.1 Thermodynamic variables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13 1.3.2 Metropolis Algorithm and limit theorem . . . . . . . . . . . . . . . . . . . . . 15 1.3.3 Kinetic Monte Carlo Simulation . . . . . . . . . . . . . . . . . . . . . . . . . 18 1.3.4 Imaginary time reaction diffusion . . . . . . . . . . . . . . . . . . . . . . . . . 24 2 Cluster Growth on Pre-patterned Surfaces 29 2.1 Nanocluster growth . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 2.1.1 Classical nucleation theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 2.1.2 Cluster growth on substrates . . . . . . . . . . . . . . . . . . . . . . . . . . . 31 2.1.3 Experimental motivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33 2.2 Local flux and surface ad-monomer diffusion . . . . . . . . . . . . . . . . . . . . . . 35 2.2.1 Surface topography and local flux . . . . . . . . . . . . . . . . . . . . . . . . 35 2.2.2 Surface gas diffusion under inhomogeneous flux . . . . . . . . . . . . . . . . . 37 2.2.3 Surface migration of ad-monomers . . . . . . . . . . . . . . . . . . . . . . . . 40 2.2.4 Simulation vs. experimental gauge . . . . . . . . . . . . . . . . . . . . . . . . 45 2.3 Nucleation models: Surface gas condensation . . . . . . . . . . . . . . . . . . . . . . 46 2.3.1 Simulation setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46 2.3.2 Simulation parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49 2.3.3 Evolution of sticking probability . . . . . . . . . . . . . . . . . . . . . . . . . 49 2.3.4 Evolution of Ag cluster growth . . . . . . . . . . . . . . . . . . . . . . . . . . 54 2.3.5 Simulation time and system evolution . . . . . . . . . . . . . . . . . . . . . . 57 2.4 Extended cluster growth model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 2.4.1 Modified setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58 2.4.2 Simulation result . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59 2.4.3 Comparison with experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . 61 2.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62 3 A Markov chain model of transition states 63 3.1 Acceleration of thin film growth simulation . . . . . . . . . . . . . . . . . . . . . . . 63 3.2 Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64 3.3 Transition states of Markov chains . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65 3.3.1 Local transition events . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65 3.3.2 The Monte-Carlo method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66 3.4 Effective transitions of objects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67 3.4.1 Convergence of the local fluctuation . . . . . . . . . . . . . . . . . . . . . . . 67 3.4.2 The importance of individual local transitions . . . . . . . . . . . . . . . . . . 68 3.4.3 The modified algorithm for effective transition states . . . . . . . . . . . . . . 69 3.5 Cluster growth simulation models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71 3.5.1 The configuration energy and migration barriers . . . . . . . . . . . . . . . . 72 3.5.2 Transition events . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75 3.5.3 Comparison with Experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . 77 3.5.4 Cluster growth stability evaluation . . . . . . . . . . . . . . . . . . . . . . . . 78 3.6 Stability of modified convergence limit . . . . . . . . . . . . . . . . . . . . . . . . . . 80 3.6.1 Acceleration of convergence to Gibbs field . . . . . . . . . . . . . . . . . . . . 80 3.6.2 Relative convergence speed . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81 3.6.3 1D Ag models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84 3.6.4 Stability theorem . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87 3.7 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 4 Ion beam inducing surface pattern formation 89 4.1 Ion-inducing pattern formation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89 4.1.1 Bradley-Harper equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89 4.1.2 Nonlinear continuum models . . . . . . . . . . . . . . . . . . . . . . . . . . . 92 4.1.3 Other approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93 4.2 Simulation of surface defects induced by ion beams . . . . . . . . . . . . . . . . . . . 94 4.2.1 MD simulation of single ion impact . . . . . . . . . . . . . . . . . . . . . . . . 94 4.2.2 Monte-Carlo simulations of surface modification . . . . . . . . . . . . . . . . 96 4.2.3 Curvature dependent surface diffusion . . . . . . . . . . . . . . . . . . . . . . 102 4.3 Continuum model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103 4.3.1 Equation of motion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104 4.3.2 A travelling wave solution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108 4.3.3 Lyapunov stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109 4.3.4 Comparison with experiment . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 4.3.5 Approximate solutions for other angles . . . . . . . . . . . . . . . . . . . . . . 110 4.4 Contribution of other effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 4.4.1 Surface diffusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111 4.4.2 Surface Sputtering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113 4.5 Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116 5 Summary 119 Appendix 123 A The discrete reaction diffusion equation . . . . . . . . . . . . . . . . . . . . . . . . . 123 B The derivation of the solution (2.20) . . . . . . . . . . . . . . . . . . . . . . . . . . . 124 C Contribution of overlapping migration area . . . . . . . . . . . . . . . . . . . . . . . 125 D The RGL potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126 E Stability of the traveling wave solution . . . . . . . . . . . . . . . . . . . . . . . . . . 127

<p dir="ltr">Thin film materials are used in many areas of our daily lives. From memory storage chips to optical coatings, these thin films are essential to the technologies on which we rely. Multiferroic thin films, a group of materials that simultaneously exhibit ferromagnetism and ferroelectricity, are of particular interest because of the new opportunities that they enable in memory storage and sensors. Bismuth-based oxide materials have proven to be excellent candidates for these applications, with multiferroic properties and anisotropic structures. This novel self-assembled structure found in layered supercell systems has applications in optical devices, such as isolators and beamsplitters. Throughout this study, thin film strain and epitaxy must be tended to as the fundamentals of film growth, adding to the complexity of these challenges.</p><p dir="ltr">In this dissertation, bismuth-based oxides, and more specifically the Bi₃Fe₂Mn₂O_x (BFMO) layered supercell phase, are studied from three perspectives. First, BFMO is integrated onto silicon substrates for commercialization using a complex buffer layer stack to mediate the differences in the crystal lattice. This allows for a demonstration of device fabrication with this film. Second, the growth and impact of strain are examined through geometric phase analysis, discovering that strain is essential for the growth of the supercell phase in BFMO. This strain can be tuned through buffer layer addition to optimize the growth of this phase. Third, two methods are demonstrated to free the BFMO material from the typical film-substrate lattice matching requirements. The process of transferring the film from the original substrate onto a different substrate removes these restrictions, allowing virtually unlimited access to applications that were previously not possible. The two methods demonstrate different solutions to the specific challenges of transferring the highly strained BFMO thin film. These findings pave a practical way to integrate multiferroic layered oxide thin films onto chips for the next generation of devices.</p>

Zentrales Thema dieser Dissertation ist die Untersuchung anorganisch/organischer Hybridsysteme (HIOS) mit besonderem Fokus auf den speziellen Prozessen an der Grenzfläche beider Materialklassen. Organische Moleküle, in Verbindung mit anorganischen Halbleitern haben ein großes Potenzial für Anwendungen in zukünftigen optoelektronischen Hybridbauteilen, indem sie Vorteile zweier unterschiedlicher Welten kombinieren. Entscheidend für die Herstellung von hybriden Strukturen ist das Verständnis der Wechselwirkungen an der Grenzfläche zwischen organischem und anorganischem Material. In dieser Arbeit werden diese Wechselwirkungen analysiert, um eine Wachstumskontrolle an der Grenzfläche zwischen konjugierten organischen Molekül und anorganischem Halbleiter zu ermöglichen. Hierfür werden unterschiedliche Ansätze verfolgt: Im ersten Teil der Arbeit wird die Wechselwirkung des Modellsystems Sexiphenyl (6P) an der Grenzfläche zu ZnO untersucht, sowie das Wachstum des Moleküls mittels verschiedener Methoden kontrolliert. Das daraus gewonnene Wissen kann im zweiten Teil dazu verwendet werden einen hybriden ZnO/6P/ZnO-Stapel zu realisieren, bei dem die organische Schicht ohne Beeinträchtigung der Kristallstruktur, mit definierten Grenzflächen bis hin zur atomaren/molekularen Ebene, überwachsen werden kann. Der letzte Teil der Arbeit befasst sich mit der optischen Echtzeit-Beobachtung während des organischen Wachstums verschiedener Moleküle. Dadurch ist es möglich Veränderungen von Struktureigenschaften und Wechselwirkungen zwischen Molekülen und dem Substrat zerstörungsfrei zu bestimmen, während diese aufgewachsen werden. Hierdurch können schlussendlich mögliche Mechanismen aufgezeigt werden, um elektronische und optische Wechselwirkung an der Grenzfläche zwischen organischem Molekül und anorganischen Halbleitern zu analysieren, sowie Wachstumsprozesse weiter zu verstehen und kontrollieren. / The central subject of this thesis are hybrid inorganic/organic systems (HIOS) with a focus on the specific processes at the interface between the two material classes. Organic molecules used together with inorganic semiconductors, have a great potential for future optoelectronic applications in hybrid components, by combining the advantages of two dissimilar worlds. Decisive for the production of hybrid structures is the understanding of the interactions at the interface between organic and inorganic material. In this thesis, the interactions are analyzed to enable growth control at the interface between conjugated organic molecules and inorganic semiconductors. In the first part of the thesis, the interaction of the model system sexiphenyl (6P) at the interface with ZnO, as well as approaches to control the growth of the molecule are being investigated. The knowledge gained here is used in the second part to realize a hybrid ZnO/6P/ ZnO stack, in which the organic layer can be overgrown without affecting the crystal structure, exhibiting defined interfaces down to the atomic/molecular level. The last part of the thesis deals with real time optical observation during organic growth of different molecules. By this changes in structural properties and interactions between molecules and the substrate can be non-destructively determined as they are growing. Ultimately, a comprehensive insight into the optical and electronic interactions at the interface between organic molecules and inorganic semiconductors can be gained and possible control mechanisms are shown.

No description available.

The exploitation of the soft x-ray/extreme ultra-violet (EUV) region of the electromagnetic spectrum is possible mainly due to the development of multilayer (ML) mirrors. This region of the electromagnetic spectrum offers great opportunities in both science and technology. The shorter wavelength allows one to see smaller features in microscopy and write finer features in lithography. High reflectivity with moderate spectral bandwidth at normal/near-normal incidence can be achieved in soft x-ray/ EUV spectral range using these ML mirrors, where natural crystals with the required large periodicity are not available. These MLs are generally artificial Bragg’s reflectors, which consist of alternative high and low density materials with periodicity in the nanometer range. The main advantages of ML optics stem from the tunability of layer thickness, composition, lateral gradient, and the gradient along the normal to the substrate; these can be tailored according to the desired wavelength regime. They have the great advantage of being adaptable to figured surfaces, enabling their use as reflective optics in these spectral regions, for focusing and imaging applications. Broadband reflectivity and wavelength tunability are also possible by using MLs with normal and lateral gradient, respectively. However, fabrication of these ML mirrors requires the capability to deposit uniform, ultra-thin (a few angstroms-thick) films of different materials with thickness control on the atomic scale. Thus, one requires a proper understanding of substrate surfaces, individual layers, chemical reactivity at interfaces and, finally, of the ML structures required for particular applications. The performance of these MLs is limited by (the lack of) contrast in optical constants of the two materials, interfacial roughness, the chemical reactivity of two materials and, finally, errors in the thickness of individual layers. Soft x-ray/extreme ultra-violet ML mirrors have found a wide range of applications in synchrotron radiation beam lines, materials science, astronomy, x-ray microscopy, x-ray laser, x-ray lithography, polarizers, and plasma diagnostics. The Indus–1 synchrotron radiation (SR) source is an operational 450 MeV machine, which produces radiation up to soft x-rays. Indus-2 is a 2.5 GeV machine, which has been commissioned recently to produce hard x-rays (E > 25 keV). The combination of Indus-1 and Indus-2 will cover a broad energy spectrum from IR to hard x-rays. Therefore, there is a significant need and opportunity to study MLs of different pairs of materials, with different parameters such as periodicity and optimum thickness of individual layers. The goal of the present thesis is to fabricate MLs for soft x-ray optics and to study their physics for application as polarizers in the wavelength range from 67 Å to 160 Å on the Indus-1 synchrotron source. To accomplish this task, a UHV electron beam evaporation system has been developed indigenously for the fabrication of MLs. Three different ML systems viz., Mo/Si, Fe/B4C and Mo/Y have been fabricated, and their surfaces and interfaces were investigated thoroughly for the polarizer application. X-ray reflectivity (XRR) has been used extensively in the investigations of these MLs. This is because XRR is a highly sensitive non-destructive technique for the characterization of buried interfaces, and gives microscopic information (at atomic resolution) over a macroscopic length scale (a few microns). Numerical analysis of XRR data has been carried out using computer programs. Depth-graded x-ray photoelectron spectroscopy (XPS) has been used for compositional analysis at interfaces for some of the ML structures, as a technique complementary to XRR. The performance of some of these MLs has been tested in the soft x-ray region, using the Indus-1 synchrotron radiation (SR) source. Prior to studying the MLs, a detailed study of the surfaces and interfaces of thin films, bi-layers, and tri-layers was carried out using XRR and the glancing incidence fluorescence technique. The discontinuous-to-continuous transition and the mode of film growth, which are vital to the optimization of layer thickness (basically for the high-atomic number or high-Z layer) in the ML structures, were also investigated using in situ sheet resistance measurement method. Indus-1 is a soft x-ray SR source that covers atomic absorption edges of many low-Z materials. The present work demonstrates the possibilities of characterizing low-Z thin films and multilayers using soft x-ray resonant reflectivity. In one case, we have shown for first time that soft x-ray resonant reflectivity can be employed as a non-destructive technique for the determination of interlayer composition. In a second study using the Indus-1 SR source, we have shown, by observing the effect of the anomalous optical constant on reflectivity pattern when photon energy is tuned across the atomic absorption edge of the constituent low-Z element, that soft x-ray resonant reflectivity is an element-specific technique. This thesis is organized into 7 chapters. A brief summary of individual chapters is presented below. Chapter 1 gives a brief general introduction to x-ray ML optics. This is followed by a discussion of the importance of the soft x-ray region of electromagnetic radiation. The optical properties of x-rays are reviewed and optical constants are calculated for some of the important materials used for x-ray MLs. The refractive index in the x-ray region being less than unity (except absorption edges), the consequent limitation of conventional transmission lenses is discussed. The limitation of glancing angle incidence optics is presented, motivating the need for ML optics, which is discussed along with a theoretically calculated reflectivity profile. The procedure for materials for the MLs for application in different spectral regions is discussed, along with a survey of literature related to the present thesis. The importance of the quality of surfaces and interfaces on the performance of ML structures has been shown through simulations. The applications of soft x-ray MLs are discussed with emphasis on polarization. This is followed by a review of different modes of growth of thin films. Finally, the scope of the present work is highlighted. Chapter 2 provides brief descriptions of the experimental techniques used in the present investigations and of the numerical methods employed for quantitative data analysis. The XRR technique is discussed elaborately because it has been used extensively. Detailed calculations of x-ray reflectivity from single surfaces, thin films and bi-layers are presented, along with simulated values. The effect of critical angle and Brewster’s angle is also discussed. Data analysis methods for computing x-ray reflectivity from multilayer structures, based on dynamical and kinematical models, have been discussed. The effect of roughness on XRR has been discussed based on the recursion formalism of dynamical theory. Simulations of XRR and experimental XRR data fitting are carried out using computer programs. The XRR experimental set up is also outlined. A theoretical background is given for the electrical measurements on thin films. This is followed by a brief overview of x-ray photoelectron spectroscopy (XPS) and interpretation of spectra. Finally, the glancing incidence x-ray fluorescence (GIXRF) technique is outlined. Chapter 3 describes in detail the ultra-high vacuum electron beam evaporation system developed in house especially for the fabrication of thin films and x-ray multilayer optics. At the outset, a brief overview of different deposition techniques commonly used for the fabrication of x-ray optical elements is presented. Design, fabrication, and assembly of different accessories are discussed. The control of thickness and uniformity of the films deposited has been checked through the experiments, whose results are provided. The results obtained for ML test structures are presented to show the capability of system in carrying out fabrication of high quality x-ray ML structures. Finally, the versatility of evaporation system incorporating in situ characterization facilities such as -situ electrical measurements for different substrate temperatures is illustrated. Chapter 4 presents a study of the growth of ultra-thin Mo films at different substrate temperatures using in situ sheet resistance measurements. First, a theoretical background is given on the different stages of island growth and on factors affecting thin film growth, followed by a discussion of the possible electrical conduction phenomena in continuous and discontinuous metal films. The nature of thin film growth and a detailed microscopic picture at different growth stages are derived from a modeling of sheet resistance data obtained in situ. The various conduction mechanisms have been identified in different stages of growth. In the island growth stage, the isotropic and anisotropic growth of Mo islands is identified from the model. In the insulator-metal transition region, experimentally determined values of critical exponent of conductivity agrees well with theoretically predicted values for a two-dimensional (2D) percolating system, revealing that Mo films on float glass substrate is predominantly a 2D structure. The minimum thickness for which Mo films becomes continuous is obtained as 1.8 nm and 2.2 nm for Mo deposited at substrate temperatures 300 K and 100 K, respectively. An amorphous-to- crystalline transition is also observed, and discussed. Chapter 5 covers the detailed study of the surfaces and interfaces studies in three different ML structures viz., Mo/Si, Fe/B4C and Mo/Y, meant for the polarizer application in the wavelength range of 67 Å to 160 Å. Multilayers with varying periodicity, varying number of layer pairs, and different ratios of high-Z layer thickness to the period, were fabricated using the electron beam system. Initially, a brief overview of the design aspects of ML structures is given, along with the theoretically calculated reflectivity at Brewster’s angle from the best material combinations. In Mo/Si MLs, the interlayer formed at the interfaces due to interdiffusion of the two elements is asymmetric in thickness, i.e., Mo-on-Si interlayer is thicker than the Si-on-Mo interlayer. To take account of these interlayers in XRR data fitting, a four layer model is considered. The effect of interlayers on reflectivity pattern was studied using simulations, and differences with respect to roughness are also discussed. The mechanism of formation of asymmetric interlayers is also discussed. The interlayer composition has determined using depth-graded XPS. The results reveal the formation of the MoSi2 composition at both the interfaces. The experimental results agree well with theoretical calculations based on solid-state amorphization reaction, which is a result of large heat of mixing. The effective heat of formation model reveals the formation of MoSi2 as the first phase. The soft x-ray reflectivity performance of the Mo/Si ML structure at Brewster’s angle is tested using Indus-1 synchrotron radiation (SR). Using XRR and GIXFR, a study of the surfaces and interfaces of bilayers of B4C-on-Fe and Fe-on- B4C, and tri-layers of Fe-B4C-Fe was carried out, with a systematic variation of Fe and B4C layer thicknesses. A sharp interface was observed in Fe-on-B4C, whereas a low density (w.r.t. Fe) interlayer is observed at the B4C-on-Fe interface. The interlayer properties fluctuates w.r.t. the bottom Fe layer thickness and is independent of the top B4C layer thickness. The nature of fluctuations has been discussed in detail. A study of the surfaces and interfaces of Fe/B4C MLs is described. Finally, a study of the surfaces and interfaces of bilayers, tri-layers, and MLs of the Mo/Y system is discussed in detail. Chapter 6 describes the application of soft x-ray resonant reflectivity for the characterization of low-Z thin films and interfaces in multilayer structures. Initially, a discussion of the energy dependence of atomic scattering factors and hence of optical constants is provided with simulations, with emphasis on the atomic absorption edge. Then, a brief overview of synchrotron radiation, with particular emphasis on the parameters of the Indus-1 synchrotron source is given. The possibilities of determining the composition of the buried interlayer with sub-nanometer scale sensitivity using soft x-ray resonant reflectivity are discussed. The methodology has been applied to study the Mo/Si interface both by simulations and by experiments on the Indus-1 SR, by tuning the photon energy to the Si L-absorption edge. Finally, direct evidence of elemental specificity of soft x-ray resonant reflectivity through the observation of the effect of anomalous optical constants on the reflectivity pattern is discussed. We demonstrate the method through simulations and experiments on the B4C material in B4C thin films and Fe/ B4C bi-layers, using Indus-1 SR tuned to the boron Kedge. Chapter 7 summarizes the main findings of the present work, and provides an outlook for further investigations in the field.

A numerical treatment of non-linear higher-order geometric evolution equations with the level set and the finite element method is presented. The isotropic, weak anisotropic and strong anisotropic situation is discussed. Most of the equations considered in this work arise from the field of thin film growth. A short introduction to the subject is given. Four different models are discussed: mean curvature flow, surface diffusion, a kinetic model, which combines the effects of mean curvature flow and surface diffusion and includes a further kinetic component, and an adatom model, which incorporates in addition free adatoms. As an introduction to the numerical schemes, first the isotropic and weak anisotropic situation is considered. Then strong anisotropies (non-convex anisotropies) are used to simulate the phenomena of faceting and coarsening. The experimentally observed effect of corner and edge roundings is reached in the simulation through the regularization of the strong anisotropy with a higher-order curvature term. The curvature regularization leads to an increase by two in the order of the equations, which results in highly non-linear equations of up to 6th order. For the numerical solution, the equations are transformed into systems of second order equations, which are solved with a Schur complement approach. The adatom model constitutes a diffusion equation on a moving surface. An operator splitting approach is used for the numerical solution. In difference to other works, which restrict to the isotropic situation, also the anisotropic situation is discussed and solved numerically. Furthermore, a treatment of geometric evolution equations on implicitly given curved surfaces with the level set method is given. In particular, the numerical solution of surface diffusion on curved surfaces is presented. The equations are discretized in space by standard linear finite elements. For the time discretization a semi-implicit discretization scheme is employed. The derivation of the numerical schemes is presented in detail, and numerous computational results are given for the 2D and 3D situation. To keep computational costs low, the finite element grid is adaptively refined near the moving curves and surfaces resp. A redistancing algorithm based on a local Hopf-Lax formula is used. The algorithm has been extended by the authors to the 3D case. A detailed description of the algorithm in 3D is presented in this work. / In der Arbeit geht es um die numerische Behandlung nicht-linearer geometrischer Evolutionsgleichungen höherer Ordnung mit Levelset- und Finite-Elemente-Verfahren. Der isotrope, schwach anisotrope und stark anisotrope Fall wird diskutiert. Die meisten in dieser Arbeit betrachteten Gleichungen entstammen dem Gebiet des Dünnschicht-Wachstums. Eine kurze Einführung in dieses Gebiet wird gegeben. Es werden vier verschiedene Modelle diskutiert: mittlerer Krümmungsfluss, Oberflächendiffusion, ein kinetisches Modell, welches die Effekte des mittleren Krümmungsflusses und der Oberflächendiffusion kombiniert und zusätzlich eine kinetische Komponente beinhaltet, und ein Adatom-Modell, welches außerdem freie Adatome berücksichtigt. Als Einführung in die numerischen Schemata, wird zuerst der isotrope und schwach anisotrope Fall betrachtet. Anschließend werden starke Anisotropien (nicht-konvexe Anisotropien) benutzt, um Facettierungs- und Vergröberungsphänomene zu simulieren. Der in Experimenten beobachtete Effekt der Ecken- und Kanten-Abrundung wird in der Simulation durch die Regularisierung der starken Anisotropie durch einen Krümmungsterm höherer Ordnung erreicht. Die Krümmungsregularisierung führt zu einer Erhöhung der Ordnung der Gleichung um zwei, was hochgradig nicht-lineare Gleichungen von bis zu sechster Ordnung ergibt. Für die numerische Lösung werden die Gleichungen auf Systeme zweiter Ordnungsgleichungen transformiert, welche mit einem Schurkomplement-Ansatz gelöst werden. Das Adatom-Modell bildet eine Diffusionsgleichung auf einer bewegten Fläche. Zur numerischen Lösung wird ein Operatorsplitting-Ansatz verwendet. Im Unterschied zu anderen Arbeiten, die sich auf den isotropen Fall beschränken, wird auch der anisotrope Fall diskutiert und numerisch gelöst. Außerdem werden geometrische Evolutionsgleichungen auf implizit gegebenen gekrümmten Flächen mit Levelset-Verfahren behandelt. Insbesondere wird die numerische Lösung von Oberflächendiffusion auf gekrümmten Flächen dargestellt. Die Gleichungen werden im Ort mit linearen Standard-Finiten-Elementen diskretisiert. Als Zeitdiskretisierung wird ein semi-implizites Diskretisierungsschema verwendet. Die Herleitung der numerischen Schemata wird detailliert dargestellt, und zahlreiche numerische Ergebnisse für den 2D und 3D Fall sind gegeben. Um den Rechenaufwand gering zu halten, wird das Finite-Elemente-Gitter adaptiv an den bewegten Kurven bzw. den bewegten Flächen verfeinert. Es wird ein Redistancing-Algorithmus basierend auf einer lokalen Hopf-Lax Formel benutzt. Der Algorithmus wurde von den Autoren auf den 3D Fall erweitert. In dieser Arbeit wird der Algorithmus für den 3D Fall detailliert beschrieben.

Das wesentliche Ziel dieser Doktorarbeit ist es, die Zusammenhänge zwischen der Struktur von kleinen organischen Molekülen, deren Anordnung in der Dünnschicht und der Effizienz organischer Solarzellen zu beleuchten. Die Kombination der komplementären Methoden spektroskopischer Ellipsometrie (VASE) und Röntgenstreuung, vor allem der unter streifendem Einfall (GIXRD), hat sich als sehr effiient für die Strukturuntersuchungen organischer Dünnschichten erwiesen. Zusammen geben sie einen detailreichen Einblick in die intermolekulare Anordnung, die Kristallinität, die molekulare Orientierung, die optischen Konstanten n und k und die Phasenseparation von organischen Schichten. Zusätzlich wird die Topografie der organischen Dünnschicht mit Rasterkraftmikroskopie untersucht. Der erste Fokus liegt auf der Analyse des Dünnschichtwachstums von Zink-Phthalocyanin (ZnPc) Einzelschichten. Für alle untersuchten Schichtdicken (5, 10, 25, 50 nm) und Substrattemperaturen (Tsub=30°C, 60°C, 90°C) zeigt ZnPc ein kristallines Schichtwachstum mit aufrecht stehenden ZnPc Molekülen. Um effiziente organische Solarzellen herzustellen, werden Donor- und Akzeptormoleküle üblicherweise koverdampft. Bei der Mischung von Donor- und Akzeptormolekülen bildet sich eine gewisse Phasenseparation aus, deren Form wesentlich für die Ladungsträgerextraktion entlang der Perkolationpfade ist. Der Ursprung dieser Phasenseparation wird innerhalb dieser Arbeit experimentell für ZnPc:C60 Absorber-Mischschichten untersucht. Um die Ausprägung der Phasenseparation zu variieren, werden verschiedene Tsub (30°C, 100°C, 140°C) und Mischverhältnisse (6:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:6) bei der Koverdampfung von ZnPc und C60 angewendet. GIXRD Messungen zeigen, dass hier der bevorzugte Kristallisationsprozess von C60 Molekülen die treibende Kraft für eine effiziente Phasenseparation ist. Solarzellen, die ZnPc:C60 Mischschichten mit verbesserter Phasenseparation enthalten (Tsub=140°C, 1:1), zeigen eine verbesserte Ladungsträgerextraktion und somit eine höhere Effizienz von 3,0% im Vergleich zu 2,5% für die entsprechende Referenzsolarzelle (Tsub=30°C, 1:1). Im zweiten Teil der Arbeit wird der Einfluss der Molekülorientierung auf die Dünnschichtabsorption beispielhaft an ZnPc und Diindenoperylen (DIP) untersucht. DIP und ZnPc Moleküle, die auf schwach wechselwirkenden Substraten wie Glas, SiO2, amorphen organischen Transportschichten oder C60 aufgedampft sind, zeigen eine eher stehende Orientierung innerhalb der Dünnschicht in Bezug zur Substratoberfläche. Im Gegensatz dazu führt die Abscheidung auf stark wechselwirkenden Substraten, wie z.B. einer Gold- oder Silberschicht oder 0.5 nm bis 2 nm dünnen PTCDA (3,4,9,10-Perylentetracarbonsäuredianhydrid) Templatschichten laut GIXRD und VASE Messungen dazu, dass sich die ZnPc und DIP Moleküle eher flach liegend orientieren. Dies führt zu einer wesentlich besseren Dünnschichtabsorption da das molekulare Übergangsdipolmoment jeweils innerhalb der Ebene des ZnPc und des DIP Moleküls liegt. Ein Einbetten von Gold- oder Silberzwischenschichten in organischen Solarzellen führt leider zu keinen klaren Abhängigkeiten, da die verbesserte Absorption durch die flach liegenden Moleküle von Mikrokavitäts- und plasmonischen Effekten überlagert wird. Ebenso wenig führte das Einfügen einer PTCDA-Zwischenschicht in organischen Solarzellen zum Erfolg, da hier Transportbarrieren den Effekt der verbesserten Absorption überlagern. Das letzte Kapitel konzentriert sich auf den Einfluss der Molekülstruktur auf das Dünnschichtwachstum am Beispiel von DIP und dessen Derivaten Ph4-DIP und P4-Ph4-DIP, Isoviolanthron und Bis-nFl-NTCDI (N,N-Bis(fluorene-2-yl)-naphthalenetetra-carboxylic Diimid) Derivaten. GIXRD Messungen belegen deutlich, dass die sterischen Behinderungen, hervorgerufen durch die Phenylringe (für Ph4-DIP und P4-Ph4-DIP) und Seitenketten (für Bis-nFl-NTCDI), ein amorphes Schichtwachstum induzieren. Im Vergleich sind die Dünnschichten von DIP und Bis-HFl-NTCDI kristallin. Bezüglich der Molekülorientierung und folglich der Absorption von DIP und dessen Derivaten kann ein starker Einfluss des Schichtwachstums beobachtet werden. In Solarzellen verhindert die Präsenz der Phenylringe eine effiziente Phasenseparation der Mischschichten aus (P4-)Ph4-DIP:C60, was zu einer verschlechterten Ladungsträgerextraktion und damit zu einem reduzierten Füllfaktor (FF) von 52% im Vergleich zu dem entsprechender DIP:C60 Solarzellen mit FF=62% führt Die Untersuchungen an der Bis-nFl-NTICDI Serie zeigen ein ähnliches Ergebnis: Auch hier zeichnen sich die amorphen Schichten aus Bis-nFl-NTCDI Molekülen mit Seitenketten durch schlechtere Transporteigenschaften aus als nanokristalline Bis-HFl-NTCDI Schichten. / The aim of this thesis is to demonstrate correlations between the molecular structure of small organic molecules, their arrangement in thin films, and the solar cell performance. For structure analysis of the organic thin films, the combination of variable angle spectroscopic ellipsometry (VASE) and grazing incidence X-ray diffraction (GIXRD) as complementary methods turned out to be a powerful combination. Using both methods, it is possible to obtain information about the crystallinity, crystallite size, intermolecular arrangement, mean molecular orientation, optical constants n and k, and phase separation within thin films. In addition, the topography of thin films is analyzed by atomic force microscopy. First, the thin film morphology of pristine zinc-phthalocyanine (ZnPc) films deposited at different substrate temperatures (Tsub=30°C, 60°C, 90°C) and for varying film thicknesses (5, 10, 25, 50 nm) is investigated. The ZnPc films grow highly crystalline with an upright standing molecular orientation with respect to the substrate surface for all investigated Tsub and all film thicknesses. In effcient organic solar cells, donor and acceptor molecules are commonly co-deposited to form a blend absorber film. This is usually accompanied by a certain phase separation between donor and acceptor molecules leads to a formation of percolation paths necessary to extract electrons and holes towards the electrodes. For ZnPc:C60 blends the origin of this phase separation process is analyzed by investigating different degrees of phase separation induced by film deposition at different Tsub (30°C, 100°C, 140°C) and for different blend ratios (6:1, ... , 1:6 (vol%)). GIXRD measurements indicate that the preferred crystallization of C60 is the driving force for good phase separation. Solar cells with improved phase separation of ZnPc:C60 blends (Tsub=140°C, 1:1) reveal a better charge carrier extraction and thus enhanced effciencies of 3.0% in comparison to 2.5% for the reference device (Tsub=30°C, 1:1). In the second part, the impact of molecular orientation within the absorber thin films on light harvesting is examined for pristine ZnPc and diindenoperylene (DIP) films. For film deposition on weakly interacting substrates like glass, SiO2, amorphous organic transport films, or C60, the orientation of DIP and ZnPc molecules is found to be upright standing. In contrast, GIXRD and VASE measurements show that films deposited onto strongly interacting substrates like Au and Ag, as well as on thin PTCDA templating layers lead to nearly flat-lying ZnPc and DIP molecules. Since the molecular transition dipole moment is oriented in the plane of the DIP and ZnPc molecules, the light absorption in films with flat-lying molecules is strongly improved. Unfortunately, an implementation of Au or Ag sublayers in organic solar cells does not result in reliable dependencies since the enhanced absorption by an improved molecular orientation is superimposed by different effects like microcavity and plasmonic effects. The implementation of PTCDA interlayers leads to transport barriers making the solar cell data interpretation difficult. In the last part, the influence of molecular structure on thin film growth is studied for DIP and its derivatives Ph4-DIP and P4-Ph4-DIP, isoviolanthrone, and Bis-nFl-NTCDI derivatives. GIXRD measurements reveal that steric hindrance is induced by the addition of side chains (for Bis-nFl-NTCDI) and phenyl rings (for Ph4-DIP and P4-Ph4-DIP) (N,N-Bis(fluorene-2-yl)-naphthalenetetra-carboxylic diimide) leading to an amorphous thin film growth. In contrast, DIP films and Bis-HFl-NTCDI films are found to be crystalline. The mean molecular orientation and hence the absorption is strongly affected by the different growth modes of DIP and its derivatives. In OSC, the presence of the phenyl rings prevents an effcient phase separation for (P4-)Ph4-DIP:C60 blends which causes diminished charge extraction in comparison to the crystalline DIP:C60 blends. For the Bis-nFl-NTCDI series, the transport properties are significantly worse in the amorphous films composed of Bis-nFl-NTCDI derivatives with alkyl chains in comparison to the nanocrystalline films made of the bare Bis-HFl-NTCDI.