Die Schriftenreihe „Werkstoffe und werkstofftechnische Anwendungen“ behandelt Themengebiete der Werkstoffwissenschaft und -technik, der Oberflächentechnik sowie deren industriellen Anwendungen. Es werden vorrangig aktuelle Forschungsergebnisse der Professuren Verbundwerkstoffe und Oberflächentechnik/Funktionswerkstoffe des Instituts für Werkstoffwissenschaft und Werkstofftechnik der TU Chemnitz vorgestellt. Weiterhin sind in der Schriftenreihe die Tagungsbände des jährlich am Institut stattfindenden „Werkstofftechnischen Kolloquium“ enthalten. Die einzelnen Bände beschäftigen sich mit den Forschungsgebieten Galvanische Metallabscheidung, Anodisieren, Thermisches und Kaltgas-Spritzen, Löten, Verbundwerkstoffe, Werkstoffverbunde, Wärmebehandlung, CVD-Beschichtungen/PVD-Beschichtungen, Simulation in der Beschichtungstechnik, Organisches Beschichten (Pulverbeschichten, Lackieren, Sol-Gel-Verfahren), Elektrochemisches Strukturieren, Thermomechanische Behandlung und Mechanische Werkstoffeigenschaften. / The book series „Werkstoffe und werkstofftechnische Anwendungen“ outlines up-to-date topics of material science and engineering, surface engineering as well as resulting industrial applications. Mainly, recent research results of the departments Composite Materials and Surface Engineering/Functional Materials of the Institute of Material Science and Engineering of Chemnitz University of Technology are presented. In addition, the book series includes the proceedings of the annual in-house conference “Werkstofftechnisches Kolloquium”. The separate volumes concentrate on the following fields of scientific research: Galvanised Coating, Anodising, Thermal and Cold Spraying, Soldering and Brazing, Composite Materials, Composite Structures, Thermal and Thermomechanical Treatment, CVD and PVD Coating, Simulation of Coating Processes, Organic coating (Powder Coating, Varnishing, Sol-Gel Processes), Electrochemical Structuring and Mechanical Material Properties.

L’objectif de cette thèse est la synthèse de composés de manganèse et de matériaux hybrides qui soient intéressants du point de vue bioinorganique et magnétique. Pour accomplir ce but, nous avons découpé la stratégie en trois étapes constituant les différents chapitres de ce manuscrit :(a) Synthèse et caractérisation des composés moléculaires de manganèse et l’étude de leurs propriétés magnétiques.Nous avons réussi à obtenir la structure cristalline des vingt-trois nouveaux composés de Mn de différentes nucléarités, d’état d’oxydation II, III ou IV. Nous avons étudié les propriétés magnétiques de ces composés et nous avons établi des corrélations magnéto-structurales. Les composés de MnII ont été aussi étudiés par spectroscopie RPE.(b) Synthèse et caractérisation des matériaux hybrides basés sur des composés moléculaires de manganèse insérés dans de la silice mésoporeuse. Les composés moléculaires sélectionnés ont été insérés dans de la silice mésoporeuse (du type MCM-41). Les complexes de Mn dans les supports ont été caractérisés par ATG, XPS, ICP-OES, spectroscopie IR et mesures magnétiques. (c) Étude des propriétés catalytiques des composés moléculaires et des matériaux hybrides.Une famille de composés moléculaires obtenus dans cette thèse sont des modèles structuraux et fonctionnels de la catalase à Mn, une enzyme présente dans certaines bactéries, ayant des propriétés antioxydantes (H2O2 « scavenger »). L’activité catalase pour ces composés et les matériaux hybrides dérivés a été étudiée dans l’acétonitrile et dans l’eau. / The main objective of this work is the synthesis of manganese compounds and hybrid materials that may be relevant from a bioinorganic and magnetic point of view. The developed strategy comprises three main steps that form different sections in this thesis:(a) Synthesis and characterization of molecular manganese compounds and study of the magnetic propertiesThe crystal structure of twenty-three new Mn compounds of different nucleartities were obtained in which the Mn oxidation state is II, III, or IV. The magnetic properties of all these compounds were profoundly studied and they have been rationalized with their structural and electronic parameters. The MnII compounds were also studied with EPR spectroscopy. (b) Synthesis and characterization of hybrid materials based on molecular manganese compounds inside mesoporous silica.Selected molecular compounds were inserted inside mesoporous silica (MCM-41 type). The Mn complexes inside the supports were characterized with TGA, XPS, ICP-OES, IR spectroscopy, and magnetic measurements.(c) Study of the catalytic properties of both molecular compounds and hybrid materials.A family of the molecular compounds obtained in this work are structural and functional models of the Mn catalase, an enzyme found in some bacteria with antioxidant properties (H2O2 scavenger). The catalase activity for these compounds and the hybrid materials was studied in acetonitrile and water.

No description available.

This thesis is focused on the description of the method of reactive sputtering of thin films. Currently, there are many ways how to create thin films and there are many applications of thin films in various industrial sectors. In this paper at the first are listed the issue of thin films, followed by an overview of the deposition techniques and of the chemical analysis of deposited thin films. It also describes the four-point measurement method of sheet resistance, mechanical test of adhesion and optical properties. At the end of the theoretical part are described the material composition of the deposited films. The goal of the practical part is to optimize the deposition process of the mixed layer of indium tin oxide (In2O3: SnO2) and contribute to the overall understanding of the influence of annealing on the layer. There were created six series of samples with that applied layers. First, the work focused on examining of the influence of annealing on the throughput in the whole measuring range, and then comparing the series due to the transmittance in the visible light spectrum. Furthermore were compared the value of sheet resistance of unannealed and subsequently annealed samples.

Dans le cadre du développement durable, les procédés rapides, propres et peu énergivores sont très recherchés particulièrement en chimie pour les réactions d’oxydation. A part les solutions de génie des procédés, la catalyse est l’un des meilleurs atouts pour améliorer le processus. Le vanadium étant l’un des meilleurs métaux catalytiques pour de tels réactions, nous avions à nous attaquer son problème de relargage dans le milieu réactionnel en vue d’applications acceptables pour l’environnement. Nous proposons donc dans cette thèse des catalyseurs au vanadium fixé à l’intérieur des nano pores de silices mésoporeuses hexagonales de type MCM-41. La grande dispersion et la rétention du vanadium sont promues grâce à la présence d’ion d’ancrage : Al(III), Ti(IV), Zr(IV) and Ce(IV). Une grande variété de catalyseurs de type V-(Al/Ti/Zr/Ce)-MCM-41 ont été préparés à partir de trois méthodes de synthèse: l’une, ultra-rapide en une étape assistée par micro-onde, la seconde à étapes séquentielles multiples mettant en œuvre une technique de pochoir moléculaire et la troisième à nombre d’étapes réduites utilisant un traitement thermique partiel d’une surface préalablement organosilylée avant le greffage des métaux. Un large panel de techniques physicochimiques fut appliqué à la caractérisation de ces solides avec une attention particulière portée à l’analyse de la bande de transfert de charge ligand-métal du vanadium au degré d’oxydation +5 dont le décalage vers le bleu est corrélé à la taille des clusters d’oxyde de ces ions. La rétention du vanadium dans le méthanol a été corrélée à la dispersion du vanadium comme la dégradation à l’air du 1,2-diphényle-2-méthoxyéthanol. Ce substrat fut choisi comme modèle pour étudier la dégradation de la lignine par clivage C-C ou C-O. Notons que ce bio-polymère produit du phénoxypropanol methylé bio-sourcé utilisé dans les bio-carburants et comme précurseur en chimie fine. Dans le cas présent, un balayage à haut débit de la dégradation de cette molécule mettant en œuvre 96 mini-réacteurs en parallèle a permis de sélectionner le solvant, le métal d’ancrage et la teneure des deux métaux donnant la plus haute conversion. Contrairement aux catalyseurs homogènes, nos catalyseurs présentent une très haute sélectivité en clivage C-C. / The search for practical large-scale, fast, clean and energy saving chemical processes are highly regarded in the frame of a sustainable development, particularly for the most problematic oxidation reactions. Apart from chemical engineering solutions, improving the process using heterogeneous catalysis is one of the most adapted solution. Vanadium being considered the best metal for such kind of reactions, one had to tackle the problem of its high dispersion on a support to minimize its high propensity for leaching and to optimize its stability for practicable, safe and clean uses. In the present thesis, vanadium is supported inside the nanopores of a mesoporous silica of MCM-41 type where the high dispersion is assisted by the presence of anchoring ions such as Al(III), Ti(IV), Zr(IV) and Ce(IV) ions. A large set of V-(Al/Ti/Zr/Ce)-MCM-41 catalysts was prepared according to three different methods of preparation: i) ultra-fast one-pot synthesis protocol using the assistance of microwave, ii) post-synthesis modification using molecular stencil patterning (MSP) technique and iii) partial thermal treatment (PTT) of the organo-silylated support. The catalysts were characterized thoroughly using a panel of physical techniques and, particularly, the blue shift of the optical gap measured from the vanadium charge transfer band known to correlated with the dispersion of the metal. In complement, the stability was tested from metal leaching using methanol as a corrosive solvent while their catalytic reactivity was estimated in the aerobic oxidation of 1,2-diphenyl-2-methoxyethanol. This is a model reaction that simulates the oxidative C-C bond cleavage in lignin, the most difficult and crucial step in the degradation of this biopolymer, then producing in a clean way valuable methoxylated phenoxy propanol units useful for biomass fuels or bio-sourced precursors for fine chemistry. A high throughput screening approach was applied to test this aerobic oxidation reaction running over 96 reactors in parallel at the same temperature and sorting out the best catalysts with the most suitable anchoring ions and metal loading for the highest catalytic efficiency. / 在可持续发展的背景下，对于清洁高效节能可行的大规模化工过程尤其是存在诸多问题的氧化反应过程的探索倍受瞩目。除化学工程解决方案之外，通过多相催化来改进反应过程也是最可行的途径之一。钒被认为是最适合于催化此类反应的金属之一，其亟待解决的问题是实现钒在载体上的高度分散，并最大限度地降低其浸出倾向，改善其稳定性，从而实现对其安全清洁有效的利用。本文提出将钒负载于MCM-41型六方介孔二氧化硅的纳米孔道中，通过锚定离子如Al(III)、 Ti(IV)、Zr(IV)、Ce(IV)离子的存在促进钒的高度分散和固载。采用三种不同的方法制备了一系列V-(Al/Ti/Zr/Ce)-MCM-41催化剂：1、超快微波一步合成法，2、使用分子复刻版技术改性的后嫁接法，3、对有机硅烷化载体进行部分热处理改性的后嫁接法。通过一系列物理化学技术对合成的催化剂进行了充分表征，特别是对与金属分散度相关的钒的电荷跃迁带的测量和与其对应的光谱带隙蓝移进行了分析。随后，以甲醇作为腐蚀溶剂对合成的钒催化剂进行了金属析出的稳定性测试。通过一种木质素模型化合物1,2-diphenyl-2-methoxyethanol的需氧氧化反应测试了所合成负载型钒催化剂的催化活性。在相同温度及反应条件下，用96通道高通量微反应器技术评价了所制催化剂对该反应的催化性能，筛选出具有最高催化效率的负载型钒催化剂及其最适合的锚定离子。该反应中的碳-碳键裂解反应是木质素降解的最关键也是最困难的步骤之一，可通过这类生物聚合物的降解以清洁的方式生产有用的生物质燃料或生物来源高附加值精细化学品前驱体。

The aim of this Master’s Degree thesis project is to design and develop point diffraction interferometer plates. In this project the PDI plates are re-designed, changing the design which was used in previous projects in Halmstad University. The transparency of PDI plates can be controlled by coating them with NiCr film. Firstly, four plates with coating of different thickness of NiCr were developed. The relationship between transmittance and the thickness of NiCr was established by testing these plates for transmittance and reflectance with the help of a laser and an optical power meter. The absorption coefficient of clear substrates and reflection of light is also taken into account to achieve the correct results. The parameters like the diameter of semi-transparent area around the pinholes and the size of pinholes is chosen after fully understanding its application. The lay-out and description of design is also included in the report.

The re-entry space vehicles encounter high temperatures when they enter the earth atmosphere and the high temperature air in the shock layer around the body undergoes partial dissociation. Also, the gas molecules injected into the shock layer from the ablative thermal protection system (TPS) undergo pyrolysis which helps in reducing the net heat flux to the vehicle surface. The chemical species due to the pyrolysis add complexity to the stagnation flow chemistry (52 chemical reactions) models which include species like NOx, CO and hydrocarbons (HCs). Although the ablative TPS is responsible for the safety of re-entry space vehicle, the induced chemical species result in variety of adverse effects on environment such as global warming, acid rain, green house effect etc. The well known three-way-catalyst (TWC) involves simultaneous removal of all the three gases (i.e, NOx, CO, Hydrocarbons) present in the shock layer. Interaction of such three-way-catalyst on the heat shield materials or on the wall of the re-entry space vehicle is to reduce the heat flux and to remove the gases in the shock layer, which is an important issue. For the re-entry vehicle the maximum aerodynamic heating occurs at an altitude ranging about 68 to 45 km during which the vehicle is surrounded by high temperature dissociated air. Then the simplest real gas model of air is the five species model which is based on N2, O2, O, NO and N. This five species model assumes no ionization and no pyrolysis gases are emitted from the heat shield materials. The experimental research work presented in this thesis is directed towards the understanding of catalytic and non-catalytic surface reactions on high temperature materials in presence of strong shock heated test gas. We have also explored the possibility of using shock tube as a high enthalpy device for synthesis of new materials. In the first Chapter, we have presented an overview of re-entry space vehicles, thermal protection system (TPS) and importance of real gas effects in the shock layer. Literature survey on TPS, ablative materials and aerothermochemistry at the stagnation point of reentry capsule, in addition to catalytic and non-catalytic surface reactions between the wall and dissociated air in the shock layer are presented. In Chapters 2 and 3, we present the experimental techniques used to study surface reactions on high temperature materials. A brief description of HST2 shock tunnel is presented and this shock tunnel is capable of generating flow stagnation enthalpies ranging from 0.7 to 5 MJ/kg and has an effective test time of ~ 800 µs. High speed data acquisition system (National Instruments and Yokogawa) used to acquire data from shock tube experiments. The experimental methods like X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), Raman and FTIR spectroscopy have been used to characterize the shock-exposed materials. Preliminary research work on surface nitridation of pure metals with shock heated nitrogen gas is discussed in Chapter 2. Surface nitridation of pure Al thin film with shock heated N2 is presented in Chapter 3. An XPS study shows that Al 2p peak at 74.2 eV is due to the formation AlN on the surface of Al thin film due to heterogeneous non-catalytic surface reaction. SEM results show changes in surface morphology of AlN film due to shock wave interaction. Thickness of AlN film on the surface increased with the increase in temperature of the shock heated nitrogen gas. However, HST2 did not produce sufficient temperature and pressure to carry out real conditions of re-entry. Therefore design and development of a new high enthalpy shock tunnel was taken up. In Chapter 4, we present the details of design and fabrication of free piston driven shock tunnel (FPST) to generate high enthalpy test gas along with the development of platinum (Pt) and thermocouple sensors for heat transfer measurement. A free piston driven shock tunnel consists of a high pressure gas reservoir, compression tube, shock tube, nozzle, test section and dump tank connected to a vacuum pumping system. Compression tube has a provision to fill helium gas and four ports, used to mount optical sensors to monitor the piston speed and pressure transducer to record pressure at the end of the compression tube when the piston is launched. Piston can attain a maximum speed of 150 m/s and compress the gas inside the compression tube. The compressed gas bursts the metal diaphragm and generates strong shock wave in the shock tube. This tunnel produces total pressure of about 300 bar and temperature of about 6000 K and is capable of producing a stagnation enthalpy up to 45 MJ/kg. The calibration of nozzle was carried out by measuring the pitot tube pressure in the dump tank. Experimentally recorded P5 pressure at end of the shock tube is compared with Numerical codes. Calibrated pressure P5 values are used to calculate the temperature T5 of the reflected shock waves. This high pressure and high temperature shock heated test gas interacts with the surface of the high temperature test materials. For the measurement of heat transfer rate, platinum thin film sensors are developed using DC magnetron sputtering unit. Hard protective layer of aluminum nitride (AlN) on Pt thin film was deposited by reactive DC magnetron sputtering to measure heat transfer rate in high enthalpy tunnel. After the calibration studies, FPST is used to study the heat transfer rate and to investigate catalytic/non-catalytic surface reaction on high temperature materials. In Chapter 5, an experimental investigation of non-catalytic surface reactions on pure carbon material is presented. The pure carbon C60 films and conducting carbon films are deposited on Macor substrate in the laboratory to perform shock tube experiments. These carbon films were exposed to strong shock heated N2 gas in the shock tube portion of the FPST tunnel. The typical shock Mach number obtained is about 7 with the corresponding pressure and temperature jumps of about 110 bar and 5400 K after reflection at end of the shock tube. Shock exposed carbon films were examined by different experimental techniques. XPS spectra of C(1s) peak at 285.8 eV is attributed to sp2 (C=N) and 287.3 eV peak is attributed to sp3 (C-N) bond in CNx due to carbon nitride. Similarly, N(1s) core level peak at 398.6 eV and 400.1 eV observed are attributed to sp3-C-N and sp2-C=N of carbon nitride, respectively. SEM study shows the formation of carbon nitride crystals. Carbon C60 had melted and undergone non-catalytic surface reaction with N2 while forming carbon nitride. Similar observations were made with conducting carbon films but the crystals were spherical in shape. Micro Raman and FTIR study gave further evidence on the formation of carbon nitride film. This experimental investigation confirms the formation of carbon nitride in presence of shock-heated nitrogen gas by non-catalytic surface reaction. In Chapters 6 and 7, we present a novel method to understand fully catalytic surface reactions after exposure to shock heated N2, O2 and Ar test gas with high temperature materials. We have employed nano ZrO2 and nano Ce0.5Zr0.5O2 ceramic high temperature materials to investigate surface catalytic reactions in presence of shock heated test gases. These nano crystalline oxides are synthesized by a single step solution combustion method. Catalytic reaction was confirmed for both powder and film samples of ZrO2. As per the theoretical model, it is known that the catalytic recombination reaction produces maximum heating on the surface of re-entry space vehicles. This was demonstrated in this experiment when a metastable cubic ZrO2 changed to stable monoclinic ZrO2 phase after exposure to shock waves. The change of crystal structure was seen using XRD studies and needle type monoclinic crystal growth with aspect ratio (L/D) more than 15 was confirmed by SEM studies. XPS of Zr(3d) core level spectra show no change in binding energy before and after exposure to shock waves, confirming that ZrO2 does not change its chemical nature, which is the signature of catalytic surface reaction. When a shock heated argon gas interacted with Ce0.5Zr0.5O2 compound, there was a change in colour from pale yellow to black due to reduction of the compound, which is the effect of heat transfer from the shock wave to the compound in presence of argon gas. The reduction reaction shows the release of oxygen from the compound due to high temperature interaction. The XPS of Ce(3d) and Zr(3d) spectra confirm the reduction of both Ce and Zr to lower valent states. The oxygen storage and release capacity of the Ce0.5Zr0.5O2 compound was confirmed by analyzing the reduction of Ce4+ and Zr4+ with high temperature gas interaction. When Ce0.5Zr0.5O2 (which is same as Ce2Zr2O8) in cubic fluorite structure was subjected to strong shock, it changed to pyrochlore (Ce2Zr2O7) structure by releasing oxygen and on further heating it changed to Ce2Zr2O6.3 which is also crystallized in pyrochlore structure by further releasing oxygen. If this heating is carried out in presence of argon test gas, fluorite structure can easily change to pyrochlore Ce2Zr2O6.3 structure, which is a good electrical conductor. Due to its oxygen storage capability (OSC) and redox (Ce4+/Ce3+) properties, Ce0.5Zr0.5O2 had been used as oxygen storage material in three-way-catalyst. Importance of these reactions is that the O2 gas released from the compound will react with gas released from the heat shield materials, like NOx, CO and hydrocarbon (HCs) species which results in reduction of temperature in the shock layer of the re-entry space vehicle. The compound Ce0.5Zr0.5O2 changes its crystal structure from fluorite to pyrochlore phase in presence of shock heated test gas. The results presented in these two Chapters are first of their kind, which demonstrates the surface catalytic reactions. In Chapter 8, we present preliminary results of the oxygen recombination on the surface of heat shield material procured from Indian Space Research Organization (ISRO) used as TPS in re-entry space capsule (Space capsule Recovery Experiment SRE-1) and on thin film SiO2 deposited on silicon substrate. The formation of SiO between the junctions of SiO2/Si was confirmed using XPS study when shock exposed oxygen reacted on these materials. The surface morphology of the ablated SiO2 film was studied using SEM. The damage induced due to impact of shock wave in presence of oxygen gas was analyzed using Focused Ion Beam (FIB) microscope. The results reveal the damage on the surface of SiO2 film and also in the cross-section of the film. We are further investigating use of FIB, particularly related to residual stress developed on thin films due to high pressure and high temperature shock wave interaction. In Chapter 9, conclusions on the performance of FPST, synthesis of high temperature materials, catalytic and non-catalytic surface reactions on the high temperature material due to shock-heated test gases are presented. Possible scope for future studies is also addressed in this Chapter.

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.

No description available.

No description available.