No description available.

Industrial production of hydrogen from the syngas, generated from steam reformation of natural gas or coal gasification, sets conditions for hydrogen separation membranes in terms of operating conditions. An alternative source for hydrogen is a syngas generated by gasification of municipal solid wastes which are likely to set more stringent conditions for the separation membranes. There is therefore, a growing demand for separation membranes with improved permeability and particularly of low cost. Among various alternatives, metallic membranes are particularly attractive due to their high selectivity and permeability for hydrogen, exemplified by palladium (Pd). However, due to high cost of Pd there is still a demand to develop alternative metallic membranes that are of low cost and have improved durability. Efforts have therefore concentrated on either alloying Pd so as to reduce its cost or on alternative membrane compositions of particularly b.c.c. structure. The current study deals with hydrogen separation membranes and aims to develop infrastructure for rapid identification of membrane compositions with improved permeability. The study is made up of three parts / i) development of sputter deposition system that would allow deposition of multiple compositions in a single experiment, ii) development of substrate material that would support the thin film membranes and would allow permeability measurement and iii) development of a set-up to measure the permeability of the thin film membranes. In the present thesis, a sputter deposition system incorporating three targets was successfully constructed. The system as tested with palladium-niobium-titanium (Pd-Nb-Ti) ternary system after necessary adjustment would yield thin films of homogenous thickness (&le / 7%) over a sample area of &asymp / 150 mm diameter. A total of 21 substrates each in 19 mm diameter arranged in triangular form in the substrate holder could successfully be deposited where composition distributions covered a greater portion of Pd-Nb-Ti ternary phase diagram. The structure of the deposited thin films can successfully be controlled by substrate temperature as well as by the pressure of plasma gas (argon). With the help of these parameters, structural diversity can also be produced beside the compositional variation. As for substrates, two materials were investigated. These were titanium dioxide (TiO2) modified porous stainless steel (PSS) and anodic porous alumina (AAO). TiO2 modified PSS due to its associated surface roughness leads to the deposition of films with defected structure which as a result is not gas tight. AAO produced via anodization of aluminum foil had a regular (40-60 nm) pore structure that provides a suitable surface for thin film depositions which could be defect free. However, AAO is very delicate and fragile which makes it difficult to adapt it as a support material for permeability measurement/hydrogen separation purposes. Finally, a set-up was developed for measurement of hydrogen permeability which is capable of measurement over a wide pressure and temperature conditions, i.e. hydrogen pressures up to 10 bar and temperature as high as 450 &deg / C. It is recommended that so as to identify compositions with improved permeability, Nb or a similar metal which has extremely high permeability could be used as a support material. This would tolerate the evaluation of the films which are not totally defect free.

Near infrared region (NIR) of the electromagnetic spectrum (EM) is defined as 700nm to 1400nm wavelength interval by International Commission on Illumination(CIE). This wavelength interval is extensively used for target acquisition, night vision, wireless communication etc. Therefore, filtering the desired portion of EM spectra becomes a need for that kind of applications. Interference filters are multilayer optical devices which can be designed and produced for the desired wavelength intervals. The production of near infrared interference filters is a process of depositing thin material layers on the suitable substrates. In this thesis, a multilayer NIR filter will be designed for a selected wavelength interval by the use of dierent materials. Then, transmission quality, thermal stability, dependence of the transmission values on the incoming beam angle, performance and durability of the filter will be studied.

The aim of this work is plasma diagnostic during the deposition of thin films based on organosilicone compounds. These layers have a wide range of applications mainly as protective coatings or intermediate phase in composites reinforced by glass fibers. The theoretical part of this work gives a basic fundaments of optical emission spectroscopy and mass spectroscopy and describes procedures for rotational, vibrational, and electron temperature calculations. The RF capacitive coupled discharge in configuration with planar electrodes was used with tetravinylsilane (TVS) organosilicone monomer in this study. The optical emission spectroscopy and mass spectroscopy were applied for the plasma diagnostics. The deposition process was carried out in continuous regime with applied power of 20, 25, 40, 50, 60, and 70 W, some experiments were done also in pulsed regime with duty cycle 1:1, 1:4 and 1:9 at fixed power of 50 W and 10 W when discharge was on. The atomic lines of hydrogen Balmer series and many rotational lines of molecular hydrogen were identified in the spectra. Besides them, the molecular bands of SiH, CH and C2 species were observed. The rotational temperature calculated from 0-0 CH band was in the range of 600 – 1000 K depending on the discharge conditions. The electron temperature in the range of 3600-7500 K was calculated from hydrogen atomic lines. In situ mass spectra collected simultaneously with optical emission spectra showed TVS monomer fragmentation increase with the increase of applied power in continuous regime. This result well correlated with OES in case of CH radical and hydrogen species, the other particles were mainly non-measurable by emission spectroscopy. The same results were also obtained with respect to the duty cycle parameter. The presented results clearly demonstrated the increase of monomer fragmentation with the increase of mean applied discharge power. Determination of prepared layer properties is a subject of other works and their relation to the plasma parameters will be a subject of further studies.

Das Ziel der vorliegenden Arbeit war die erstmalige, umfassende und systematische Untersuchung aller Teilprozesse bei der ionenstrahlgestützten Schichtabscheidung (IBSD). Silber (Metall) und Germanium (Halbleiter) wurden als Beispielsysteme ausgewählt, da auf Grund der unterschiedlichen Eigenschaften der beiden Materialien prinzipielle Unterschiede in der Zerstäubung und Schichtabscheidung zu erwarten sind. Zur Bearbeitung der wissenschaftlichen Fragestellung erfolgte eine Charakterisierung der Primärteilchen sowie der zerstäubten und gestreuten Teilchen bezüglich ihrer Energie und Winkelverteilung sowie eine Charakterisierung der abgeschiedenen Schichten bezüglich ihrer Schichtdicke, Komposition, Struktur, Oberflächentopographie, elektrischen und optischen Eigenschaften unter Variation der Art (Argon und Xenon), der Energie (0.5 keV–1.5 keV) und des Einfallswinkels der Primärteilchen relativ zur Targetnormalen (0°–60°) sowie des betrachteten polaren Emissionswinkels (-40°–90°). Die dargestellten Ergebnisse demonstrieren den systematischen Einfluss der primären Prozessparameter (Ionenart, Energie, Einfallswinkel und Emissionswinkel) auf die Eigenschaften der zerstäubten und gestreuten Teilchen und auf die Eigenschaften der erzeugten Silber- und Germaniumschichten, wobei die Eigenschaften der abgeschiedenen Schichten mit den Eigenschaften der schichtbildenden Teilchen korrelieren. Bei der IBSD von Silber führt der Einfluss der hochenergetischen zerstäubten und gestreuten Teilchen auf die Schichten zu kleineren mittleren Korngrößen und damit zu höheren spezifischen Widerständen und Variationen in den optischen Eigenschaften. Die Untersuchungen zur IBSD von Germanium zeigen, dass der Einbau von Prozessgas in die abgeschiedenen Schichten mit der Anzahl der gestreuten Primärionen, deren Energie hoch genug für eine Implantation in die Schicht ist, korreliert werden kann.

No description available.

The aim of this thesis is a study of processes during organosilicone thin film deposition via plasma polymerization. Recently, thin films are the most expanding way of surface modification of materials. They are used as protective coatings, functional layers, they can increase or decrease adhesion to different compounds (e.g. water), or just improve mechanical properties of bulk materials. Plasma polymers, which are not known so long, are a modern trend in evolution of thin film deposition. They have perfect adhesion to the substrate and they are highly resistant against most of chemical compounds. Their structure is quite different from the structure of classical polymers. Recently, organosilicon compounds are used as precursors for plasma polymers because silicon built in the structure of plasma polymer allows thin film deposition on glass substrate and the organic part of monomer gives us infinite possibilities of modification. In our case dimethylphenylsilane (DMPS) was used as a monomer. Various RF low pressure discharges were used during this study. Plasma diagnostic was performed by optical emission spectroscopy of inductive coupled plasma. This method allows us to determine plasma composition during the deposition process. Thus we can predict the composition of deposited thin film according to input parameters. From relative populations of fragments we are able to find out optimal conditions for deposition process. We can also calculate temperature of particles in plasma which gives us some information about particle energies. The first part of the study deals with the identification of particles (fragments) created by fragmentation of monomer in plasma environment. We successfully identified hydrogen atomic lines of Balmer’s series in the spectra. Many rotational lines of hydrogen molecule were also detected. Atomic carbon occurred only in small amount. Much more carbon was detected in the form of CH radical. We also found some weak lines connected to atomic silicon. When we used a mixture of DMPS and oxygen, OH radical and O2+ were present in spectra. Next, optimal settings of deposition were determined for particular fragments from relative intensities of these fragments in optical emission spectra. Using this information we are able to set up the process to deposit thin films of desired composition and properties. We calculated electron temperature from intensities of hydrogen lines in Balmer’s series. Rotational temperature was obtained from CH radical intensity. Unfortunately, there was no convenient radical from which intensity we would be able to calculate vibrational temperature. All results and information obtained during the research can be used in industrial plasma polymerization processes and development of new coatings and functional thin films. Other studies on DMPS or similar monomer may also be realized to get more knowledge about processes in plasma and this thesis could serve as a basis for further research. Moreover, this study is a part of an international project. The aim of this project is to study processes during plasma polymerization both theoretically and practically. Once finished, the project and its results will be presented in scientific literature and at international conferences.

The scope of this thesis is the study of the interplay between structure and magnetism in amorphous materials. The investigations focus on the growth of amorphous layers and the study of the influence of structural disorder and reduced physical extension on the magnetic properties of thin films and multilayers. The examined magnetic materials are FeZr alloys, as well as other amorphous transition metal alloys such as CoZr and FeCoZr. Thin films and multilayers of the studied materials were deposited using magnetron sputtering in ultra-high vacuum conditions. Their amorphous structure and layering quality was investigated using X-ray scattering techniques and in several cases with transmission electron microscopy. The chemical composition of the alloys was determined with Rutherford Backscattering Spectrometry. The magnetic properties were investigated using the magneto-optic Kerr effect and SQUID magnetometry, as well as polarized neutron reflectometry and X-ray magnetic circular dicroism measurements. For FeZr alloys deposited as multilayers with Al2O3 as spacer layer, it was found that Fe-rich nanocrystallites, formed at the metal/oxide interfaces, exert large influence on the magnetic properties. The use of AlZr alloys as buffer layers promotes the growth of highly amorphous FeZr layers. FeZr/AlZr multilayers with good layering quality can also be obtained. The influence of the reduced layer thickness on the magnetic moment, Curie temperature and magnetic dimensionality of the magnetic layers is addressed for FeZr/AlZr multilayers. Thin FeZr layers in these structures are found to belong to the 2D XY dimensionality class. The change of the magnetic moment and Curie temperature with reduced FeZr layer thickness is quantified. In addition, the induced magnetic moment in the alloy element Zr was investigated in FeZr and CoZr alloy films. The possibility to imprint a preferred magnetization direction during thin film preparation was demonstrated for FeCoZr layers. Lastly, AlZr alloy films were studied with respect to their oxidation stability at room and elevated temperatures, aiming towards development of materials with passivating properties.

Interference filters are multilayer thin film devices. They use interference effects between the incident and reflected radiation waves at each layer interface to select wavelengths. The production of interference filters depend on the precise deposition of thin material layers on substrates which have suitable optical properties. In this thesis, the main target is to design and produce two optical filters (short-pass filter and long-pass filter) for the CCDs that will be used in the electronics of a space camera. By means of these filters, it is possible to take image in different bands (RGB and NIR) by identical two CCDs. The filters will be fabricated by plasma ion-assisted deposition technique.

Combustion chemical vapor deposition (combustion CVD) is a thin film deposition process that uses a flame created by the ignition of an aerosol containing precursors dissolved in a flammable solvent. Combustion CVD is a relatively new technique for creating thin film oxide coatings. Combustion CVD has been successfully used to deposit high quality thin oxide films for potential applications such as thermal barrier coatings, dielectric thin films, composite interlayer coatings, etc. The present work involved developing the optimum parameters for deposition of thin films of yttria-stabilized zirconia (YSZ), alumina (Al₂O₃), and YSZ-alumina composites followed by a determination of the mechanical properties of the films (measured using nanoindentation) as a function of composition. The optimized parameters for deposition of YSZ, alumina, and YSZ-alumina composites onto single crystal a-plane alumina involved using an organic liquid as the flammable solvent and Y 2-ethylhexanoate, Zr 2-ethylhexanoate and Al acetylacetonate as the metal precursors at a 0.002 M concentration delivered at 4 ml/min at flame temperatures of 155 ℃ and substrate temperatures of 105 ℃. The resulting films were grown with deposition rates of ~ 1.5 μm/hr. Measurement of the mechanical properties (hardness, elastic modulus and fracture toughness) of the films was performed using a mechanical properties microprobe called the Nanoindenter®. In order to obtain valid results from nanoindentation, the combustion CVD films were optimized for minimum surface roughness and grown to a thickness of approximately 0.8 μm. With the penetration depth of the indenter at approximately 150 nm, the 800 nm thickness of the film made influences of the substrate on the measurements negligible. The hardnesses and elastic moduli of the YSZ-alumina films did not vary with the composition of the film. The fracture toughness, however, did show a dependence on the composition. It was found that second phase particles of alumina grown into a YSZ matrix increased the fracture toughness of the films (on average, 1.76 MPa• m⁰.⁵ for 100% YSZ to 2.49 MPa• m⁰.⁵ for 70 mol% YSZ/30 mol% alumina). Similarly, second phase particles of YSZ grown into an alumina matrix also increased the fracture toughness (on average, 2.20 MPa• m⁰.⁵ for 100% alumina to 2.45 MPa• m⁰.⁵ for 37.2 mol% YSZ/62.8 mol% alumina). Modeling of the fracture toughness of the YSZ-alumina films was successfully achieved by using the following toughening mechanisms: crack deflection from the second phase particles, grain bridging around the particles, and residual stress from the CTE mismatch between the film and the substrate and between the second phase particles and the matrix of the film.