The rapid development of micro/nanofabrication techniques have enabled engineering of material interfacial properties. Micro/nanostructures with unique electrical, mechanical, thermal, magnetic, optical, and biological properties, have found applications in a wide range of fields such as electronics, photonics, biological/chemical sensing, tissue engineering, and diagnostics, etc. As such, numerous strategies have been developed for structuring materials into micro/nano- scale. However, the challenge still lies in the high cost, low throughput, complexity in fabrication, and difficulty in scaling up. This thesis aims to explore fabrication strategies for micro/nanostructured surfaces that are versatile, simple, and inexpensive. The thin film stencil lift-off technique with both Parylene and self-adhesive vinyl has been explored for this purpose. Further applications of the resulted micro/nanostructured surfaces are also presented in this thesis. Through improved Parylene stencil fabrication process, both spontaneously phase-segregated and arbitrary binary supported lipid bilayer patterns have been achieved. Also, the microstructured Parylene surfaces have been ddemonstrated for patterning stacked SLBs that are either homogeneous or phase-segregated. Without any lithography technique involved, vinyl stencil lift-off offers as a facile and inexpensive benchtop method for patterning thin films such as metal and glassy films. Combining the thermal shrinking of shape memory polymer, the patterned feature sizes are further decreased by 60% in both x and y dimensions, pushing the patterning resolution to down to sub-100 μm range. In addition, the shrinking process induces micro/nanostructures onto the deposited thin film, and the structure sizes are easily tunable with film thickness deposited. Further applications of such patterned micro/nanostructured surfaces has also been explored. The structured gold films have served as high-surface-area electrodes for electrochemical sensing. By introducing photoresist as a sacrificial layer, the structured gold thin films can be lifted off and transferred onto elastomeric substrate, and serve stretchable and flexible sensors. Such sensing devices exhibit great stability and reproducibility even when working under external strain. Finally, the micro/nanostructured glassy surfaces have been employed as substrate for cell growth to study topographical effect on cell morphology. It has been concluded that rougher surfaces lead to cell elongation, and finer structures promote filopodia generation. These results underscore the strength and suitability of thin film stencil lift-off as a powerful technique for creating micro- and nanostructured surfaces. These structured surfaces could find applications in many other areas, due to their great properties such as tunable structure size, high surface area, flexibility, and long-term stability. / Thesis / Doctor of Philosophy (PhD)

Dealloying refers to the partial, selective dissolution of the less noble component(s) of a binary or ternary alloy precursor, resulting in a noble-rich, porous structure that has high surface area. Such surface structure is beneficial for fuel cells (FC) because FC uses platinum (Pt), a scarce metal, to catalyze the oxygen reduction reaction (ORR) at the cathode surface. In order to characterize the benefit of the dealloying process in FC ORR catalysts with the rotating disk electrode (RDE) technique, a high surface area catalyst support, namely 3M Co’s nanostructured thin film (NSTF), was incorporated into the RDE measurements. NSTF-coated glassy carbon (GC) disks were used in RDE experiments on a Pt/Pt1-xIrx (0.05 < x < 0.3) composition spread. ORR measurements using NSTF-coated GC disks measure the catalytic properties with the same morphology, composition and surface structure as would be found in a fuel cell. A series of Pt1-xCox and Pt1-xNix (0.5 < x < 0.8) dealloy catalyst precursor films were tested using NSTF-coated GC disks in RDE studies. The value of x in Pt1-xMx (M = Ni, Co) was selected to be high in order to examine the dealloying process. The catalyst films were examined by a RDE test protocol that tracked the surface enhancement factor (SEF) and ORR current densities over a large number of test cycles. The aim was to measure the catalytic performance of the Pt-M materials as dealloying took place. The SEF of the PtCo and PtNi materials increased rapidly at the beginning and reached a plateau as high as 50 cm2/cm2 while the specific ORR activities increased as the initial M content in the catalyst precursor increased. The impact of the dealloying process on morphology was examined by completely dealloying a Pt3Ni7 precursor, deposited on mirror-polished GC disks, at a constant potential. As the dealloying process continued, the SEF of the material increased from about 1 cm2/cm2 to > 30 cm2/cm2 and resulted in the formation of whisker-like structures.

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M. Tech. (Mechanical Engineering, Faculty of Engineering and Technology): Vaal University of Technology / Presently there exist a lot of controversies about the mechanical properties of nanomaterials. Several convincing reasons and justifications have been put forward for the controversies. Some of the reasons are varying processing routes, varying ways of defining equations, varying grain sizes, varying internal constituent structures, varying techniques of imposing strain on the specimen etc. It is therefore necessary for scientists, engineers and technologists to come up with a clearer way of defining and dealing with nanomaterials’ mechanical properties. The parameters of the internal constituent structures of nanomaterials are random in nature with random spatial patterns. So they can best be studied using random processes, specifically as stochastic processes. In this dissertation the tools of stochastic processes have been used as they offer a better approach to understand and analyse random processes. This research adopts the approach of ascertaining the correct mathematical models to be used for experimentation and modelling. After a thorough literature survey it was observed that size and temperature are two important parameters that must be considered in selecting the relevant mathematical definitions for nanomaterials’ mechanical properties. Temperature has a vital role to play during grain refinement since all severe plastic deformation involves thermomechanical processes. The second task performed in this research is to develop the mathematical formulations based on the experimental observation of 2-D grains and 3-D grains deformed by Accumulative Roll-Bonding and Equal Channel Angular Pressing. The experimental observations revealed that grains deformed by Accumulative Roll-Bonding and Equal Channel Angular Pressing are elongated when observed from the rolling direction, and transverse direction, and equiaxed when observed from the normal direction. In this dissertation, the different experimental observations for the grain size variants during grain refinement were established for 2-D and 3-D grains. This led to the development of a stochastic model of grain-elongation for 2-D and 3-D grains. The third task was experimentations and validation of proposed models. Accumulative Roll-Bonding, Equal Channel Angular Pressing and mechanical testing (tensile test) experiments were performed. The effect of size on elongation and material properties were studied to validate the developed models since size has a major effect on material’s properties. The fourth task was obtaining results and discussion of theoretical developed models and experimental results. The following facts were experimentally observed and also revealed by the models. Different approaches of measuring grain size reveal different strains that cannot be directly obtained from plots of the corresponding grain sizes. Grain elongation evolved as small values for larger grains, but became larger for smaller grains. Material properties increased with elongation reaching a maximum and started decreasing as is evident in the Hall-Petch to the Reverse Hall-Petch Relationship. This was alluded to the fact that extreme plastic straining led to distorted structures where grain boundaries and curvatures were in “non-equilibrium” states. Overall, this dissertation contributed new knowledge to the body of knowledge of nanomaterials’ mechanical properties in a number of ways. The major contributions to the body of knowledge by his study can be summarized as follows: (1) The study has contributed in developing a model of elongation for 2-D grain and 3-D grains. It has been generally reported by researchers that materials deformed by Accumulative Roll-Bonding and Equal Channel Angular Pressing are generally elongated but none of these researchers have developed a model of elongation. Elongation revealed more information about “size” during grain refinement. (2) The Transmission Electron Microscopy revealed the grain shape in three directions. The rolling direction or sliding direction, the normal direction and the transverse direction. Most developed models ignored the different approaches of measuring nanomaterials’ mechanical properties. Most existing models dealt only with the equivalent radius measurement during grain refinement. In this dissertation, the different approaches of measuring nanomaterials’ mechanical properties have been considered in the developed models. From this dissertation an accurate correlation can be made from microscopy results and theoretical results. (3) This research has shown that most of the published results on nanomaterials’ mechanical properties may be correct although controversies exist when comparing the different results. This research has also shown that researchers might have considered different approaches to measure nanomaterials’ mechanical properties. The reason for different results is due to different approaches of measuring nanomaterials’ mechanical properties as revealed in this research. Since different approaches of measuring nanomaterials’ mechanical properties led to different obtained results, this justify that most published results of nanomaterials’ mechanical properties may be correct. This dissertation revealed more properties of nanomaterials that are ignored by the models that considered only the equivalent length. (4) This research has contributed to the understanding of nanomaterials controversies when comparing results from different researchers.

Planar two-dimensional (2-D) nanostructured indium oxide (InOx) and one-dimensional (1-D) tin oxide (SnO2) semiconductor metal-oxide layers have been utilised for gas sensing applications. Novel layered Surface Acoustic Wave (SAW) based sensors were developed consisting of InOx/SiOxNy/36°YXLiTaO3, InOx/SiNx/SiO2/36°YXLiTaO3 and InOx/SiNx/36°YXLiTaO3 The 1 µm intermediate layers of silicon oxynitride (SiOxNy), silicon nitride (SiNx) and SiO2/SiNx matrix were deposited on lithium tantalate (36°YXLiTaO3) substrates by r.f. magnetron sputtering, electron-beam evaporation and plasma enhanced chemical vapour deposition (PECVD) techniques, respectively. As a gas sensitive layer, a 100 nm thin layer of InOx was deposited on the intermediate layers by r.f. magnetron sputtering. The targeted gases were ozone (O3) and hydrogen (H2). An intermediate layer has multiple functions: protective role for the interdigital transducers' electrodes as well as an isolating effect from InOx sensing layer, thereby improving the sensor performance. The developed SAW sensors' exhibited high response magnitudes with repeatable, reversible and stable responses towards O3 and H2. They are capable of sensing concentrations as low as 20 parts-per-billion for O3 and 600 parts-per-million for H2. Additionally a conductometric type novel sensing structure of SnO2/36°YX LiTaO3 was also developed by depositing a thin layer of SnO2 nanorods by PECVD. The gas sensing performance exhibited repeatable, reversible, stable responses towards NO2 and CO. The surface morphology, crystalline structure and preferred orientation of the deposited layers were investigated by Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). A polycrystalline, oxygen deficient non-stoichiometric InOx with grain sizes of 20-40 nm was revealed. The 1-D nanostructures were characterised by Transmission Electron Microscopy (TEM) showing nanorods with needle-like shape , diameters of 10-20 nm a t the top and 30-40 nm at the base as well as a preferential growth orientation of [ ] on the LiTaO3 substrate. The developed sensors are promising for O3, H2 and CO sensing.

In the last decades, significant improvements regarding the design, materials and technology of rock drills have been made. Likewise, in sheet metal forming, forming tools experience very high contact pressures when processing high strength steel sheets. In both applications components operate under extremely tough contact conditions that result in an accelerated component failure. Enhancements on mechanical properties of components material subjected to extreme contact conditions are highly required in order to withstand the application loads and prevent severe wear. The present thesis was focused on understanding of machinery component damage mechanisms under severe contact conditions. A case study of worn components used in rock drilling and sheet metal cold work was carried out. Thread joints from rock drilling and punches from sheet metal pressing were selected for the investigation. For these components, sliding contact under high contact pressure is a common load condition under the components usage. Then, to understand and quantify the influence of contact parameters, load and surface quality on material performance, laboratory simulations were performed. The results were used for a comparative analysis of the typical damage mechanisms observed in the tests and the case study of the components. The case study results showed that the threaded surfaces underwent severe plastic deformation due to the high-pressure sliding contact. The microstructure beneath the worn surface was altered and surface cracks and delamination were frequently observed at the worn surface. The dominant damage mechanism found on the investigated punches was adhesive wear. Material transfer adds friction stresses at the punch surface and ultimately, with repeated punch strokes, it leads to initiation and propagation of fatigue cracks. Wear process in thread joint and punch wear was simulated using the SOFS. The worn specimens tested experimentally showed similar wear mechanisms obtained in the case study. The thread joint wear simulation showed that the total damage at the worn surface was a result of adhesive wear, plastic deformation, and initiation and propagation of fatigue cracks. In addition, the results showed that the type of motion had a significant influence on the worn volume and crack initiation, and more severe wear was observed at reciprocal motion. The punch wear simulation showed that the friction quickly increased as work material from metal sheets transferred to the disc surface. The rate of the material transfer was strongly dependent on the combination of sheet material and tool steel. Further, the present experimental simulations were applicable to characterize and predict wear of components in the application. / Components used in rock drilling and sheet metal forming operate under harsh contact conditions that result in an early-life component failure. Wear and fatigue are considered as the most common damage mechanism for these components. Commonly, the service life of a component is designed based on its fatigue life. However, wear might have a significant effect on the components life too. Wear results in a surface damage that in turn may cause a fatigue crack initiation. Therefore, knowledge about wear of materials and components is a key factor in design and prediction of the lifetime of the components. In order to predict wear of a certain component, a thorough understanding of the component with regards to its material properties, application loads and working environment, and damage mechanisms is required. The overall aim of the present work was to define the typical wear mechanisms occurred on machinery components used in rock drilling and sheet metal forming. A comparative analysis of the case studies and results from performed laboratory tests simulated wear mechanisms in the applications highlighted wear mechanisms and factors influencing severity of wear in the applications. Obtained information is crucial for ranking and selection of the best material in the applications. / <p>The presentation will will be via zoom. PhD student will together with the supervisors will be in Karlstad while the opponent is in Luleå. </p>

Title: Nano-structured multicomponent plasma polymers for controlled immobilization of biomolecules Author: Iurii Melnichuk Department / Institute: Department of Macromolecular Physics/Charles University Supervisor of the doctoral thesis: Doc. Ing. Andrey Shukurov, Ph.D. Abstract: The aim of this thesis is to highlight the feasibility of tailored nano- structures in functionalizing surfaces for biointerfacial interactions. Development of new techniques for the production of nanoscaled biomaterials can be of use in a variety of medical and biological applications, e.g. biosensors, microarrays, drug sensors, implants, blood-contacting devices. This thesis first examines the early stages of nano-structured thin film growth fabricated by vapor phase deposition of poly(ethylene). We discuss island growth within a framework of rate equation theory, dynamic scaling theory and capture zone distribution. In a second stage, we test dielectric barrier discharge to activate PE nano-pattern for covalent immobilization of proteins. Finally, we assess cell behavior on surfaces in dependence on morphology and the presence of cell adhesive protein tropoelastin. We employ plasma polymerization to produce ultrathin hydrocarbon layer capable of protein anchoring. The thesis findings for the first time manifest the critical...

The current study is focused on the characterization of four natural leaf species (quaking, bigtooth and columnar european aspen as well as black locust) possessing a unique dual-scale cuticle structure composed of micro- and nano-scale asperities, which are able to effectively resist wetting (superhydrophobic), characteristic of The Lotus Effect. Scanning Electron Microscopy (SEM) was used to track the growth and evolution of their distinctive nano-scale epicuticular wax (ECW) morphologies over one full growing season. In addition, the stability of their superhydrophobic property was tested in various environments. It was determined that the long-term stability of these surfaces is tentatively linked to various environmental stress factors. Specifically, a combination of high temperature and humidity caused the degradation of nano-scale asperities and loss of the superhydrophobic property. The dual-scale surface structure was found to provide a suitable template for the design of future superhydrophobic engineering materials.

The current study is focused on the characterization of four natural leaf species (quaking, bigtooth and columnar european aspen as well as black locust) possessing a unique dual-scale cuticle structure composed of micro- and nano-scale asperities, which are able to effectively resist wetting (superhydrophobic), characteristic of The Lotus Effect. Scanning Electron Microscopy (SEM) was used to track the growth and evolution of their distinctive nano-scale epicuticular wax (ECW) morphologies over one full growing season. In addition, the stability of their superhydrophobic property was tested in various environments. It was determined that the long-term stability of these surfaces is tentatively linked to various environmental stress factors. Specifically, a combination of high temperature and humidity caused the degradation of nano-scale asperities and loss of the superhydrophobic property. The dual-scale surface structure was found to provide a suitable template for the design of future superhydrophobic engineering materials.

The widespread adoption of photonic circuits requires the economics of volume manufacturing offered by integration technology. A Complementary Metal-Oxide Semiconductor compatible silicon material platform is particularly attractive because it leverages the huge investment that has been made in silicon electronics and its high index contrast enables tight confinement of light which decreases component footprint and energy consumption. Nevertheless, there remain challenges to the development of photonic integrated circuits. Although the density of integration is advancing steady and the integration of the principal components – waveguides, optical sources and amplifiers, modulators, and photodetectors – have all been demonstrated, the integration density is low and the device library far from complete. The integration density is low primarily because of the difficulty of confining light in structures small compared to the wavelength which measured in micrometers. The device library is incomplete because of the immaturity of hybridisation on silicon of other materials required by active devices such as III-V semiconductor alloys and ferroelectric oxides and the difficulty of controlling the coupling of light between disparate material platforms. Metamaterials are nanocomposite materials which have optical properties not readily found in Nature that are defined as much by their geometry as their constituent materials. This offers the prospect of the engineering of materials to achieve integrated components with enhanced functionality. Metamaterials are a class of photonic crystals includes subwavelength grating waveguides, which have already provided breakthroughs in component performance yet require a simpler fabrication process compatible with current minimum feature size limitations. The research reported in this PhD thesis advances our understanding of the structure-property relations of key planar light circuit components and the metamaterial engineering of these properties. The analysis and simulation of components featuring structures that are only just subwavelength is complicated and consumes large computer resources especially when a three dimensional analysis of components structured over a scale larger than the wavelength is desired. This obstructs the iterative design-simulate cycle. An abstraction is required that summarises the properties of the metamaterial pertinent to the larger scale while neglecting the microscopic detail. That abstraction is known as homogenisation. It is possible to extend homogenisation from the long-wavelength limit up to the Bragg resonance (band edge). It is found that a metamaterial waveguide is accurately modeled as a continuous medium waveguide provided proper account is taken of the emergent properties of the homogenised metamaterial. A homogenised subwavelength grating waveguide structure behaves as a strongly anisotropic and spatially dispersive material with a c-axis normal to the layers of a one dimensional multi-layer structure (Kronig-Penney) or along the axis of uniformity for a two dimensional photonic crystal in three dimensional structure. Issues with boundary effects in the near Bragg resonance subwavelength are avoided either by ensuring the averaging is over an extensive path parallel to boundary or the sharp boundary is removed by graded structures. A procedure is described that enables the local homogenised index of a graded structure to be determined. These finding are confirmed by simulations and experiments on test circuits composed of Mach-Zehnder interferometers and individual components composed of regular nanostructured waveguide segments with different lengths and widths; and graded adiabatic waveguide tapers. The test chip included Lüneburg micro-lenses, which have application to Fourier optics on a chip. The measured loss of each lens is 0.72 dB. Photonic integrated circuits featuring a network of waveguides, modulators and couplers are important to applications in RF photonics, optical communications and quantum optics. Modal phase error is one of the significant limitations to the scaling of multimode interference coupler port dimension. Multimode interference couplers rely on the Talbot effect and offer the best in-class performance. Anisotropy helps reduce the Talbot length but temporal and spatial dispersion is necessary to control the modal phase error and wavelength dependence of the Talbot length. The Talbot effect in a Kronig-Penny metamaterial is analysed. It is shown that the metamaterial may be engineered to provide a close approximation to the parabolic dispersion relation required by the Talbot effect for perfect imaging. These findings are then applied to the multimode region and access waveguide tapers of a multi-slotted waveguide multimode interference coupler with slots either in the transverse direction or longitudinal direction. A novel polarisation beam splitter exploiting the anisotropy provided by a longitudinally slotted structure is demonstrated by simulation. The thesis describes the design, verification by simulation and layout of a photonic integrated circuit containing metamaterial waveguide test structures. The test and measurement of the fabricated chip and the analysis of the data is described in detail. The experimental results show good agreement with the theory, with the expected errors due to fabrication process limitations. From the Scanning Electron Microscope images and the measurements, it is clear that at the boundary of the minimum feature size limit, the error increases but still the devices can function.