Universiẗat, Diss., 2001--Stuttgart.

Implantable electrodes are the central tool for many techniques and treatments in biomedical research and medicine. There is a trend in these tools towards arrays of tissue-penetrating microelectrodes with low geometric surface areas for purposes of both increasing the specificity of recording/stimulation and reducing tissue damage due to insertion trauma and reactive immune responses. However, smaller electrode sizes present new constraints – both difficulty in fabrication as well as significant limitations on effective charge storage/injection capacities as well as higher impedances, making smaller electrodes less capable of easily passing charge safely and efficiently. Fabricating structures on the scale of tens of microns and below poses significant challenges compared to well established machining at larger sizes. Established sets of techniques such as classic MEMS processes are limited to relatively specific shapes, with significant limitations in their ability to produce curved surfaces and surfaces which are not composed of highly distinct stepped layers. We developed a method for improvement of impedance and charge storage capacity of flat electrodes without affecting geometric surface area (footprint) using Resonant Direct Laser Writing (rDLW) 3D printing to fabricate high surface area 3D structures, which were then rendered conductive. The ability to perform DLW printing at a range of laser powers on opaque reflective surfaces is demonstrated, previously a known limitation of direct laser writing. This is demonstrated through a variety of example prints. This capability opens the door to many new possibilities in micron resolution polymer printing which were previously inaccessible, with potentially far reaching ramifications for microfabrication.

No description available.

Silk proteins have provided a source of unique and versatile building blocks in the fabrication of biomedical devices for addressing a range of applications. Critical to advancing this field is the ability to establish an understanding of these proteins in their native and engineered states as well as in developing scalable processing strategies, which can fully exploit or enhance the stability, structure, and functionality of the two constituent proteins, silk fibroin and sericin. The research outlined in this dissertation focuses on the evolution in architecture and capability of silks, to effectively position a functionally-diverse, renewable class of silk materials within the rapidly expanding field of smart biomaterials. Study of the process of building macroscopic silk fibers provides insight into the initial steps in the broader picture of silk assembly, yielding biomaterials with greatly improved attributes in the assembled state over those of protein precursors alone. Self-organization processes in silk proteins enable their aggregation into highly organized architectures through simple, physical association processes. In this work, a model is developed for the process of aqueous behavior and aggregation, and subsequent two-dimensional behavior of natural silk sericin, to enable formation of a range of distinct, complex architectures. This model is then translated to an engineered system of fibroin microparticles, demonstrating the role of similar phenomena in creating autonomously-organized structures, providing key insight into future “bottom up” assembly strategies. The aqueous behavior of the water-soluble silk sericin protein was then exploited to create biocomposites capable of enhanced response and biocompatibility, through a novel protein-template strategy. In this work, sericin was added to the biocompatible and biodegradable poly(amino acid), poly(aspartic acid), to improve its pH-dependent swelling response. This work demonstrated the production of a range of porous scaffolds capable providing meaningful response to environmental stimuli, with application in tissue engineering scaffolds and biosensing technologies. Finally, to expand the capabilities of silk proteins beyond process-driven parameters to directly fabricate engineered architectures, a method for silk photopatterning was explored, enabling the direct fabrication of biologically-relevant structures at the micro and nanoscales. Using a facile bioconjugation strategy, native silk proteins could be transformed into proteins with a photoactive capacity. The well-established platform of photolithography could then be incorporated into fabrication strategies to produce a range of architectures capable of addressing spatially-directed material requirements in cell culture and further applications in the use of non-toxic, renewable biological materials.

The benefits of microwave technology in materials processing is well documented and researched. It offers many potential advantages over conventional processing such as rapid heating, faster processing times and more consistent product quality. However the actual implementation of this technology has been lacking and the benefits have gone largely unrealised. This is due largely in part to the non-uniform heating obtained in multimode cavities in conventional microwave processing. Recently, a new processing method dubbed the Variable Frequency Microwave (VFM) Technique has been developed to overcome the inherent problems associated with conventional microwave processing. By sweeping through a bandwidth of frequencies, the limitations observed in conventional processing, and specifically the problem of heat uniformity, are avoided. With the increase in research activities in alternative processing methods for new and current materials that will provide better product quality as well as time and cost savings, the VFM technique has the potential to rejuvenate interest in microwave processing. This thesis documents the research work undertaken on the VFM technique with emphasis on its characterization, optimisation and implementation to suitable applications in particular in the upcoming area of Microfabrication. A commercial Variable Frequency Microwave with an operating bandwidth of 2.5-8.0 GHz was investigated through modelling and experimental work to determine the energy distribution within a multimode cavity and to provide an insight of the mechanisms of the method. Modelling was found to be an efficient and cost-effective tool to simulate VFM and to examine the reported advantages of this new technique. Results obtained confirm the superiority of the VFM method over the conventional fixed-frequency processing showing a marked improvement in the heating uniformity achieved. Quantitative analysis of the three major VFM parameters that influence heat uniformity - Sweep Rate, Bandwidth and Central Frequency - indicate that although slight variation in heat uniformity was observed when changing these parameters, these variations are only small which implies that the VFM technique is quite insensitive to changes in the parameters making it quite a robust system. An analytical model of the Variable Frequency Microwave technique was developed and it was found that the heating uniformity could be further optimised using a sweep rate that varies as the inverse of the frequency squared (weighted-sweep). In this study, VFM Technique was successfully extended to the Micro-Electro- Mechanical Systems (MEMS) industry as an alternative method for the processing of a polymer system - negative-tone SU8 photoresist - which is gaining widespread use in Microfabrication. The VFM method was compared to conventional hotplate curing as well as a new hybrid curing method introduced in this work and the product quality assessed optically and by thermal analysis. Results from this work indicate that the Variable Frequency Microwave technique is a viable alternative to the conventional cure currently used in practice. With proper optimisation of the VFM parameters, VFM was found to provide samples that are comparable or better than conventionally cured samples in terms of properties and microstructure quality. Using the VFM method, enhancement in cure rates and drying rates, which are described by others as microwave effects, were observed and investigated. A significant increase on the degree of cure of up to 20% greater than conventional cure was observed when VFM was utilized and an apparent enhancement in solvent evaporation in the thin SU8 films observed. Experiments undertaken show that microwaves irradiation can enhance diffusion rates of cyclopentanone in the SU8 system by approximately 75-100%. The findings signify that SU8 curing at lower temperatures or rapid curing are possible and long drying times could be reduced significantly thus alleviating many of the problems associated with conventional thermal curing. Outcomes of this study demonstrate the ability of the new VFM technique to provide uniform heating which is essential for materials processing. Its application to the emerging field of Microfabrication exhibits its unique advantages over conventional curing methods and establishes itself to be a versatile and robust processing tool. The experimental observations made under microwave irradiation are further proof of the existence of specific microwave effects which is one of the most debatable topics in the Microwave processing field. A mechanism based on the Cage Model by Zwanzig [1983] was put forward to explain the increase in transport rates.

This thesis deals with different methods to improve the adhesion between sputtered aluminium and positive photoresist. Factors controlling the adhesion and different ways to measure the adhesion have been investigated. Different surface treatments prior to resist disposition have been investigated as well. The investigated surface treatments and adhesion measurements are compatible with the available equipment and the existing process cycle at Strand Interconnect AB. All tests were made in class 1000 clean room. All tests in this thesis were performed with MICROPOSIT S1818 SP16, which is a commercial and commonly used positive resist manufactured by Shipley. To provide sufficient adhesion on the aluminium surface some kind of surface treatment must be used. Today a wet chemical treatment is used at Strand Interconnect. In this report methods to modify the surface properties and to measure the adhesion have been investigated. The three methods to modify the aluminium surface were oxygen plasma, wet chemicals and primers and were used in this thesis. The RF power and time duration of the oxygen plasma were varied, while the temperature, gas flow and pressure were fixed. The adhesion was determined indirectly from measuring contact angles of 50 µl DI water droplets on sputtered aluminium in the wettability test as well as directly from the undercut caused by the etch fluid at the interface between the photoresist and the aluminium surface. An oxygen plasma with 200 W power for 30 s resulted in the lowest measured contact angle, which means that the resist adheres well on the surface. The angle was 2.99 degrees compared to 6.34 degrees for the wet chemical treatment used today. The same treatment also resulted in the lowest undercut, which correlates well with the result from the contact angle measurements. The measured undercut for a 25µm wide conductor was 1.41 µm, corresponding to an undercutting constant (ku) of 1410. The wet chemical surface treatment used today resulted in an undercut of 1.60 µm, equivalent to a ku of 1233. Similar results were obtained for a 15 µm wide conductor.

A MEMS-based micro-electro-discharge machining technique that is enabled by the actuation of micromachined planar electrodes defined on the surfaces of the workpiece is developed that eliminates the need of numerical control machines. First, the planar electrodes actuated by hydrodynamic force is developed. The electrode structures are defined by patterning l8-µm-thick copper foil laminated on the stainless steel workpiece through an intermediate photoresist layer and released by sacrificial etching of the resist layer. The planer electrodes are constructed to be single layer structures without particular features underneath. All the patterning and sacrificial etching steps are performed using dry-film photoresists towards achieving high scalability of the machining technique to large-area applications. A DC voltage of 80-140 V is applied between the electrode and the workpiece through a resistance-capacitance circuit that controls the pulse energy and timing of spark discharges. The parasitic capacitance of the electrode structure is used to form a resistance capacitance circuit for the generation of pulsed spark discharge between the electrode and the workpiece. The suspended electrodes are actuated towards the workpiece using the downflow of dielectric machining fluid, initiating and sustaining the machining process. Micromachining of stainless steel is experimentally demonstrated with the machining voltage of 90V and continuous flow of the fluid at the velocity of 3.4-3.9 m/s, providing removal depth of 20 µm. The experimental results of the electrode actuation match well with the theoretical estimations. Second, the planar electrodes are electrostatically actuated towards workpiece for machining. In addition to the single-layer, this effort uses double-layer structures defined on the bottom surface of the electrode to create custom designed patterns on the workpiece material. The suspended electrode is electrostatically actuated towards the wafer based on the pull-in, resulting in a breakdown, or spark discharge. This instantly lowers the gap voltage, releasing the electrode, and the gap value recovers as the capacitor is charged up through the resistor. Sequential pulses are produced through the self-regulated discharging-charging cycle. Micromachining of the stainless-steel wafer is demonstrated using the electrodes with single-layer and double-layer structures. The experimental results of the dynamic built-capacitance and mechanical behavior of the electrode devices are also analyzed.

<p>This thesis deals with different methods to improve the adhesion between sputtered aluminium and positive photoresist. Factors controlling the adhesion and different ways to measure the adhesion have been investigated. Different surface treatments prior to resist disposition have been investigated as well. The investigated surface treatments and adhesion measurements are compatible with the available equipment and the existing process cycle at Strand Interconnect AB. All tests were made in class 1000 clean room. All tests in this thesis were performed with MICROPOSIT S1818 SP16, which is a commercial and commonly used positive resist manufactured by Shipley. </p><p>To provide sufficient adhesion on the aluminium surface some kind of surface treatment must be used. Today a wet chemical treatment is used at Strand Interconnect. In this report methods to modify the surface properties and to measure the adhesion have been investigated. The three methods to modify the aluminium surface were oxygen plasma, wet chemicals and primers and were used in this thesis. The RF power and time duration of the oxygen plasma were varied, while the temperature, gas flow and pressure were fixed. The adhesion was determined indirectly from measuring contact angles of 50 µl DI water droplets on sputtered aluminium in the wettability test as well as directly from the undercut caused by the etch fluid at the interface between the photoresist and the aluminium surface. </p><p>An oxygen plasma with 200 W power for 30 s resulted in the lowest measured contact angle, which means that the resist adheres well on the surface. The angle was 2.99 degrees compared to 6.34 degrees for the wet chemical treatment used today. The same treatment also resulted in the lowest undercut, which correlates well with the result from the contact angle measurements. The measured undercut for a 25µm wide conductor was 1.41 µm, corresponding to an undercutting constant (k_u) of 1410. The wet chemical surface treatment used today resulted in an undercut of 1.60 µm, equivalent to a ku of 1233. Similar results were obtained for a 15 µm wide conductor.</p>

This dissertation describes the assessment and use of carbon optically transparent electrodes (C-OTEs) based on pyrolyzed photoresist films (PPFs) as a platform for spectroelectrochemical investigations. C-OTEs are examined for use in UV-Vis spectroelectrochemistry and electrogenerated chemiluminescence and compared to non-transparent glassy carbon (GC) and the conventional transparent electrode indium tin oxide (ITO). Chapter 1 provides a general overview of transparent electrodes, carbon electrodes, and spectroelectrochemistry. Chapter 2 details a UV-Vis spectroelectrochemical investigation of electrogenerated graphitic oxides (EGO) on the surface of the C-OTE in the presence of KCl. X-ray photoelectron spectroscopy and time of flight secondary ion mass spectroscopy are used to determine EGO composition. Several supporting electrolytes are investigated to determine the mechanism of EGO formation. Chapter 3 details experiments to electrochemically access the exciton emission from self-assembled double-walled tubular J-aggregates via electrogenerated chemiluminescence (ECL). Optimization of ECL intensity with respect to the coreactant concentration and the supporting electrolyte pH is performed on opaque glassy carbon electrodes. ECL and fluorescence spectra are compared, and C-OTEs are utilized to determine the source of disagreement between the spectra. Chapter 4 describes the preparation and characterization (i.e. transparency, thickness, sheet resistance, rms roughness, and electroactive surface area) of C-OTEs and explores C-OTEs for general use in ECL under a variety of conditions. Simultaneous cyclic voltammograms and ECL transients are obtained for three thicknesses of PPFs and compared to non-transparent GC and the conventional transparent electrode ITO in both front face and transmission electrode cell geometries. Despite positive potential shifts in oxidation and ECL peaks, attributed to the internal resistance of the PPFs that result from their nanoscale thickness, the PPFs display similar ECL activity to GC, including the low oxidation potential observed for amine coreactants on hydrophobic electrodes. Overall, C-OTEs are promising electrodes for spectroelectrochemical applications because they yield higher ECL than ITO in both oxidative-reductive and reductive-oxidative ECL modes, are more stable in alkaline solutions, display a wide potential window of stability, and have tunable transparency for more efficient detection of light in the transmission cell geometry. Future directions for this research are discussed in Chapter 5, which outlines several approaches to designing and improving spectroelectrochemical sensors. / text

A MEMS-based micro-electro-discharge machining technique that is enabled by the actuation of micromachined planar electrodes defined on the surfaces of the workpiece is developed that eliminates the need of numerical control machines. First, the planar electrodes actuated by hydrodynamic force is developed. The electrode structures are defined by patterning l8-µm-thick copper foil laminated on the stainless steel workpiece through an intermediate photoresist layer and released by sacrificial etching of the resist layer. The planer electrodes are constructed to be single layer structures without particular features underneath. All the patterning and sacrificial etching steps are performed using dry-film photoresists towards achieving high scalability of the machining technique to large-area applications. A DC voltage of 80-140 V is applied between the electrode and the workpiece through a resistance-capacitance circuit that controls the pulse energy and timing of spark discharges. The parasitic capacitance of the electrode structure is used to form a resistance capacitance circuit for the generation of pulsed spark discharge between the electrode and the workpiece. The suspended electrodes are actuated towards the workpiece using the downflow of dielectric machining fluid, initiating and sustaining the machining process. Micromachining of stainless steel is experimentally demonstrated with the machining voltage of 90V and continuous flow of the fluid at the velocity of 3.4-3.9 m/s, providing removal depth of 20 µm. The experimental results of the electrode actuation match well with the theoretical estimations. Second, the planar electrodes are electrostatically actuated towards workpiece for machining. In addition to the single-layer, this effort uses double-layer structures defined on the bottom surface of the electrode to create custom designed patterns on the workpiece material. The suspended electrode is electrostatically actuated towards the wafer based on the pull-in, resulting in a breakdown, or spark discharge. This instantly lowers the gap voltage, releasing the electrode, and the gap value recovers as the capacitor is charged up through the resistor. Sequential pulses are produced through the self-regulated discharging-charging cycle. Micromachining of the stainless-steel wafer is demonstrated using the electrodes with single-layer and double-layer structures. The experimental results of the dynamic built-capacitance and mechanical behavior of the electrode devices are also analyzed.