This thesis presents the development of integrated silicon photonic devices. These devices are compatible with the present and near future CMOS technology. High-khorizontal grating couplers and waveguides are proposed. This work consists of simulations and device design, as well as the layout for the fabrication process, device fabrication, process development, characterization instrument development and electro-optical characterizations.

The work demonstrates an alternative solution to costly silicon-on-insulator photonics. The proposed solution uses bulk silicon wafers and thin film deposited waveguides. Back-end deposited horizontal slot grating couplers and waveguides are realized by multi-layers of amorphous silicon and high-k materials.

The achievements of this work include: A theoretical study of fully etched slot grating couplers with Al₂O₃, HfO2 and AIN, an optical study of the high-k films with spectroscopic ellipsometry, an experimental demonstration of fully etched SiO2 single slot grating couplers and double slot Al₂O₃ grating couplers, a practical demonstration of horizontal double slot high-k waveguides, partially etched Al₂O₃ single slot grating couplers, a study of a scheme for integration of the double slot Al₂O₃  waveguides with selectively grown germanium PIN photodetectors, realization of test chips for the integrated germanium photodetectors, and study of integration with graphene photodetectors through embedding the graphene into a high-k slot layer.

From an application point of view, these high-k slot waveguides add more functionality to the current silicon photonics. The presented devices can be used for low cost photonics applications. Also alternative optical materials can be used in the context of this photonics platform.

With the robust design, the grating couplers result in improved yield and a more cost effective solution is realized for integration of the waveguides with the germanium and graphene photodetectors.

Alginate and cellulose nanofibrils (CNF) are attractive materials for tissue engineering and regenerative medicine. CNF gels are generally weaker and more brittle than alginate gels, while alginate gels are elastic and have high rupture strength. Alginate properties depend on their guluronan and mannuronan content and their sequence pattern and molecular weight. Likewise, CNF exists in various qualities with properties depending on, e.g., morphology and charge density. In this study combinations of three types of alginate with different composition and two types of CNF with different charge and degree of fibrillation have been studied. Assessments of the composite gels revealed that attractive properties like high rupture strength, high compressibility, high gel rigidity at small deformations (Young’s modulus), and low syneresis was obtained compared to the pure gels. The effects varied with relative amounts of CNF and alginate, alginate type, and CNF quality. The largest effects were obtained by combining oxidized CNF with the alginates. Hence, by combining the two biopolymers in composite gels, it is possible to tune the rupture strength, Young’s modulus, syneresis, as well as stability in physiological saline solution, which are all important properties for the use as scaffolds in tissue engineering.

Knowledge of wheel–rail interaction is crucial to wheel and rail maintenance. In this interaction, some of theworn-off material is transformed into airborne particles. Although such wear is well understood, few studiestreat the particles generated. We investigated friction modifiers' effects on airborne particles characteristicsgenerated in wheel-rail contacts in laboratory conditions. Pin-on-disc machine testing with a round-head pinloaded by a dead weight load 40 N simulated maximum contact pressure over 550 MPa. Airborne particlecharacteristics were investigated in dry contacts and in ones lubricated with biodegradable rail grease andwater- and oil-based friction modifiers. The number of particles declined with the grease; the number ofultrafine particles increased with the water-based friction modifier, mainly due to water vaporization.

Two-dimensional metal-organic frameworks show increasing research attention due to their unique properties including tunable thickness, simple packing into a film and membrane, and high surface-to-volume atom ratios. A bottom-up synthesis strategy using cetyltrimethylammonium bromide for the synthesis of copper-benzenedicarboxylate (Cu(BDC)) nanosheets is reported. The method offers the synthesis of hierarchical porous Cu(BDC) lamellae with micrometer lateral dimensions, and nanometer thickness (100-150 nm). Electron microscope (scanning and transmission), and N-2 adsorption isotherms confirm the formation of lamellae Cu(BDC) with mesopore size of 5-80 nm. The material has thermal stability up to 400 degrees C with good chemical stability in several organic solvents. However, the material transforms to another phase (Cu(BDC)(H2O)(2)) when soaked in water and alcohols. The transformation reduces crystal size and offers the formation of hydrogen bond resulting in an increase in the sorption of CO2 by similar to 10% compared to the pristine material Cu(BDC).

Ultrafast fluorescence spectroscopy was used to investigate the hole injection in CdxSeyZn1-xS1-y gradient core-shell quantum dot (CSQD) sensitized p-type NiO photocathodes. A series of CSQDs with a wide range of shell thicknesses was studied. Complementary photoelectrochemical cell measurements were carried out to confirm that the hole injection from the active core through the gradient shell to NiO takes place. The hole injection from the valence band of the QDs to NiO depends much less on the shell thickness when compared to the corresponding electron injection to n-type semiconductor (ZnO). We simulate the charge carrier tunneling through the potential barrier due to the gradient shell by numerically solving the Schrodinger equation. The details of the band alignment determining the potential barrier are obtained from X-ray spectroscopy measurements. The observed drastic differences between the hole and electron injection are consistent with a model where the hole effective mass decreases, while the gradient shell thickness increases.

In this study, strain relaxed and compressive strained Ge1-x-ySnxSiy (0.015≤x≤0.15 and 0≤y≤0.15) layers were epitaxially grown on Si substrate in a chemical vapor deposition reactor at atmospheric pressure. Digermane (Ge2H6) and germane (GeH4) were used as Ge precursors and tin tetrachloride (SnCl4) was used as Sn precursor. The growth temperature was kept below 400ᵒC to suppress Sn out diffusion. The layers crystal quality and strain were characterized using XRD, high resolution reciprocal lattice mapping and transmission electron microscopy and the surface morphology was investigated by atomic force microscopy (AFM). Furthermore, the low temperature epitaxial growth up to 15% Si atoms incorporation in Ge0.94Sn0.06 was demonstrated by adding silane (SiH4) as Si precursor. Sn contents calculated from high resolution XRD patterns were confirmed by Rutherford backscattering spectroscopy which shows that Sn atoms are mostly positioned in substitutional sites. AFM analysis showed below 1nm surface roughness for both strained and strain relaxed GeSn layers which make the promising materials for photonics and electronics applications.

We evaluate various metal gate/high-K/Si capacitors by their resulting electrical characteristics. Therefore, we process MOS gate stacks incorporating aluminium (Al), nickel (Ni), titanium-nitride (TiN), and molybdenum (Mo) as the gate material, and metal organic chemical vapour deposited (MOCVD) ZrO2 and HfO2 as the gate dielectric, respectively. The influence of the processing sequence - especially of the thermal annealing treatment - on the electrical characteristics of the various gate stacks is being investigated. Whereas post metallization annealing in forming gas atmosphere improves capacitance-voltage behaviour (due to reduced interface-, and oxide charge density), current-voltage characteristics degrade due to a higher leakage current after thermal treatment at higher temperatures. The Flatband-voltage values for the TiN-, Mo-, and Ni-capacitors indicate mid-gap pinning of the metal gates, however, Ni seems to be thermally unstable on ZrO2, at least within the process scheme we applied.

In this work we compare the impacts of nickel (Ni), titanium-nitride (TiN), molybdenum (Mo), and aluminium (Al), gates on MOS capacitors incorporating HfO2- or ZrO2-dielectrics. The primary focus lies on interface trapping, oxide charging, and thermodynamical stability during different annealing steps of these gate stacks. Whereas Ni, Mo, and especially TIN are investigated as most promising candidates for future CMOS devices, Al acted as reference gate material to benchmark the parameters. Post-metallization annealing of both, TiN- and Mo-stacks, resulted in very promising electrical characteristics. However, gate stacks annealed at temperatures of 800 degrees C or 950 degrees C show thermodynamic instability and related undesirable high leakage currents.

We compare metal oxide semiconductor capacitors, investigating Titanium-Nitride and Molybdenum as gate materials, as well as metal organic chemical vapor deposited ZrO2 and HfO2 as high-kappa dielectrics, respectively. The impact of different annealing steps on the electrical characteristics of the various gate stacks is a further issue. The positive effect of post metallization annealing in forming gas atmosphere as well as observed mid-gap pinning of TiN and Mo metal gates is presented.

We have previously shown that gadolinium oxide (Gd2O3) nanoparticles are promising candidates to be used as contrast agents in magnetic resonance (MR) imaging applications. In this study, these nanoparticles were investigated in a cellular system, as possible probes for visualization and targeting intended for bioimaging applications. We evaluated the impact of the presence of Gd2O3 nanoparticles on the production of reactive oxygen species (ROS) from human neutrophils, by means of luminol-dependent chemiluminescence. Three sets of Gd2O3 nanoparticles were studied, i.e. as synthesized, dialyzed and both PEG-functionalized and dialyzed Gd2O3 nanoparticles. In addition, neutrophil morphology was evaluated by fluorescent staining of the actin cytoskeleton and fluorescence microscopy. We show that surface modification of these nanoparticles with polyethylene glycol (PEG) is essential in order to increase their biocompatibility. We observed that the as synthesized nanoparticles markedly decreased the ROS production from neutrophils challenged with prey (opsonized yeast particles) compared to controls without nanoparticles. After functionalization and dialysis, more moderate inhibitory effects were observed at a corresponding concentration of gadolinium. At lower gadolinium concentration the response was similar to that of the control cells. We suggest that the diethylene glycol (DEG) present in the as synthesized nanoparticle preparation is responsible for the inhibitory effects on the neutrophil oxidative burst. Indeed, in the present study we also show that even a low concentration of DEG, 0.3%, severely inhibits neutrophil function. In summary, the low cellular response upon PEG-functionalized Gd2O3 nanoparticle exposure indicates that these nanoparticles are promising candidates for MR-imaging purposes.

Water is the source of all life, but unfortunately, the water quality is getting only worse due to many factors like overuse, contamination, indifference and even by nature itself. By identifying the problem, we are one step closer to solving the problem, and that is why an intelligent water quality device is required to examine water and detect impurities within it. In this project, we are developing a device that uses an entirely new method to measure water quality. Even though the theory behind the device is very advanced, the device is still primitive in its functions and needs development to increase the usefulness and accuracy of the measurements!

The field of precision medicine allows for tailor-made treatments specific to a patient and thereby improve the efficiency and accuracy of disease prevention, diagnosis, and treatment and at the same time would reduce the cost, redundant treatment, and side effects of current treatments. Here, the combination of organ-on-a-chip and bioprinting into engineering high-content in vitro tissue models is envisioned to address some precision medicine challenges. This strategy could be employed to tackle the current coronavirus disease 2019 (COVID-19), which has made a significant impact and paradigm shift in our society. Nevertheless, despite that vaccines against COVID-19 have been successfully developed and vaccination programs are already being deployed worldwide, it will likely require some time before it is available to everyone. Furthermore, there are still some uncertainties and lack of a full understanding of the virus as demonstrated in the high number new mutations arising worldwide and reinfections of already vaccinated individuals. To this end, efficient diagnostic tools and treatments are still urgently needed. In this context, the convergence of bioprinting and organ-on-a-chip technologies, either used alone or in combination, could possibly function as a prominent tool in addressing the current pandemic. This could enable facile advances of important tools, diagnostics, and better physiologically representative in vitro models specific to individuals allowing for faster and more accurate screening of therapeutics evaluating their efficacy and toxicity. This review will cover such technological advances and highlight what is needed for the field to mature for tackling the various needs for current and future pandemics as well as their relevancy towards precision medicine.

The engineering of multifunctional biomaterials using a facile sustainable methodology that follows the principles of green chemistry is still largely unexplored but would be very beneficial to the world. Here, the employment of catalytic reactions in combination with biomass-derived starting materials in the design of biomaterials would promote the development of eco-friendly technologies and sustainable materials. Herein, we disclose the combination of two catalytic cycles (combined catalysis) comprising oxidative decarboxylation and quinone-catechol redox catalysis for engineering lignin-based multifunctional antimicrobial hydrogels. The bioinspired design mimics the catechol chemistry employed by marine mussels in nature. The resultant multifunctional sustainable hydrogels (1) are robust and elastic, (2) have strong antimicrobial activity, (3) are adhesive to skin tissue and various other surfaces, and (4) are able to self-mend. A systematic characterization was carried out to fully elucidate and understand the facile and efficient catalytic strategy and the subsequent multifunctional materials. Electron paramagnetic resonance analysis confirmed the long-lasting quinone-catechol redox environment within the hydrogel system. Initial in vitro biocompatibility studies demonstrated the low toxicity of the hydrogels. This proof-of-concept strategy could be developed into an important technological platform for the eco-friendly, bioinspired design of other multifunctional hydrogels and their use in various biomedical and flexible electronic applications.

The conventional ion-sensitive field-effect transistor (ISFET) with SiO2 as the insulator of choice has been used as an electrochemical sensor to measure ion concentrations in solutions for many decades. With the ongoing progress in use of silicon nanoribbon (SiNR) FET sensors for fast reliable sensing and the recent demand for pH-sensing technologies in biological applications, it is important to identify the true pH response of the device. However, it has become much more difficult to achieve reliable results across a broad range of pH using SiO2-gated SiNR FET sensors and limitations such as long term drift and hysteresis (also referred to as memory effects) during pH measurements need to be addressed. In this work, we have investigated the electrochemical pH response behavior of silicon oxide-gated SiNR FET sensors and compared it with similar devices (same NR size) but with Al2O3 as the gate oxide. Our studies show that devices passivated with SiO2 show a large hysteresis in the pH response both in acidic and in basic direction, whereas Al2O3 surfaces show slight hysteresis and only in the acidic pH range. Furthermore, in case of SiO2, the total response-time after a pH change appears to be a combination of a fast transient and a slow drift which is related both to the type of oxide and the concentration of the background electrolyte. Consequently, to minimize errors in pH measurements caused by hysteresis and delayed response, we advise performing the measurements at low ionic concentrations and preferably to replace SiO2 by Al2O3 as the gate oxide. In biological applications, we also recommend the integration of an on-chip reference nanoribbon FET for real-time monitoring of problems such as long-term drift and slow response.

Over the past decade, the field of medical diagnostics has seen an incredible amount of research towards the integration of one-dimensional nanostructures such as carbon nanotubes, metallic and semiconducting nanowires and nanoribbons for a variety of bio-applications. Among the mentioned one-dimensional structures, silicon nanoribbon (SiNR) field-effect transistors (FET) as electro-chemical nanosensors hold particular promise for label-free, real-time and sensitive detection of biomolecules using affinity-based detection. In SiNR FET sensors, electrical transport is primarily along the nanoribbon axis in a thin sheet (< 30 nm) serving as the channel. High sensitivity is achieved because of the large surface-to-volume ratio which allows analytes to bind anywhere along the NR affecting the entire conductivity by their surface charge. Unfortunately, sensitivity without selectivity is still an ongoing issue and this thesis aims at addressing the detection challenges and further proposing effective developments, such as parallel and multiple detection through using individually functionalized SiNRs.We present here a comprehensive study on design, fabrication, operation and device performance parameters for the next generation of SiNR FET sensors towards multiplexed, label-free detection of biomolecules using an on-chip microfluidic layer which is based on a highly cross-linked epoxy. We first study the sensitivity of different NR dimensions followed by analysis of the drift and hysteresis effects. We have also addressed two types of gate oxides (namely SiO2 and Al2O3) which are commonly used in standard CMOS fabrication of ISFETs (Ion sensitive FET). Not only have we studied and compared the hysteresis and response-time effects in the mentioned two types of oxides but we have also suggested a new integrated on-chip reference nanoribbon/microfluidics combination to monitor the long-term drift in the SiNR FET nanosensors. Our results show that compared to Al2O3, silicon-oxide gated SiNR FET sensors show high hysteresis and slow-response which limit their performance only to background electrolytes with low ionic strength. Al2O3 on the other hand proves more promising as the gate-oxide of choice for use in nanosensors. We have also illustrated that the new integrated sensor NR/Reference NR can be utilized for real-time monitoring of the above studied sources of error during pH-sensing. Furthermore, we have introduced a new surface silanization (using 3-aminopropyltriethoxysilane) method utilizing microwave-assisted heating which compared to conventional heating, yields an amino-terminated monolayer with high surface coverage on the oxide surface of the nanoribbons. A highly uniform and dense monolayer not only reduces the pH sensitivity of the bare-silicon oxide surface in a physiological media but also allows for more receptors to be immobilized on the surface. Protocols for surface functionalization and biomolecule immobilization were evaluated using model systems. Selective spotting of receptor molecules can be used to achieve localized functionalization of individual SiNRs, opening up opportunities for multiplexed detection of analytes.Additionally, we present here a novel approach by integrating droplet-based microfluidics with the SiNR FET sensors. Using the new system we are able to successfully detect trains of droplets with various pH values. The integrated system enables a wide range of label-free biochemical and macromolecule sensing applications based on detection of biological events such as enzyme-substrate interactions within the droplets.

Colloidal quantum dots (QD) have tuneable optoelectronic properties and can be easily handled by simple solution processing techniques, making them very attractive for a wide range of applications. Over the past decade synthesis of morphology controlled high quality (crystalline, monodisperse) colloidal QDs by thermal decomposition of organometallic precursors has matured and is well studied. Recently, synthesis of colloidal QDs by microwave irradiation as heating source is being studied due to the inherently different mechanisms of heat transfer, when compared to solvent convection based heating. Under microwave irradiation, polar precursor molecules directly absorb the microwave energy and heat up more efficiently. Here we report synthesis of colloidal II-VI semiconductor QDs (CdS, CdSe, CdTe) by microwave irradiation and compare it with conventional synthesis based on convection heating. Our findings show that QD synthesis by microwave heating is more efficient and the chalcogenide precursor strongly absorbs the microwave radiation shortening the reaction time and giving a high reaction yield.

We present a novel microfluidic system that integrates droplet microfluidics with a silicon nanoribbon field-effect transistor (SiNR FET), and utilize this integrated system to sense differences in pH. The device allows for selective droplet transfer to a continuous water phase, actuated by dielectrophoresis, and subsequent detection of the pH level in the retrieved droplets by SiNR FETs on an electrical sensor chip. The integrated microfluidic system demonstrates a label-free detection method for droplet microfluidics, presenting an alternative to optical fluorescence detection. In this work, we were able to differentiate between droplet trains of one pH-unit difference. The pH-based detection method in our integrated system has the potential to be utilized in the detection of biochemical reactions that induce a pH-shift in the droplets.

Application specific architectures are highly desirable in embedded parallel computing systems at the same time as designers strive for using one embedded parallel computing platform for several applications. If this can be achieved, the cost can be decreased in comparison to using several different embedded parallel computing systems. This paper presents a novel approach of running several high-performance applications concurrently on one single parallel computing system. By using a reconfigurable backplane interconnection system, the applications can be run efficiently with high network flexibility since the interconnect network can be adapted to fit the application that is being processed for the moment. More precisely, this paper investigates how the space time adaptive processing (STAP) radar algorithm and the stripmap synthetic aperture radar (SAR) algorithm can be mapped on a multi-cluster processing system with a reconfigurable optical interconnection system realized by a micro-optical-electrical mechanical system (MOEMS) crossbars. The paper describes the reconfigurable platform, the two algorithms and how they individually can be mapped on the targeted multiprocessor system. It is also described how these two applications can be mapped simultaneously on the optical reconfigurable platform. Implications and requirements on communication bandwidth and processor performance in different critical points of the two applications are presented. The results of the analysis show that an implementation is feasible with today's MOEMS technology, and that the two applications can be successfully run in a time-sharing scheme, both at the processing side and at the access for interconnection bandwidth.

This letter reports on a systematic investigation of sputter induced damage in graphene caused by low energy Ar+ ion bombardment. The integral numbers of ions per area (dose) as well as their energies are varied in the range of a few eV's up to 200 eV. The defects in the graphene are correlated to the dose/energy and different mechanisms for the defect formation are presented. The energetic bombardment associated with the conventional sputter deposition process is typically in the investigated energy range. However, during sputter deposition on graphene, the energetic particle bombardment potentially disrupts the crystallinity and consequently deteriorates its properties. One purpose with the present study is therefore to demonstrate the limits and possibilities with sputter deposition of thin films on graphene and to identify energy levels necessary to obtain defect free graphene during the sputter deposition process. Another purpose is to disclose the fundamental mechanisms responsible for defect formation in graphene for the studied energy range.

This paper presents the use of graphene as a diffusion barrier to a eutectic Ga-In-Sn alloy, i.e., galinstan, for electrical contacts in electronics. Galinstan is known to be incompatible with many conventional metals used for electrical contacts. When galinstan is in direct contact with Al thin films, Al is readily dissolved leading to the formation of Al oxides present on the surface of the galinstan droplets. This reaction is monitored ex situ using several material analysis methods as well as in situ using a simple circuit to follow the time-dependent resistance variation. In the presence of a multilayer graphene diffusion barrier, the Al-galinstan reaction is effectively prevented for galinstan deposited by means of drop casting. When deposited by spray coating, the high-impact momentum of the galinstan droplets causes damage to the multilayer graphene and the Al-galinstan reaction is observed at some defective spots. Nonetheless, the graphene barrier is likely to block the formation of Al oxides at the Al/galinstan interface leading to a stable electrical current in the test circuit.

In the industry of today, materials which can adsorb and hold large amounts of water are playing an important role. Here, the free and bound water carrying capacity of an amorphous magnesium carbonate is investigated. It is also determined how these parameters depend on the relative humidity of the surrounding environment. To do this, the technique of dielectric spectroscopy is employed. Along with the water binding properties, the concentration of charge carriers and the diffusion coefficient was determined. A smaller part of around 10-30 % of the water adsorbed was shown to behave as free water in the material. The concentration of charge carriers was calculated to be in an order of magnitude of 10¹⁸-10²² m^-3 for the higher relative humidity environments. The diffusion coefficient was shown to be about 5*10^-9 m²/s for the adsorption spectrum. This value is in good agreement with the value for OH^- ions in water.

Nickel was loaded onto hydrothermally-grown ZnO nanorods on cordierite substrates and tested as catalysts in microwave-enhanced degradation of phenol from its aqueous solution (100 ppm) at 70 degrees C. Effects of metal loadings (1, 10 and 20 mM impregnation solutions) on the degradation of phenol in aqueous solution was investigated. The catalyst performances were monitored based on phenol degradation, product distributions and carbon dioxide (CO2) evolutions. Based on the type of the catalysts, two different mechanistic pathways for the decomposition were observed-through catechol and/or hydroquinone as intermediates. It was found that the 10mM nickel loaded sample catalyzed the degradation through one pathway with hydroquinone as the benzenediol intermediate formed, while the 20 mM nickel impregnated sample catalyzed the reaction through two pathways, producing catechol as well as hydroquinone by products. These differences in reaction pathways were attributed to the variation in the composition of the nickel compounds and surface structures between the two catalysts. Furthermore, the effect of hydrogen peroxide (H2O2) as an oxidant was explored. It was found that although addition of H2O2 led to an increase in the degree of phenol degradation, it also led to enhanced catalyst leaching. There was also an increase in CO2 evolution due to the addition of H2O2. It was observed that 20 mM nickel-loaded sample without the addition of H2O2 exhibited optimum performance in terms of phenol degradation and CO2 evolution with no drawback of catalyst leaching. Catalytic microwave enhanced degradation is an effective means for the removal of dissolved organic compounds from wastewater.

Nanopore-based sequencing has demonstrated a significant potential for the development of fast, accurate, and cost-efficient fingerprinting techniques for next generation molecular detection and sequencing. We propose a specific multilayered graphene-based nanopore device architecture for the recognition of single biomolecules. Molecular detection and analysis can be accomplished through the detection of transverse currents as the molecule or DNA base translocates through the nanopore. To increase the overall signal-to-noise ratio and the accuracy, we implement a new 'multi-point cross-correlation' technique for identification of DNA bases or other molecules on the single molecular level. We demonstrate that the cross-correlations between each nanopore will greatly enhance the transverse current signal for each molecule. We implement first-principles transport calculations for DNA bases surveyed across a multilayered graphene nanopore system to illustrate the advantages of the proposed geometry. A time-series analysis of the cross-correlation functions illustrates the potential of this method for enhancing the signal-to-noise ratio. This work constitutes a significant step forward in facilitating fingerprinting of single biomolecules using solid state technology.

We use functionalized iron oxide magnetic multi-core particles of 100 nm in size (hydrodynamic particle diameter) and AC susceptometry (ACS) methods to measure the binding reactions between the magnetic nanoparticles (MNPs) and bio-analyte products produced from DNA segments using the rolling circle amplification (RCA) method. We use sensitive induction detection techniques in order to measure the ACS response. The DNA is amplified via RCA to generate RCA coils with a specific size that is dependent on the amplification time. After about 75 min of amplification we obtain an average RCA coil diameter of about 1 µm. We determine a theoretical limit of detection (LOD) in the range of 11 attomole (corresponding to an analyte concentration of 55 fM for a sample volume of 200 µL) from the ACS dynamic response after the MNPs have bound to the RCA coils and the measured ACS readout noise. We also discuss further possible improvements of the LOD.

A flexible nanoparticle-based phospholipase (PL) assay is demonstrated in which the enzymatic substrate is decoupled from the nanoparticle surface. Liposomes are loaded with a polypeptide that is designed to heteroassociate with a second polypeptide immobilized on gold nanoparticies. Release of this polypeptide from the liposornes, triggered by PL, induces a folding-dependent nanoparticle bridging aggregation. The colorimetric response from this aggregation enables straightforward and continuous detection of PL in the picomolar range. The speed, specificity, and flexibility of this assay make it appropriate for a range of applications, from point of care diagnostics to high throughput pharmaceutical screening.

Bioanalytical techniques that enable simple, fast and reliable high sensitivity monitoring of biomolecular interactions are of immense importance for diagnostics and drug development. This tutorial review provides an overview of recent progress in the development of peptide-based hybrid nanomaterials that transduce molecular interactions by exploiting the optical and magnetic properties of nanoparticles. Peptides have emerged as an interesting alternative to conventional biomolecular receptors, such as antibodies, and are facilitating the design of responsive hybrid nanomaterials that are both robust and sensitive for biodiagnostic applications.

Hard X-ray scanning microscopes, or nanoprobes, make it possible to image samples and probe their chemical, elemental and structural properties at nanoscale resolution. This is enabled by the use of nanofocusing optics. Commonly used optics in nanoprobes for high resolution X-ray experiments are zone plates. Zone plates are circular diffraction optics with radially decreasing grating periods. Their performance depends on their geometrical properties and material. The width of the outermost zone, which today is in the order of a few tens of nanometers, defines the zone plate resolution, while the zone thickness and the material define the X-ray focusing efficiency. For hard X-ray zone plates, the required zone thickness is several micrometers. Therefore, high-aspect ratio nanostructures are a prerequisite for high-resolution, high-efficiency zone plates. The very small structures together with the high-aspect ratios make zone plates one of the most challenging devices to fabricate. A wet-chemical nanofabrication process that has proved its capability of providing silicon nanostructures with ultra-high aspect ratios is metal-assisted chemical etching (MACE). MACE is an electroless, autocatalytic pattern transfer method that uses an etching solution to selectively etch a predefined noble metal pattern into silicon. In this thesis, MACE is optimized specifically for zone plate nanostructures and used in the development of a new zone plate device nanofabrication process. The MACE optimization for silicon zone plate nanostructures involved a systematic investigation of a wide parameter space. The preferable etching solution composition, process temperature, zone plate catalyst design and silicon type were identified. Parameter dependencies were characterized with respect to etching depth and verticality, mechanical stability of zones and silicon surface roughness. Zone plate molds with aspect ratios of 30:1 at 30 nm zone widths were nanofabricated using the optimized MACE process. For use with hard X-rays, the silicon molds were metallized with palladium using electroless deposition (ELD). The first order diffraction efficiency of such a palladium/silicon zone plate was characterized as 1.9 %. Both MACE for the zone plate pattern transfer and ELD for the silicon mold metalization are conceptually simple, relatively low-cost and accessible methods, which opens up for further developments of zone plate device nanofabrication processes.

For supported heterogeneous catalysis, the interface between a metal nanoparticle and the support plays an important role. In this work the dependency of the catalytic efficiency on the bonding chemistry of platinum nanoparticles supported on zinc oxide (ZnO) nanorods is studied. Platinum nanoparticles were deposited on ZnO nanorods (ZnO NR) using thermal and photochemical processes and the effects on the size, distribution, density and chemical state of the metal nanoparticles upon the catalytic activities are presented. The obtained results indicate that the bonding at Pt-ZnO interface depends on the deposition scheme which can be utilized to modulate the surface chemistry and thus the activity of the supported catalysts. Additionally, uniform distribution of metal on the catalyst support was observed to be more important than the loading density. It is also found that oxidized platinum Pt(IV) (platinum hydroxide) provided a more suitable surface for enhancing the transfer hydrogenation reaction of cyclohexanone with isopropanol compared to zero valent platinum. Photochemically synthesized ZnO supported nanocatalysts were efficient and potentially viable for upscaling to industrial applications.

This thesis work describes the fabrication and surface enhanced Raman spectroscopy (SERS) characterization of vertically aligned nitrogen (N) doped multi walled carbon nanotube (MWCNT) forests coated by silver (Ag) and gold (Au) nanoparticles. In the present work, the CNT forests were grown from a catalyst metal layer by the chemical vapor deposition (CVD) process at temperature of 800 ^oC and a physical vapor deposition (PVD) and annealing processes were applied subsequently for the evaporation and diffusion of noble metal nanoparticles on the forest.

Transistor patterning of 20, 50 and 100 μm were made onto the silicon-oxide (SiO₂) wafers through the photolithography process with and without depositing a thickness of 10 nm titanium (Ti) buffer layer on the Si-surfaces. Iron (Fe) and cobalt (Co) were used together to deposite a thickness of 5 nm catalyst layer onto the Single Side Polished (SSP) wafers. As carbon and nitrogen precursor for the CNT growth was used pyridine. Two different treatment times (20 and 60 minutes) in the CVD process determined the CNT forest height. Scanning Electron Microscopy (SEM) imaging was employed to characterize the CNT forest properties and Ag and Au nanoparticle distribution along the CNT walls.

The existence of “hot spots” created by the Ag and Au nanoparticles through the surface roughness and plasmonic properties was demonstrated by the SERS measurements. Accordingly, the peak intensity at wave number of 1076 cm^-1 was picked up from each SERS spectra to establish the Ag- and Au-trend curves with different concentrations of 4-ATP solution. The SERS mapping was also carried out to study the Ag- and Au-coated CNT surface homogeneity and “hot spots” distribution on the CNT surface. The SERS enhancement factors (EF) were calculated by applying an analyte solution of ethanolic 4-ATP on the CNT surface. The calculated values of EF from Ag- and Au-coated CNT forests were 9×10⁶ and 2.7×10⁵ respectively. 

Cellulose nanofibrils based on wood pulp fibres are most promising for biomedical applications. Bacterial cellulose has been suggested for some medical applications and is presently used as wound dressing. However, cost-efficient processes for mass production of bacterial cellulose are lacking. Hence, fibrillation of cellulose wood fibres is most interesting, as the cellulose nanofibrils can efficiently be produced in large quantities. However, the utilization of cellulose nanofibrils from wood requires a thorough verification of its biocompatibility, especially with fibroblast cells which are important in regenerative tissue and particularly in wound healing. The cellulose nanofibril structures used in this study were based on Eucalyptus and Pinus radiata pulp fibres. The nanofibrillated materials were manufactured using a homogenizer without pre-treatment and with 2,2,6,6-tetramethylpiperidine-1-oxy radical as pre-treatment, thus yielding nanofibrils low and high level of anionic charge, respectively. From these materials, two types of nanofibril-based structures were formed; (1) thin and dense structures and (2) open and porous structures. Cytotoxicity tests were applied on the samples, which demonstrated that the nanofibrils do not exert acute toxic phenomena on the tested fibroblast cells (3T3 cells). The cell membrane, cell mitochondrial activity and the DNA proliferation remained unchanged during the tests, which involved direct and indirect contact between the nano-structured materials and the 3T3 cells. Some samples were modified using the crosslinking agent polyethyleneimine (PEI) or the surfactant cetyl trimethylammonium bromide (CTAB). The sample modified with CTAB showed a clear toxic behaviour, having negative effects on cell survival, viability and proliferation. CTAB is an antimicrobial component, and thus this result was as expected. The sample crosslinked with PEI also had a significant reduction in cell viability indicating a reduction in DNA proliferation. We conclude that the neat cellulose nanostructured materials tested in this study are not toxic against fibroblasts cells. This is most important as nano-structured materials based on nanofibrils from wood pulp fibres are promising as substrate for regenerative medicine and wound healing.

In laboratory experiments, the antifouling (AF) properties of zinc oxide (ZnO) nanorod coatings were investigated using the marine bacterium Acinetobacter sp. AZ4C, larvae of the bryozoan Bugula neritina and the microalga Tetraselmis sp. ZnO nanorod coatings were fabricated on microscope glass substrata by a simple hydrothermal technique using two different molar concentrations (5 and 10 mM) of zinc precursors. These coatings were tested for 5 h under artificial sunlight (1060 W m(-2) or 530 W m(-2)) and in the dark (no irradiation). In the presence of light, both the ZnO nanorod coatings significantly reduced the density of Acinetobacter sp. AZ4C and Tetraselmis sp. in comparison to the control (microscope glass substratum without a ZnO coating). High mortality and low settlement of B. neritina larvae was observed on ZnO nanorod coatings subjected to light irradiation. In darkness, neither mortality nor enhanced settlement of larvae was observed. Larvae of B. neritina were not affected by Zn2+ ions. The AF effect of the ZnO nanorod coatings was thus attributed to the reactive oxygen species (ROS) produced by photocatalysis. It was concluded that ZnO nanorod coatings effectively prevented marine micro and macrofouling in static conditions.

The influence of heterogeneous semiconductors on the photodegradation of phenol in water was investigated using doped tin dioxide (SnO₂) nanoparticles. Photocatalysts of SnO₂ were synthesized with lanthanum (La), cerium (Ce), and neodymium (Nd) dopants. These photocatalysts were synthesized from tin tetrachloride by sol-gel method with different dopant concentrations, and its photocatalytic degradation was investigated up to 0.8 % under UV-A light in aqueous suspensions. The photocatalytic oxidation reactions were studied by varying photocatalyst composition, light intensity, reaction time, pH of the reaction medium, and phenol concentration. It was found that the photocatalytic activity of rare earth-doped SnO₂ for phenol decomposition under UV light irradiation was considerably higher than that of pure SnO₂ nanoparticles. The experimental results also indicate that more than 95 % phenol was effectively oxidized in the presence of an aqueous suspension of La: SnO₂ nanoparticles within 120 min of UV light irradiation.

Iodine doped tin oxide (SnO2:I) nanoparticles were prepared by sol-gel synthesis and their photocatalytic activities with phenol as a test contaminant were studied. In the presence of the catalysts, phenol degradation under direct sunlight was comparable to what was achieved under laboratory conditions. Photocatalytic oxidation reactions were studied by varying the catalyst loading, light intensity, illumination time, pH of the reactant and phenol concentration. Upon UV irradiation in the presence of SnO2:I nanoparticles, phenol degrades very rapidly within 30 min, forming carboxylic acid which turns the solution acidic. Phenol degradation rate with 1% iodine doped SnO2 nanoparticles is at least an order of magnitude higher compared to the degradation achieved through undoped SnO2 nanoparticles under similar illumination conditions.

Potential-pH diagram assisted-design for controlled precipitation is an attractive method to obtain engineered binary and ternary oxide particles. Aqueous synthesis conditions of zinc stannate (ZnSnO3) particles at low temperature were formulated with the assistance of potential-pH diagram. The pH of a solution containing stoichiometric amounts of Zn2+ and Sn4+ was controlled for the precipitation in a one pot synthesis step at room temperature (25 degrees C). The effect of the concentration of the reactants on the particle size was studied by varying the concentration of the precursor (Zn2+ + Sn4+) solution. Scanning electron micrographs show that the particles are monodispersed micron sized cubes formed by the self-organization olnano-sized crystallites. The obtained microcubes characterized by X-ray Diffraction and thermo gravimetric analysis (TGA) show that the particles are in ZnSnO3.3H(2)O form.

Phase transformation studies in ZnO-SnO2 system from zinc metastannate (ZnSnO3) to zinc orthostannate (Zn2SnO4) with annealing temperature are reported. Non-centrosymmetric oxides show unique symmetry dependent and spontaneous polarization properties, which are technologically important. ZnSnO3 particles were synthesized by a simple aqueous synthesis at low temperatures designed with the assistance of potential-pH diagrams. ZnSnO3 particles synthesized at 4 A degrees C are more porous losing the ilmenite structure upon annealing at 200 A degrees C, while the other samples prepared at higher temperatures (25-65 A degrees C) becomes amorphous at 300 A degrees C. The phase transformation into the inverse spinel orthostannate phase occurs around 750 A degrees C in all the samples.

The magnetic properties of thin metallic films are significantly different from the bulk properties due to the presence of interfaces. The properties shown by such thin films are influenced by the atomic level structure of the films and the interfaces. Transmission electron microscope (TEM) has the potential to analyse the structure and the magnetic properties of such systems with atomic resolution. In this work, the TEM is employed to characterize the structure of the Fe/V and Fe/Ni multilayers and the technique of electron magnetic circular dichroism (EMCD) is developed to obtain the quantitative magnetic measurements with high spatial resolution.

From TEM analysis of short period Fe/V  multilayers, a coherent superlattice structure is found. In short period Fe/Ni multilayer samples with different repeat frequency, only the TEM technique could verify the existence of the multilayer structure in the thinnest layers. The methods of scanning TEM imaging and electron energy loss spectroscopy (EELS) results were used and refined to determine interdiffusion at the interfaces. The confirmation of the multilayer structure helped to explain the saturation magnetization of these samples.

Electron magnetic circular dichroism (EMCD) has the potential to quantitatively measure the magnetic moments of the materials with atomic resolution, but the technique presents several challenges. First, the EMCD measurements need to acquire two EELS spectra at two different scattering angles. These spectra are mostly acquired one after the other which makes it difficult to guaranty the identical experimental conditions and the spatial registration between the two acquisitions. We have developed a technique to simultaneously acquire the two angle-resolved EELS spectra in a single acquisition. This not only ensures the accuracy of the measurements but also improves the signal to noise ratio as compared to the previously used methods. The second important question is the effect of crystal orientations on the measured EMCD signals, considering the fact that the crystal orientation of a real crystal does not remain the same in the measured area. We developed the methodology to simultaneously acquire the EMCD signals and the local crystal orientations with high precision and experimentally showed that the crystal tilt significantly changes the magnetic signal. The third challenge is to obtain EMCD measurements with atomic resolution  which is hampered by the need of high beam convergence angles. We further developed the simultaneous acquisition technique to obtain the quantitative EMCD measurements with beam convergence angles corresponding to atomic size electron probes.