No description available.

No description available.

"Previous studies carried out in our laboratory resulted in the development of noncovalently assembled multilayered thin films incorporating metal ions such as Cu(II) and organic ligands including dicarboxypyridine. In one study, a SAM consisting of 4-[(10- mercaptodecyl)oxy]pyridine-2,6-dicarboxylic acid was deposited on gold. The pyridine group was then used to complex a layer of Cu(II) ions which in turn were capped by cis- 2,2’-dipyridylethylene. This stilbene analog undergoes photoinduced cis-trans isomerization on the surface resulting in a substantial increase in the hydrophilicity of the surface leading to the possibility of creating virtual microfluidic valves and pumps. However, the photoswitchable wettability was irreversible. Stilbene-4,4-dicarboxylic acid was the ligand selected for generating a reversible system. The decision to use this stilbene moiety was based on molecular modeling and the commercial availability of both cis and trans forms. When 4-[(10-mercaptodecyl)oxy]pyridine-2,6-dicarboxylic acid was used as SAM, the stilbene-4,4’-dicarboxylic acid did not undergo photoisomerization. Prolonged irradiation leads to photodegradation of film. A mixed SAM of dodecanethiol and mercaptoundecanoic acid was used to create space on the surface and facilitate isomerization. But cis-trans isomerization of the stilbene moiety was not achieved by this system. When a mixed SAM of 4-[(10-mercaptodecyl)oxy]pyridine-2,6-dicarboxylic acid and 4-tert butylbenzenethiol was used, stilbene-4,4-dicarboxylic acid showed reversible photoinduced cis-trans isomerization for one complete cycle leading to a reversible change in wettability. After one cycle of isomerization the film photodegrades."

No description available.

Silicon nanocrystals embedded in silicon nitride have received attention as promising materials for optoelectronic applications. More specifically, band gap engineering of novel materials based on silicon nanocrystals has been proposed for possible application in an all-silicon tandem solar cell within the field of `third generation' photovoltaics. Such an application would require nanocrystals to exhibit quantum confinement whereby the optical and electrical properties of a film could be tuned by controlling the size of these `quantum dots'. This thesis investigates the correlation between the structural and optical properties of silicon nanocrystals grown in silicon nitride multilayer structures via solid phase crystallisation, as part of an experimental investigation into quantum confinement. A study of the relevant processing parameters for the solid phase crystallization of silicon nanocrystals in amorphous silicon nitride is presented and the effectiveness of the multilayer approach for controlling nanocrystal size is demonstrated. Structural characterisation using transmission electron microscopy and glancing incidence x-ray diffraction is complemented with a new application of Fourier transform infrared spectroscopy for the detection of silicon nanocrystals. A case study on the effects of annealing temperature on the photoluminescence from silicon nitride multilayers is presented. While a clear correlation between the structural, molecular and optical properties is demonstrated, evidence of quantum confinement remains ambiguous. The investigation into the limits of parameter space for the formation of silicon nanocrystals in silicon nitride multilayers also leads to the formation of a novel Si-Si3N4 nanocomposite material. A comprehensive study of the photoluminescence from silicon nanocrystals embedded in nitride is presented in the context of homogeneous and multilayer nitride films. Size dependent PL and absorption is demonstrated for silicon nitride multilayers with silicon-rich silicon nitride layer thicknesses varying from 1 to 4.5 nm, indicating the formation of quantum wells. These same structures are annealed to form arrays of silicon nanocrystals. Although the PL and absorption spectra suggest quantum effects, inherent ambiguities remain. The findings in this thesis provide greater insight into the nature of confinement and indicate the need for further research if the successful implementation of these structures into an all silicon tandem cell is to be achieved.

The development of nanostructured coatings which exhibit enhanced mechanical properties is currently of interest due to the importance of high performance coatings in a large range of applications. Single layer coatings have predominantly been used for these demanding applications, however the promising mechanical properties observed in multilayer coatings has shifted the focus of current research. In particular, there has been reports of the use of alternating materials with opposing mechanical properties, as seen in the abalone shell, which have exhibited hardness and toughness values significantly greater than either of their constituent materials. The main objective of this thesis was to fabricate Al/W nanostructured multilayers and determine if they exhibit enhanced mechanical properties. The Al/W nanostructured multilayers were fabricated using two different deposition techniques: pulsed magnetron sputtering and cathodic arc deposition. These two techniques differ in the energy of the depositing species and this results in significant differences in film properties. The indentation hardness of the coatings was measured using a Hysitron Nanoindenter. The relationship between the mechanical properties and microstructure was obtained using a range of characterisation techniques. Auger electron spectroscopy (AES), energy dispersive spectroscopy (EDS) and electron energy loss spectroscopy (EELS) were used to determine the chemical composition and stoichiometry, while cross-sectional transmission electron microscopy (XTEM) and energy filtered transmission electron microscopy (EFTEM) were used to explore the microstructure. The findings of this thesis showed very different results for the two deposition techniques. Although sputtering successfully produced well defined multilayers, no evidence of enhanced hardness was found for periods between 5 and 200 nm. On the other hand, arc deposited samples with intended periods between 1 and 200 nm showed a hardness enhancement above that of pure W, however the samples of highest hardness did not contain Al layers for much of their thickness. Arc deposited samples with the finest nominal periods (1 and 2 nm) contained W-Al intermetallics and were soft. The hardening mechanism was not attributed to a multilayer structure, rather to the introduction of defects in the W layers which acted as pinning sites for dislocations. A modified Hall-Petch equation for hardness enhancement fitted the data for W films prepared by pulsed cathodic arc in which the grain diameter was replaced by the nominal multilayer period. The difficulty producing Al layers on W surfaces in the cathodic arc was overcom e by changing the film growth mechanism by introducing Ar or O2 at the W/Al interface. In the latter case, Al2O3/W multilayers were formed but again showed no hardness enhancements. Complete microanalysis and characterisation of the multilayer structures is vital in determining the mechanisms which govern the hardness enhancements. The evidence in this thesis suggests that the defect density, and not the presence of interfaces are responsible for the hardness enhancement effect.

Silicon nanocrystals embedded in silicon nitride have received attention as promising materials for optoelectronic applications. More specifically, band gap engineering of novel materials based on silicon nanocrystals has been proposed for possible application in an all-silicon tandem solar cell within the field of `third generation' photovoltaics. Such an application would require nanocrystals to exhibit quantum confinement whereby the optical and electrical properties of a film could be tuned by controlling the size of these `quantum dots'. This thesis investigates the correlation between the structural and optical properties of silicon nanocrystals grown in silicon nitride multilayer structures via solid phase crystallisation, as part of an experimental investigation into quantum confinement. A study of the relevant processing parameters for the solid phase crystallization of silicon nanocrystals in amorphous silicon nitride is presented and the effectiveness of the multilayer approach for controlling nanocrystal size is demonstrated. Structural characterisation using transmission electron microscopy and glancing incidence x-ray diffraction is complemented with a new application of Fourier transform infrared spectroscopy for the detection of silicon nanocrystals. A case study on the effects of annealing temperature on the photoluminescence from silicon nitride multilayers is presented. While a clear correlation between the structural, molecular and optical properties is demonstrated, evidence of quantum confinement remains ambiguous. The investigation into the limits of parameter space for the formation of silicon nanocrystals in silicon nitride multilayers also leads to the formation of a novel Si-Si3N4 nanocomposite material. A comprehensive study of the photoluminescence from silicon nanocrystals embedded in nitride is presented in the context of homogeneous and multilayer nitride films. Size dependent PL and absorption is demonstrated for silicon nitride multilayers with silicon-rich silicon nitride layer thicknesses varying from 1 to 4.5 nm, indicating the formation of quantum wells. These same structures are annealed to form arrays of silicon nanocrystals. Although the PL and absorption spectra suggest quantum effects, inherent ambiguities remain. The findings in this thesis provide greater insight into the nature of confinement and indicate the need for further research if the successful implementation of these structures into an all silicon tandem cell is to be achieved.

Previous research on new novel substrates for giant magnoresistance structures has indicated that a net increase in the effect is present. The substrates studied were V-grooved or stepped, however research presented in this thesis used an embossed surface manufactured from alumina oxide which consisted of regular hexagonal arrays with spacing of 110 nm and pore diameter of 60 nm. The physical properties measurements unveiled a net enhancement of the giant magnetoresistance effect thru the whole range of the copper spacer thicknesses deposited with direct current magnetron sputter. The maximum net increase appeared for a spacer thickness of 4.0 nm where the flat silicon substrate yielded a 3 % increase but the embossed surface substrate generated a 12% increase with an overall effect of a 4-fold net enhancement of the effect. Both the aluminum oxide substrates and the thin films structures can be manufactured inexpensively and can be also mass-produced, which are welcoming advantages for the technology sector of magnetic sensing.

The layer-by-layer assembly (LBL) of polyelectrolytes has been extensively studied for the preparation of ultrathin films due to the versatility of the build-up process. The control of the permeability of these layers is particularly important as there are potential drug delivery applications. Multilayered polyelectrolyte microcapsules are also of great interest due to their possible use as microcontainers. This work will present two methods that can be used as employable drug delivery systems, both of which can encapsulate an active molecule and tune the release properties of the active species. <br><br> Poly-(N-isopropyl acrylamide), (PNIPAM) is known to be a thermo-sensitive polymer that has a Lower Critical Solution Temperature (LCST) around 32oC; above this temperature PNIPAM is insoluble in water and collapses. It is also known that with the addition of salt, the LCST decreases. This work shows Differential Scanning Calorimetry (DSC) and Confocal Laser Scanning Microscopy (CLSM) evidence that the LCST of the PNIPAM can be tuned with salt type and concentration. Microcapsules were used to encapsulate this thermo-sensitive polymer, resulting in a reversible and tunable stimuli- responsive system. The encapsulation of the PNIPAM inside of the capsule was proven with Raman spectroscopy, DSC (bulk LCST measurements), AFM (thickness change), SEM (morphology change) and CLSM (in situ LCST measurement inside of the capsules). The exploitation of the capsules as a microcontainer is advantageous not only because of the protection the capsules give to the active molecules, but also because it facilitates easier transport. <br><br> The second system investigated demonstrates the ability to reduce the permeability of polyelectrolyte multilayer films by the addition of charged wax particles. The incorporation of this hydrophobic coating leads to a reduced water sensitivity particularly after heating, which melts the wax, forming a barrier layer. This conclusion was proven with Neutron Reflectivity by showing the decreased presence of D2O in planar polyelectrolyte films after annealing creating a barrier layer. The permeability of capsules could also be decreased by the addition of a wax layer. This was proved by the increase in recovery time measured by Florescence Recovery After Photobleaching, (FRAP) measurements. <br><br> In general two advanced methods, potentially suitable for drug delivery systems, have been proposed. In both cases, if biocompatible elements are used to fabricate the capsule wall, these systems provide a stable method of encapsulating active molecules. Stable encapsulation coupled with the ability to tune the wall thickness gives the ability to control the release profile of the molecule of interest. / Verkapselung ist ein vielseitiges Werkzeug, das zum Schutz und zum Transport von Molekülen ebenso eingesetzt werden kann, wie zur Verbindung von Reaktionspartnern in einem gemeinsamen, von der Umgebung abgeschirmten Raum. Es basiert auf einem einfachen Vorbild der Natur. Pflanzen schützen ihren Samen zum Beispiel durch eine harte, nahezu undurchdringbare Schale (Nüsse) oder durch eine selektiv durchlässige Hülle, wie bei Weizen, der sobald er feucht wird zu keimen beginnt. Die Natur setzt durch den Einsatz des Hülle-Kern Prinzips sehr effizient die Kontrolle über Durchlässigkeit und Anpassung an bestimmte Aufgaben um. <br><br> Wird das Hülle-Kern-Prinzip zum Schutz oder Transport von Molekülen eingesetzt, so sind die zu verwendenden Kapseln nur wenige Mikrometer groß. Sie werden dann als Mikrokapseln bezeichnet. Zur Erzeugung dieser Mikrokapseln werden verschiedene Methoden verwendet. Der heute übliche Weg geht von einer ca. 5-10 Mikrometer großen Kugel (Kern) aus, die mit einer stabilen und an die gewünschten Eigenschaften angepassten Schicht von wenigen Nanometern versehen wird. Im Anschluss wird der Kern herausgelöst und eine hohle, stabile Kapsel erhalten. <br><br> Schichten von wenigen Nanometern Dicke können aus Polyelektrolyten durch das Layer-by-Layer-Verfahren (LbL) hergestellt werden. Dieses Verfahren eignet sich auf Grund seiner vielen Anpassungsmöglichkeiten besonders zum Aufbau der Schichten für Mikrokapseln, da sich die Eigenschaften der Beschichtung bereits beim Aufbau der Schicht auf die Bedürfnisse maßschneidern lassen. Diese Arbeit befasst sich mit der Erzeugung von Mikrokapseln, deren Eigenschaften temperaturabhängig sind. Dies wurde auf zwei Wegen erreicht. Zum einen wurden Kapseln aus Polyelektrolyten und Wachs aufgebaut. Bei Temperaturerhöhung schmilzt das Wachs und versiegelt die Kapsel. Zum anderen werden Kapseln mit einem Wärme empfindlichen Polymer gefüllt. Bei Temperaturerhöhung kollabiert das Polymergerüst. Der enthaltene Wirkstoff wird freigesetzt.

The knowledge of growth and characterizing techniques is essential for the preparation of high quality thin films and multilayers. Here, structural properties have been investigated by X-ray reflectivity, X-ray diffraction, and transmission electron microscopy while the composition was determined by Rutherford backscattering spectrometry. For the magnetic studies, magneto-optical Kerr effect and X-ray magnetic circular dichroism have been used. The structural properties of the metal/insulator multilayer system, Fe/MgO, have been investigated. The coherency of the layers was influenced by the difference of the atomic distance in the Fe and MgO layers, resulting in long range strain fields. As a consequence, the coherency between the layers is not maintained. The atomic steps can not exist in amorphous materials, due to the absence of well defined atomic distances. Furthermore, the magnetic properties of amorphous materials allow a tuning of magnetic properties such as magnetic anisotropy and ordering temperature. The possibility to imprint arbitrary magnetic anisotropy in nanolaminated magnetic amorphous Co68Fe24Zr8 was demonstrated. The ratio of the orbital to spin moments for both Fe and Co was determined, for both thick and thin layers embedded in amorphous Al70Zr30 layers. When growing Co68Fe24Zr8 /Al2O3 the layers exhibit large changes in layer quality with thickness of the layers, ultimately affecting the magnetic properties of the stack. The use of protective layers is of large importance when performing ex-situ measurements. Most of the materials used were capped by Al2O3, effectively hindering both the reaction with oxygen and water. The penetration of hydrogen through different thicknesses of alumina was investigated. The experiments confirmed high degree of passivation as well as the possibility to selectively diffuse hydrogen through these layers. The use of element specific diffusion barriers allows the tailoring of magnetic properties of magnetic thin films and multilayers.