The properties of a polymer surface can be manipulated by the addition of a small quantity of surface active functionalised polymer to the bulk. On annealing above the glass transition these low surface energy functional groups attach to the air/polymer interface forming a brush like layer. To quantify this effect perdeuterated polystyrenes with fluoroalkane groups at specific locations in the polymer have been blended with unmodified polystyrene. Three key areas have been studied; effect of molecular architecture; effect of the molecular weight of the matrix polymer; and the rate of formation of the segregating layer. The complementary techniques of neutron reflectometry and nuclear reaction analysis have been used to determine the near surface depth profile of the deuterated polymer. Architectures studied were linear polystyrene with functional groups at both ends of the polymer chain, a 3-armed star with a functional core and linear polystyrene with functional groups evenly spaced along the chain. The architecture affected the shape of the composition profile but had little effect on the surface volume fraction and surface excess values obtained for the same bulk volume fraction. Self-consistent field theory simulations were carried out to determine the 'sticking energy' of the functional groups and good comparisons were obtained between the experimental volume fraction profiles and those predicted. Some segregation of functional polymer was observed during sample preparation and equilibrium segregation was obtained in less than one hour for 50000 M(_W) linear polymer up to eight hours for the 3-armed star after annealing under vacuum at 413K. For the difunctional polystyrene the functional groups did not have a significant affect on the rate of diffusion compared to non-functional polystyrene and diffusion coefficients obtained ranged from 6x10(^-16) to 9x10(^-15) cm(^2)s(^-1) The 3-armed star had the lowest diffusion coefficient value of 2xl0(^-16) cm(^-2)s(^-1) because of the inability for branched molecules to diffuse by reptation.

Energetic polyatomic cluster beams are increasingly used in materials processing and surface analysis applications. In secondary ion mass spectrometry (SIMS) such beams have previously been utilised to investigate the chemical distribution of organic molecules (polymers, biological molecules and pharmaceuticals etc). One important application is in organic electronics, where the depth-distribution of organic components is important in the device performance. Massive gas cluster ion beams (GCIBs) have produced more successful depth-profiles for organic electronic devices that smaller projectiles including SF5+ and C60+. However, further work is needed to investigate and optimise experimental parameters to deliver the necessary SIMS performance. This study focused on molecular depth profiling of organic insulator (PMMA) and semiconductor (PTAA and TIPS-pentacene) materials, in single and bi-layered combinations, utilising cluster SIMS, using C60+ and Arn+, at different temperatures and energies. In general, at room temperature, the best depth resolution was obtained, using large Ar-GCIBs of low energy per atom (E/n ~10 eV), in comparison with the smaller Ar-GCIBs or with C60+ beams at the same total impact energy. On materials which sputtering under C60+ bombardment, ion and neutral yields were greatest due to the higher E/n, compared with GCIBs. Data from PMMA show that the sputter yield under C60 and Arn projectiles conform to the published 'universal' dependence of Y/n to E/n. Depth profiling of the semiconductor compounds were unsuccessful, using C60+ projectiles. For depth profiles using large GCIB projectiles, an increase in the secondary ion yield was observed at the interface with the silicon substrate - a phenomenon which was not observed for the smaller projectiles. In general, the most successful depth profiles (i.e. more constant molecular and fragment secondary ion yields, observed at pseudo-steady-state regions) and best depth resolutions were obtained at cryogenic temperatures - conditions under which corresponding sputtering yields and secondary ion yields were suppressed.

The objective of this research project was to establish a better understanding of the mechanism(s) and route(s) by which selenium (Se) may enter an aquatic ecosystem that has been receiving treated metal mine effluent from an upstream uranium milling operation. Synchrotron based X-ray absorption spectroscopy (XAS) and X-ray fluorescence (XRF) imaging, which require little sample pre-treatment, were employed to study the speciation and distribution of Se in complex sediment and benthic invertebrates samples collected from the field. Laboratory based inductively coupled plasma mass spectrometry (ICP-MS) provided quantitative Se concentrations. Samples were taken from Fox Lake and Unknown Lakes, downstream of the mill, and Yeoung Lake as a control. The variation in Se speciation as a function of depth in intact sediment cores may provide insight into the species of Se available to the sediment dwelling benthic invertebrate communities. Therefore, a custom sample holder was designed to facilitate analysis of intact sediment cores at cryogenic temperatures. Additionally, laboratory reared chironomids were water-exposed to various Se species, to compare their Se speciation and localization to chironomids collected in the field. The successful demonstration of the custom sample holder and viable use of synchrotron XAS and XRF in studying sediment and chironomid samples have revealed that biologically relevant Se forms were present in sediment at depths accessible by the benthic invertebrate community. These Se forms included selenomethionine-like and selenite species, and to a lesser degree elemental Se; an increased proportion of reduced Se species was observed as depth increased. Other elements measured concurrently with Se included As, Zn, Cu, Ni, Fe, and Mn, providing an estimation of the redox boundary found both in Fox and Unknown Lake, as well as suggesting the presence of iron species that could aid in the reduction of Se. Field and laboratory reared chironomids showed similar Se species, and XRF imaging revealed the localization of Se in 4 distinct regions: head capsule, brain, salivary glands, and gut lining. Overall, the project has provided important insights into the interactions of Se with this aquatic ecosystem, which may have future applications in cold water systems with elevated Se concentrations.

This investigation examines band gap engineering of the GaAsN alloy by means of plasma ion implantation. The strong redshift of the alloy's band gap is suitable for telecommunication applications and thus stimulated much interest in recent years. Nitrogen (N) ion implantation into gallium arsenide (GaAs) results in a thin shallow N-rich layer below the surface. However, the violent implantation process also modifies the concentrations of gallium and arsenide. The core of this thesis is a novel method for prediction of the band gap from the conditions in the processing plasma.<p>The first important variable, the number of implanted ions, is obtained from the Lieberman model for the current during high-voltage Plasma Ion Implantation (PII). A review of the model's assumptions is provided as well as a comprehensive discussion of the implantation which includes error boundaries. The predicted and measured ion currents agree within error boundaries. The number of implanted ions can therefore be obtained from the prediction.<p>The distribution of the implanted ions was subsequently explored by simulations such as TRIM and TRIDYN. It was found that the nitrogen content in GaAs is limited by the sputtering of the surface atoms. Furthermore, the content of gallium increases near the surface while the content of arsenic decreases. The predicted ratios of the constituents in the implanted layer is such that the alloy cannot form by ion implantation alone; it could be reconciled by annealing.<p>Preliminary samples were produced and tested for the formation of the GaAsN alloy by Raman spectroscopy. No evidence for bonds between N and either Ga or As was found in the as-implanted samples. The thesis concludes with a discussion of the necessary steps to synthesize the GaAsN alloy.

This investigation examines band gap engineering of the GaAsN alloy by means of plasma ion implantation. The strong redshift of the alloy's band gap is suitable for telecommunication applications and thus stimulated much interest in recent years. Nitrogen (N) ion implantation into gallium arsenide (GaAs) results in a thin shallow N-rich layer below the surface. However, the violent implantation process also modifies the concentrations of gallium and arsenide. The core of this thesis is a novel method for prediction of the band gap from the conditions in the processing plasma.<p>The first important variable, the number of implanted ions, is obtained from the Lieberman model for the current during high-voltage Plasma Ion Implantation (PII). A review of the model's assumptions is provided as well as a comprehensive discussion of the implantation which includes error boundaries. The predicted and measured ion currents agree within error boundaries. The number of implanted ions can therefore be obtained from the prediction.<p>The distribution of the implanted ions was subsequently explored by simulations such as TRIM and TRIDYN. It was found that the nitrogen content in GaAs is limited by the sputtering of the surface atoms. Furthermore, the content of gallium increases near the surface while the content of arsenic decreases. The predicted ratios of the constituents in the implanted layer is such that the alloy cannot form by ion implantation alone; it could be reconciled by annealing.<p>Preliminary samples were produced and tested for the formation of the GaAsN alloy by Raman spectroscopy. No evidence for bonds between N and either Ga or As was found in the as-implanted samples. The thesis concludes with a discussion of the necessary steps to synthesize the GaAsN alloy.

タンデトロン加速器質量分析計業績報告 Summaries of Researches Using AMS 2005 (平成17)年度

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Ziel dieser Arbeit war die Entwicklung neuer Methoden in der Rasterkraftmikroskopie, um die Qualität und Interpretierbarkeit von Oberflächenabbildungen auf der Nanometerskala, vor allem jener sehr weicher Proben, entscheidend zu verbessern. Der für polymere und biologische Materialien standardmäßig verwendete intermittierende Kontaktmodus führt auf weichen Oberflächen zu verfälschten Abbildungen der Topographie und der mechanischen Eigenschaften. In dieser Arbeit wurden Techniken entwickelt, die einerseits zerstörungsfreie, tiefenaufgelöste Rasterkraftmikroskopie und andererseits Einzelmessungen mit variabler Dämpfung im intermittierenden Kontaktmodus ermöglichen. Die laterale Auflösung beider Methoden liegt dabei im Rahmen herkömmlicher Techniken (< 10 nm). Die Tiefenauflösung konnte im Vergleich zu anderen Methoden um eine Größenordnung auf unter 1 nm verbessert werden. Die neuen Methoden wurden auf einer breiten Palette polymerer Materialien angewandt. Die räumliche Struktur oberflächennaher Bereiche eines Blockcopolymerfilms konnte im Vergleich zu herkömmlichen Methoden deutlich genauer abgebildet werden. Gleiches wurde auf elastomerem Polypropylen erreicht. Es konnten weiche, amorphe Deckschichten auf teilkristallinen Polymeren nachgewiesen und vermessen werden, was in der organischen Elektronik eine wichtige Rolle spielen kann. Die innere Struktur selbstangeordneter Nanodrähte aus Oligothiophen-Aggregaten konnte aufgelöst werden und es wurde die Selbstanordnung von Kollagenfibrillen im gequollenen Zustand beobachtet.

Ziel dieser Arbeit war die Entwicklung neuer Methoden in der Rasterkraftmikroskopie, um die Qualität und Interpretierbarkeit von Oberflächenabbildungen auf der Nanometerskala, vor allem jener sehr weicher Proben, entscheidend zu verbessern. Der für polymere und biologische Materialien standardmäßig verwendete intermittierende Kontaktmodus führt auf weichen Oberflächen zu verfälschten Abbildungen der Topographie und der mechanischen Eigenschaften. In dieser Arbeit wurden Techniken entwickelt, die einerseits zerstörungsfreie, tiefenaufgelöste Rasterkraftmikroskopie und andererseits Einzelmessungen mit variabler Dämpfung im intermittierenden Kontaktmodus ermöglichen. Die laterale Auflösung beider Methoden liegt dabei im Rahmen herkömmlicher Techniken (< 10 nm). Die Tiefenauflösung konnte im Vergleich zu anderen Methoden um eine Größenordnung auf unter 1 nm verbessert werden. Die neuen Methoden wurden auf einer breiten Palette polymerer Materialien angewandt. Die räumliche Struktur oberflächennaher Bereiche eines Blockcopolymerfilms konnte im Vergleich zu herkömmlichen Methoden deutlich genauer abgebildet werden. Gleiches wurde auf elastomerem Polypropylen erreicht. Es konnten weiche, amorphe Deckschichten auf teilkristallinen Polymeren nachgewiesen und vermessen werden, was in der organischen Elektronik eine wichtige Rolle spielen kann. Die innere Struktur selbstangeordneter Nanodrähte aus Oligothiophen-Aggregaten konnte aufgelöst werden und es wurde die Selbstanordnung von Kollagenfibrillen im gequollenen Zustand beobachtet.