The present thesis addresses two research areas related to film growth in a highly ionized magnetron sputtering system: plasma characterization, and thin film growth and analysis. The deposition technique used is called high power pulsed magnetron sputtering (HPPMS). Characteristic for this technique are high energy pulses (a few Joules) of length 50-100 µs that are applied to the target (cathode) with a duty time of less than 1 % of the total pulse time. This results in a high electron density in the discharge (>1x1019 m-3) and leads to an increase of the ionization fraction of the sputtered material reaching up to 70 % for Cu. In this work the spatial and temporal evolution of the plasma parameters, including the electron energy distribution function (EEDF), the electron density and the electron temperature are determined using electrostatic Langmuir probes. Electron temperature measurements reveal a low effective temperature of 2-3 eV. The degree of ionization in the HPPMS discharge is explained in light of the self-sputtering yield of the target material. A simple model is therefore provided in order to compare the sputtering yield in HPPMS and that in dc magnetron sputtering (dcMS) for the same average power. Thin Ta films are grown using HPPMS and dcMS and their properties are studied. It is shown that enhanced microstructure and morphology of the deposited films is achieved by HPPMS. The Ta films are also deposited at a number of substrate inclination angles ranging from 0o (i.e., facing the target surface) up to 180 o (i.e., facing away from the target). Deposition rate measurements performed at all inclination angles for both techniques, reveal that growth made using HPPMS resulted in an improved film thickness at higher inclination. Furthermore, the high ionization of the Ta atoms in HPPMS discharge is found to allow for phase tailoring of the deposited films at all inclination angles by applying a bias voltage to the substrate. Finally, highly ionized magnetron sputtering of a compound MAX-phase material (Ti3SiC2) is performed, demonstrating that the HPPMS discharge could also be used to tailor the composition of the growing Ti-Si-C films. / On the day of the public defence of the doctoral thesis, the status of articles III and IV was Submitted. The titles of papers VI and VII changed between their manuscript forms and when they were published.

The benefits of low UV dose treatment of horticultural produce – also known as hormetic treatment - have been attested to in numerous studies conducted over the last 15 years. However, commercial growers have not adopted the concept of hormesis. With increasingly stringent controls on the use of fungicides and other chemical agents the time has come to examine how hormetic treatment might be applied in the horticulture sector. The objectives of this work were firstly, to confirm UV-induced hormetic effects applied postharvest for a number of different types of produce, namely, tomatoes, broccoli, strawberries and mangoes. Secondly, to evaluate the use of rollers to ensure full surface treatment of produce, and thirdly to evaluate the possibility of treating produce preharvest. In order to investigate surface UV dose distributions, a polystyrene sphere (Diameter 70 mm) was used to simulate fruits such as tomatoes, apples, peaches etc., that have an approximately spherical form. Biodosimetry based on spores of Bacillus subtilis was employed to experimentally determine UV doses and to compare the results obtained with theoretical predictions. Good agreement was obtained and the modelling approach was extended to other types of produce. This showed the amenability of mechanical rollers to ensure full surface treatment of produce. Postharvest treatment of produce was carried using conventional low intensity UV sources principally emitting at 254 nm and also a commercially available high energy pulsed UV source. Treatment using the conventional UV source was carried out on mechanical rollers within a UV cabinet designed for this work at a fixed distance from the source and at an intensity of 1000 μW/cm2. A 5 minute conventional UV treatment of tomatoes was approximately comparable to fruit given a 3-pulsed treatment using the pulsed source (507 J/pulse of polychromatic light). The colour and texture of both groups of fruit were significantly maintained as compared with controls. The treated tomatoes also showed a significant increase in the ascorbic acid levels during storage. Similarly, a 15 minute conventional UV treatment of broccoli heads was comparable to heads given a 10-pulsed treatment using the pulsed source. Where both treatments gave rise to a statistically significant retention of green colour of treated broccoli. In addition, mangoes given a 10 minute conventional UV treatment were comparable to fruit given a 20-pulsed treatment using the pulsed source with both treatments leading to maintenance of texture as compared to control fruit. This confirmed the UV-hormetic effects. The effects of conventional and pulsed treatments are compared and discussed. Preharvest treatment of tomatoes and strawberries was carried out in commercial glasshouses. Doses of either 3 or 8 kJ/m2 were delivered to the fruits using a treatment device designed for the work, which delivered a combined intensity of 2000 μW/cm2 from two low pressure UV sources. The treated tomatoes showed a delay in development of colour as measured on the vine and after picking. Picked tomatoes were inoculated with P. digitatum and C. gloeosporioides and the results obtained showed a significant inhibition of the development of the fungi in the treated fruit during the storage period. These results suggest that the beneficial response shown by the preharvest treatment is not a localised one but a systematically induced resistance observable throughout the treated plant. This was shown by monitoring tomato fruits on treated plants which themselves where not directly exposed to the UV light. The two doses elicited different responses in the treated strawberries, with the 8 kJ/m2 dose causing the fruit to redden significantly faster than the 3 kJ/m2 treated fruits and controls. This could have significant nutritional benefit as the red colour of strawberries has been correlated with anthocyanin levels. On the other hand, treatment at the lower UV dose led to a lag in colour development. The amenability of the equipment utilised for commercial application is discussed.

No description available.

River incision into a widespread, upland low-relief landscape, and related patterns of exhumation recorded by low-temperature thermochronology, together underpin geodynamic interpretations for crustal thickening and uplift of the eastern Tibetan Plateau. We report results from a suite of 11 (U-Th-Sm)/He cooling-age samples. Eight samples comprise a 1.2 km relief section collected from elevations up to 4800 m in the Jiulong Shan, an elevated, rugged region located in the hinterland of the Yalong-Longmen Shan Thrust Belt, and surrounded on three sides by upland low-relief landscape surfaces. Zircon and apatite cooling ages record two episodes of rapid exhumation in the early Oligocene and late Miocene, that were separated by a period of stability from similar to 30 to 15 Ma. The first episode is consistent with a similar pulse evident from the Longmen Shan. The second episode is ongoing, and when integrated with adjacent cooling-age data sets, shows that doming of the Jiulong Shan has resulted in 2 to 4 km of differential exhumation of the plateau interior. We show from a compilation of glacial landform-mapping that the elevation of the plateau surface closely tracks global last glacial maximum equilibrium line altitude. We hypothesize that smoothing of highlands by efficient glacial and periglacial erosion, coupled with potential river captures and conveyance of sediments via external drainage, can yield an apparently continuous low-relief plateau landscape formed diachronously at high elevation. (C) 2016 Elsevier B.V. All rights reserved.

<p>Thin film deposition techniques are indispensable to the development of modern technologies as thin film based optical coatings, optoelectronic devices, sensors, and biological implants are the building blocks of many complicated technologies, and their performance heavily depends on the applied deposition technique. Particularly, the emergence of novel solution-processed materials, such as soft organic molecules, inorganic compounds and colloidal nanoparticles, facilitates the development of flexible and printed electronics that are inexpensive, light weight, green and smart, and these thin film devices represent future trends for new technologies. One appealing feature of solution-processed materials is that they can be deposited into thin films using solution-processed deposition techniques that are straightforward, inexpensive, high throughput and advantageous to industrialize thin film based devices. However, solution-processed techniques rely on wet deposition, which has limitations in certain applications, such as multi-layered film deposition of similar materials and blended film deposition of dissimilar materials. These limitations cannot be addressed by traditional, vacuum-based deposition techniques because these dry approaches are often too energetic and can degrade soft materials, such as polymers, such that the performance of resulting thin film based devices is compromised.</p><p>The work presented in this dissertation explores a novel thin film deposition technique, namely emulsion-based, resonant infrared, matrix-assisted pulsed laser evaporation (RIR-MAPLE), which combines characteristics of wet and dry deposition techniques for solution-processed materials. Previous studies have demonstrated the feasibility of emulsion-based RIR-MAPLE to deposit uniform and continuous organic, nanoparticle and blended films, as well as hetero-structures that otherwise are difficult to achieve. However, fundamental understanding of the growth mechanisms that govern emulsion-based RIR-MAPLE is still missing, which increases the difficulty of using rational design to improve the performance of initial RIR-MAPLE devices that have been demonstrated. As a result, it is important to study the fundamentals of emulsion-based RIR-MAPLE in order to provide insight into the long-term prospects for this thin film deposition technique.</p><p>This dissertation explores the fundamental deposition mechanisms of emulsion-based RIR-MAPLE by considering the effects of the emulsion target composition (namely, the primary solvent, secondary solvent, and surfactant) on the properties of deposited polymer films. The study of primary solvent effects on hydrophobic polymer deposition helps identify the unique method of film formation for emulsion-based RIR-MAPLE, which can be described as cluster-by-cluster deposition of emulsified particles that yields two levels of ordering (i.e., within the clusters and among the clusters). The generality of this film formation mechanism is tested by applying the lessons learned to hydrophilic polymer deposition. Based on these studies, the deposition design rules to achieve smooth polymer films, which are important for different device applications, are identified according to the properties of the polymer.</p><p>After discussion of the fundamental deposition mechanisms, three applications of emulsion-based RIR-MAPLE, namely thin film deposition of organic solar cells, polymer/nanoparticle hybrid solar cells, and antimicrobial/fouling-release multifunctional films, are studied. The work on organic solar cells identifies the ideal deposition mode for blended films with nanoscale domain sizes, as well as demonstrates the relationships among emulsion target composition, film properties, and corresponding device performance. The studies of polymer/nanoparticle hybrid solar cells demonstrate precise control of colloidal nanoparticle deposition, in which the integrity of nanoparticles is maintained and a distinct film morphology is achieved when co-deposited with polymers. Finally, the application of antimicrobial and fouling-release multifunctional films demonstrates the importance of blended film deposition with nanoscale phase separation, a key feature to achieving reusable bio-films that can kill bacteria when illuminated with ultraviolet light.</p><p>Thus, this dissertation provides great insight to the fundamentals of emulsion-based RIR-MAPLE, serves as a valuable reference for future development, and paves the pathway for wider adoption of this unique thin film deposition technique, especially for organic solar cells.</p> / Dissertation

Pulsed laser flash photolysis with both visible and infrared detection has been applied to the study of the displacement of weakly coordinating ligands (Lw) by strongly "trapping" nucleophiles (Ls) containing either an olefinic functionality (Ls = 1-hexene, 1-decene, 1-tetradecene) or nitrogen (Ls = acetonitrile, hydrocinnamonitrile) from the photogenerated 16 electron pentacarbonylchromium (0) intermediate. 5-Chloropent-l-ene (Cl-ol), a potentially bidentate ligand, has been shown to form (ol-Cl) pentacarbonylchromium (0), in which Cl-ol is bonded to Cr via a lone pair on the chlorine, and isomerize to (Cl-ol) pentacarbonylchromium (0), in which Cl-ol is bonded to the olefinic functionality on the submillisecond time scale. This process has been studied in both the infrared and visible region employing both fluorobenzene or n-heptane as the "inert" diluent. Parallel studies employing 1-chlorobutane and 1-hexene were also evaluated and showed great similiarity with the Cl-ol system. The data supported a largely dissociative process with a possibility of a small interchange process involving the H's on the alkyl chain. Studies were also carried out for various Cr(CO)6/arene/Ls systems (arene = various alkyl or halogenated substituted benzenes). The data indicated that for both C6H5R (R=various alkyl chains) or multi-alkyl substituted arenes (i.e. o-xylene, 1,2,3-trimethylbenzene) containing an "unhindered" ring-edge, bonding to the the Cr(CO)5 moiety occurs "edge on" via a partially delocalized center of unsaturation on the ring. The data indicated that both electronic and steric properties of the arenes influence the kinetics, and that an interchange pathway takes place at least, in part, through the alkyl chains on both the arenes and "trapping" nucleophiles. Moreover, halogenated arenes bond through the lone pair on the halogen for both CI- and Br- derivatives but "edge-on" for the fluorinated arenes. Finally, in the case of arene complexes without and "unhindered" ring-edge (i.e., 1,2,3,4,5-pentamethylbenzene) bonding can occur either "edge-on" or through the ring center of the arene or combination of the two. Carbonyl stretching frequencies for the arenes are also indicative of the type of bonding.

Acute effects of a pulsed external electric field (PEEF) at 20 V/cm and a d.c. EEF at 90 V/cm on light transmittance in an isolated compound crayfish nerve was measured. In a third series, the nerve was pre-treated with the Na+ channel blocker tetrodotoxin (TTX). A PEEF produced an irreversible increase in the variation of light transmittance in normal nerves but a reversible increase in TTX treated nerves. This data was statistically insignificant. The d.c. EEFs produced a reversible and statistically significant enhancement of variation in light transmittance in both untreated and TTX-treated nerves. The findings may be due to either (1) an alteration in the ion/fluid flux within the nerve or (2) a physical alteration of protein molecules in the membranes.

This work examines the use of higher order multiphoton resonances in higher harmonic generation together with judicious exploitation of coherent interaction properties to achieve efficient harmonic generation. A detailed experimental study on third harmonic generation in two photon resonant coherent interaction and a theoretical study on four photon resonant coherent interaction have been conducted. Two photon resonant coheren propagation in lithium vapor (2S-4S and 2S-3D interaction) has been studied in detail as a function of phase and delay of the interacting pulse sequence. Under coherent lossless propagation of 90 phase shifted pulse pair, third harmonic generation is enhanced. A maximum energy conversion efficiency of 1% was measured experimentally. This experiment shows that phase correlated pulse sequence can be used to control multiphoton coherent resonant effects. A larger two photon resonant enhancement does not result in more efficient harmonic generation, in agreement with the theoretical prediction. An accurate (to at least 0.5 A°) measurement of intensity dependent Stark shift has been done with the newly developed "interferometric wavemeter." Stark shifts as big as several pulse bandwidths (of picosecond pulses) result in a poor tuning of multiphoton resonance and become a limiting factor of resonant harmonic generation. A complete theory has been developed for harmonic generation in a four photon resonant coherent interaction. A numerical application of the theory to the Hg atom successfully interprets the experimental observations in terms of the phase dependent stimulated Raman scattering. With the intensity required for four photon resonant transition, the calculation predicts a dramatic Stark shift effect which completely destroys the resonance condition. This model provides a basis for the development of future schemes for efficient higher order coherent upconversion.

The development of the field of the science of ultra-cold matter has opened some exciting possibilities in exploring the quantum-mechanical processes which dominate matter interactions at the sub-microscopic scale. Although methods of cooling atoms are well established, molecular cooling is made difficult by molecules’ additional vibrational and rotational degrees of freedom. It was the goal of the research in this work to approach molecular cooling indirectly, by using broadband shaped-pulse photoassociation for the generation of tightly bound ultracold Rb₂ molecules. The experiments towards this goal conducted by our group included a pumpdecay experiment to observe the generation of ground state singlet or triplet molecules. However, attempts to observe an increase in ground state population have been unsuccessful. A pump-probe study of wavepacket dynamics in the 5s+5p electronic state was conducted in order to determine the appropriate timing for the application of an additional pulse to dump population into the ground state. Although the attempt to observe wavepacket oscillations has been unsuccessful, pump-probe studies have yielded the observation of loosely bound excited state molecules as a result of the photoassociation pulse. These results are promising as a first stage in a fully coherent pump-dump approach to stabilisation into the lowest vibrational ground state. This thesis will provide an introduction and overview to the concerns involved in addressing the problem of molecular cooling and generation. Experimental techniques will be discussed including pulsed laser systems, optical parametric amplifi- cation, and the presentation of an original design for pulse shaping with an acoustooptic modulator. The emphasis of these discussions will be on the principles and operating procedures required for the use of these devices as home-built systems. The thesis will conclude with the results of pump-probe experiments utilising the pulse shaper as a spectral cutting device.

We measured the diffraction efficiency response of two photorefractive polymer devices according to the duration of the single laser pulse used to record the hologram. The pulse duration was varied from 6 nanoseconds to 1 second, while the pulse energy density was maintained constant at 30 mJ/cm(2). This changed the peak power from 5 x 10(9) mW to 30 mW. We observed a strong reciprocity failure of the efficiency according to the pulse duration, with a reduction as large as a factor 35 between 1 second and 30 mu s pulse duration. At even lower pulse duration (< 30 mu s), the efficiency leveled out and remained constant down to the nanosecond exposure time. The same behavior was observed for samples composed of the same material but with and without buffer layers deposited on the electrodes, and different voltages applied during the holographic recording. We explained these experimental results based on the charge transport mechanism involved in the photorefractive process. The plateau is attributed to the single excitation of the charge carriers by short pulses (T-p < 30 mu s). The increase of efficiency for longer pulse duration (T-p > 30 mu s) is explained by multiple excitations of the charge carriers that allows longer distance to be traveled from the excitation sites. This longer separation distance between the carriers increases the amplitude of the space-charge field, and improves the index modulation. The understanding of the response of the diffraction efficiency according to the pulse duration is particularly important for the optimization of photorefractive materials to be used at high refresh rate such as in videorate 3D display.