Atomic Layer Deposition for optical applications: metal fluoride thin films and novel devices

Thin films of various metal fluorides are suited for optical coatings from infrared (IR) to ultraviolet (UV) range due to their excellent light transmission. In this work, novel metal fluoride processes have been developed for atomic layer deposition (ALD), which is a gas phase thin film deposition method based on alternate saturative surface reactions. Surface controlled self-limiting film growth results in conformal and uniform films. Other strengths of ALD are precise film thickness control, repeatability and dense and pinhole free films. All these make the ALD technique an ideal choice also for depositing metal fluoride thin films. Metal fluoride ALD processes have been largely missing, which is mostly due to a lack of a good fluorine precursor. In this thesis, TiF4 precursor was used for the first time as the fluorine source in ALD for depositing CaF2, MgF2, LaF3 and YF3 thin films. TaF5 was studied as an alternative novel fluorine precursor only for MgF2 thin films. Metal-thd (thd = 2,2,6,6-tetramethyl-3,5-heptanedionato) compounds were applied as the metal precursors. The films were grown at 175 450 °C and they were characterized by various methods. The metal fluoride films grown at higher temperatures had generally lower impurity contents with higher UV light transmittances, but increased roughness caused more scattering losses. The highest transmittances and low refractive indices below 1.4 (at 580 nm) were obtained with MgF2 samples. MgF2 grown from TaF5 precursor showed even better UV light transmittance than MgF2 grown from TiF4. Thus, TaF5 can be considered as a high quality fluorine precursor for depositing metal fluoride thin films. Finally, MgF2 films were applied in fabrication of high reflecting mirrors together with Ta2O5 films for visible region and with LaF3 films for UV region. Another part of the thesis consists of applying already existing ALD processes for novel optical devices. In addition to the high reflecting mirrors, a thin ALD Al2O3 film on top of a silver coating was proven to protect the silver mirror coating from tarnishing. Iridium grid filter prototype for rejecting IR light and Ir-coated micro channel plates for focusing x-rays were successfully fabricated. Finally, Ir-coated Fresnel zone plates were shown to provide the best spatial resolution up to date in scanning x-ray microscopy.

Atomic Layer Deposition and Photocatalytic Properties of Titanium Dioxide Thin Films

Photocatalytic TiO2 thin films can be highly useful in many environments and applications. They can be used as self-cleaning coatings on top of glass, tiles and steel to reduce the amount of fouling on these surfaces. Photocatalytic TiO2 surfaces have antimicrobial properties making them potentially useful in hospitals, bathrooms and many other places where microbes may cause problems. TiO2 photocatalysts can also be used to clean contaminated water and air. Photocatalytic oxidation and reduction reactions proceed on TiO2 surfaces under irradiation of UV light meaning that sunlight and even normal indoor lighting can be utilized. In order to improve the photocatalytic properties of TiO2 materials even further, various modification methods have been explored. Doping with elements such as nitrogen, sulfur and fluorine, and preparation of different kinds of composites are typical approaches that have been employed. Photocatalytic TiO2 nanotubes and other nanostructures are gaining interest as well. Atomic Layer Deposition (ALD) is a chemical gas phase thin film deposition method with strong roots in Finland. This unique modification of the common Chemical Vapor Deposition (CVD) method is based on alternate supply of precursor vapors to the substrate which forces the film growth reactions to proceed only on the surface in a highly controlled manner. ALD gives easy and accurate film thickness control, excellent large area uniformity and unparalleled conformality on complex shaped substrates. These characteristics have recently led to several breakthroughs in microelectronics, nanotechnology and many other areas. In this work, the utilization of ALD to prepare photocatalytic TiO2 thin films was studied in detail. Undoped as well as nitrogen, sulfur and fluorine doped TiO2 thin films were prepared and thoroughly characterized. ALD prepared undoped TiO2 films were shown to exhibit good photocatalytic activities. Of the studied dopants, sulfur and fluorine were identified as much better choices than nitrogen. Nanostructured TiO2 photocatalysts were prepared through template directed deposition on various complex shaped substrates by exploiting the good qualities of ALD. A clear enhancement in the photocatalytic activity was achieved with these nanostructures. Several new ALD processes were also developed in this work. TiO2 processes based on two new titanium precursors, Ti(OMe)4 and TiF4, were shown to exhibit saturative ALD-type of growth when water was used as the other precursor. In addition, TiS2 thin films were prepared for the first time by ALD using TiCl4 and H2S as precursors. Ti1-xNbxOy and Ti1-xTaxOy transparent conducting oxide films were prepared successfully by ALD and post-deposition annealing. Highly unusual, explosive crystallization behaviour occurred in these mixed oxides which resulted in anatase crystals with lateral dimensions over 1000 times the film thickness.

Cellulose Derivatives : Synthesis, Properties and Applications

Even though cellulose is the most abundant polymer on Earth, its utilisation has some limitations regarding its efficient use in the production of bio-based materials. It is quite clear from statistics that only a relatively small fraction of cellulose is used for the production of commodity materials and chemicals. This fact was the driving force in our research into understanding, designing, synthesising and finding new alternative applications for this well-known but underused biomaterial. This thesis focuses on the developing advanced materials and products from cellulose by using novel approaches. The aim of this study was to investigate and explore the versatility of cellulose as a starting material for the synthesis of cellulose-based materials, to introduce new synthetic methods for cellulose modification, and to widen the already existing synthetic approaches. Due to the insolubility of cellulose in organic solvents and in water, ionic liquids were applied extensively as the reaction media in the modification reactions. Cellulose derivatives were designed and fine-tuned to obtain desired properties. This was done by altering the inherent hydrogen bond network by introducing different substituents. These substituents either prevented spontaneous formation of hydrogen bonding completely or created new interactions between the cellulose chains. This enabled spontaneous self-assembly leading to supramolecular structures. It was also demonstrated that the material properties of cellulose can be modified even those molecules with a low degree of substitution when highly hydrophobic films and aerogels were prepared from fatty acid derivatives of nanocellulose. Development towards advanced cellulose-based materials was demostrated by synthesising chlorophyllcellulose derivatives that showed potential in photocurrent generation systems. In addition, liquid crystalline cellulose derivatives prepared in this study, showed to function as UV-absorbers in paper.

Single network adaptive critic design for power system stabilisers

The recently developed single network adaptive critic (SNAC) design has been used in this study to design a power system stabiliser (PSS) for enhancing the small-signal stability of power systems over a wide range of operating conditions. PSS design is formulated as a discrete non-linear quadratic regulator problem. SNAC is then used to solve the resulting discrete-time optimal control problem. SNAC uses only a single critic neural network instead of the action-critic dual network architecture of typical adaptive critic designs. SNAC eliminates the iterative training loops between the action and critic networks and greatly simplifies the training procedure. The performance of the proposed PSS has been tested on a single machine infinite bus test system for various system and loading conditions. The proposed stabiliser, which is relatively easier to synthesise, consistently outperformed stabilisers based on conventional lead-lag and linear quadratic regulator designs.

Protection of a Static Frequency Converter fed traction network, a case study

Aurizon, Australia's largest rail freight operator, is introducing the Static Frequency Converter (SFC) technology into its electric railway network as part of the Bauhinia Electrification Project. The introduction of SFCs has significant implications on the protection systems of the 50kV traction network. The traditional distance protection calculation method does not work in this configuration because of the effect that the SFC in combination with the remote grid has on the apparent impedance, and was substantially reviewed. The standard overcurrent (OC) protection scheme is not suitable due to the minimum fault level being below the maximum load level and was revised to incorporate directionality and under-voltage inhibit. Delta protection was reviewed to improve sensitivity. A new protection function was introduced to prevent back-feeding faults in the transmission network through the grid connection. Protection inter-tripping was included to ensure selectivity between the SFC protection and the system downstream.

Residential tariff structure and battery energy storage impact in queensland LV network

Distributed renewable energy has become a significant contender in the supply of power in the distribution network in Queensland and throughout the world. As the cost of battery storage falls, distribution utilities turn their attention to the impacts of battery storage and other storage technologies on the low voltage (LV) network. With access to detailed residential energy usage data, Energex's available residential tariffs are investigated for their effectiveness in providing customers with financial incentives to move to Time-of Use based tariffs and to reward use of battery storage.

Australian feature films and distribution: Industry or cottage industry?

Feature films remain critical flagships to any national film industry. Australian feature films can be highly commercial endeavours that also perform symbolic functions by embodying the national imaginary in big screen based sound and imagery. They conduct a dialogue with domestic audiences as well as showcase key aspects of Australia in the global film festival circuit. As the pre-eminent filmmaking form, feature films also serve as important launchpads for the careers of many Australian writers, directors, actors and technical crew. In the wake of over a decade of diminished share of local box office obtained by Australian feature films, Australian Feature Films and Distribution: Industry or cottage industry, examines issues in the production sector affecting the performance of Australian feature films and some responses by the central funding and support screen agency, Screen Australia.

Relaxation Time of Chemical Reactions from Network Thermodynamics

The relationship for the relaxation time(s) of a chemical reaction in terms of concentrations and rate constants has been derived from the network thermodynamic approach developed by Oster, Perelson, and Katchalsky.Generally, it is necessary to draw the bond graph and the “network analogue” of the reaction scheme, followed by loop or nodal analysis of the network and finally solving of the resulting differential equations. In the case of single-step reactions, however, it is possible to obtain an expression for the relaxation time. This approach is simpler and elegant and has certain advantages over the usual kinetic method. The method has been illustrated by taking different reaction schemes as examples.

Electrical and optical properties of amorphous semiconducting GeSe and GeSbSe films

The electrical activation energy and optical band-gap of GeSe and GeSbSe thin films prepared by flash evaporation on to glass substrates have been determined. The conductivities of the films were found to be given by Image , the activation energy Ea being 0.53 eV and 0.40 eV for GeSe and GeSbSe respectively. The optical absorption constant α near the absorption edge could be described by Image from which the optical band-gaps E0 were found to be 1.01 eV for GeSe and 0.67 eV for GeSbSe at 300°K. At 110°K the corresponding values of E0 were 1.07 eV and 0.735 eV respectively. The significance of these values is discussed in relation to those of other amorphous semiconductors.

Experimental investigation of catalytic and non-catalytic surface reactions on SiO2 thin films with shock heated oxygen gas

The present study is to investigate the interaction of strong shock heated oxygen on the surface of SiO2 thin film. The thermally excited oxygen undergoes a three-body recombination reaction on the surface of silicon dioxide film. The different oxidation states of silicon species on the surface of the shock-exposed SiO2 film are discussed based on X-ray Photoelectron Spectroscopy (XPS) results. The surface morphology of the shock wave induced damage at the cross section of SiO2 film and structure modification of these materials are analyzed using scanning electron microscopy and ion microscopy. Whether the surface reaction of oxygen on SiO2 film is catalytic or non-catalytic is discussed in this paper.

Viscoelastic Properties of Nanocrystalline Films of Semiconducting Chalcogenides at Liquid/Liquid Interface

The interfacial shear rheological properties of a continuous single-crystalline film of CuS and a 3D particulate gel of CdS nanoparticles (3−5 nm in diameter) formed at toluene−water interfaces have been studied. The ultrathin films (50 nm in thickness) are formed in situ in the shear cell through a reaction at the toluene−water interface between a metal−organic compound in the organic layer and an appropriate reagent for sulfidation in the aqueous layer. Linear viscoelastic spectra of the nanofilms reveal solid-like rheological behavior with the storage modulus higher than the loss modulus over the range of angular frequencies probed. Large strain amplitude sweep measurements on the CdS nanofilms formed at different reactant concentrations suggest that they form a weakly flocculated gel. Under steady shear, the films exhibit a yield stress, followed by a steady shear thinning at high shear rates. The viscoelastic and flow behavior of these films that are in common with those of many 3D “soft” materials like gels, foams, and concentrated colloidal suspensions can be described by the “soft” glassy rheology model.

Evaluation of packaging films to extend storage life of indigenous Australian vegetables and herbs

A study undertaken in Hervey Bay, Queensland, investigated the potential of creating an indigenous agribusiness opportunity based on the cultivation of indigenous Australian vegetables and herbs. Included were warrigal greens (WG) (Tetragonia tetragonioides), a green leafy vegetable and the herb sea celery (SC) (Apium prostratum); both traditional foods of the indigenous population and highly desirable to chefs wishing to add a unique, indigenous flavour to modern dishes. Packaging is important for shelf life extension and minimisation of postharvest losses in horticultural products. The ability of two packaging films to extend WG and SC shelf life was investigated. These were Antimisted Biaxial Oriented Polypropylene packaging film (BOPP) without perforations and Antifog BOPP Film with microperforations. Weight loss, packaging headspace composition, colour changes, sensory differences and microbial loads of packed WG and SC leaves were monitored to determine the impact of film oxygen transmission rate (OTR) and film water vapour transmission (WVT) on stored product quality. WG and SC were harvested, sanitised, packed and stored at 4°C for 16 days. Results indicated that the OTR and WVT rates of the package film significantly (PKLEINERDAN0.05) influenced the package headspace and weight loss, but did not affect product colour, total bacteria, yeast and mould populations during storage. There was no significant difference (PGROTERDAN0.05) in aroma, appearance, texture and flavour for WG and SC during storage. It was therefore concluded that a shelf life of 16 days at 4°C, where acceptable sensory properties were retained, was achievable for WG and SC in both packaging films.

Data mining for telecommunications network log analysis

Telecommunications network management is based on huge amounts of data that are continuously collected from elements and devices from all around the network. The data is monitored and analysed to provide information for decision making in all operation functions. Knowledge discovery and data mining methods can support fast-pace decision making in network operations. In this thesis, I analyse decision making on different levels of network operations. I identify the requirements decision-making sets for knowledge discovery and data mining tools and methods, and I study resources that are available to them. I then propose two methods for augmenting and applying frequent sets to support everyday decision making. The proposed methods are Comprehensive Log Compression for log data summarisation and Queryable Log Compression for semantic compression of log data. Finally I suggest a model for a continuous knowledge discovery process and outline how it can be implemented and integrated to the existing network operations infrastructure.

The Most Probable Bayesian Network and Beyond

This doctoral dissertation introduces an algorithm for constructing the most probable Bayesian network from data for small domains. The algorithm is used to show that a popular goodness criterion for the Bayesian networks has a severe sensitivity problem. The dissertation then proposes an information theoretic criterion that avoids the problem.