Functional alkali tantalate 2D structures for microelectronics and related applications

Alkali tantalates and niobates, including K(Ta / Nb)O3, Li(Ta / Nb)O3 and Na(Ta / Nb)O3, are a very promising ferroic family of lead-free compounds with perovskite-like structures. Their versatile properties make them potentially interesting for current and future application in microelectronics, photocatalysis, energy and biomedics. Among them potassium tantalate, KTaO3 (KTO), has been raising interest as an alternative for the well-known strontium titanate, SrTiO3 (STO). KTO is a perovskite oxide with a quantum paraelectric behaviour when electrically stimulated and a highly polarizable lattice, giving opportunity to tailor its properties via external or internal stimuli. However problems related with the fabrication of either bulk or 2D nanostructures makes KTO not yet a viable alternative to STO. Within this context and to contribute scientifically to the leverage tantalate based compounds applications, the main goals of this thesis are: i) to produce and characterise thin films of alkali tantalates by chemical solution deposition on rigid Si based substrates, at reduced temperatures to be compatible with Si technology, ii) to fulfil scientific knowledge gaps in these relevant functional materials related to their energetics and ii) to exploit alternative applications for alkali tantalates, as photocatalysis. In what concerns the synthesis attention was given to the understanding of the phase formation in potassium tantalate synthesized via distinct routes, to control the crystallization of desired perovskite structure and to avoid low temperature pyrochlore or K-deficient phases. The phase formation process in alkali tantalates is far from being deeply analysed, as in the case of Pb-containing perovskites, therefore the work was initially focused on the process-phase relationship to identify the driving forces responsible to regulate the synthesis. Comparison of phase formation paths in conventional solid-state reaction and sol-gel method was conducted. The structural analyses revealed that intermediate pyrochlore K2Ta2O6 structure is not formed at any stage of the reaction using conventional solid-state reaction. On the other hand in the solution based processes, as alkoxide-based route, the crystallization of the perovskite occurs through the intermediate pyrochlore phase; at low temperatures pyrochlore is dominant and it is transformed to perovskite at >800 °C. The kinetic analysis carried out by using Johnson-MehlAvrami-Kolmogorow model and quantitative X-ray diffraction (XRD) demonstrated that in sol-gel derived powders the crystallization occurs in two stages: i) at early stage of the reaction dominated by primary nucleation, the mechanism is phase-boundary controlled, and ii) at the second stage the low value of Avrami exponent, n ~ 0.3, does not follow any reported category, thus not permitting an easy identification of the mechanism. Then, in collaboration with Prof. Alexandra Navrotsky group from the University of California at Davis (USA), thermodynamic studies were conducted, using high temperature oxide melt solution calorimetry. The enthalpies of formation of three structures: pyrochlore, perovskite and tetragonal tungsten bronze K6Ta10.8O30 (TTB) were calculated. The enthalpies of formation from corresponding oxides, ∆Hfox, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -203.63 ± 2.84 kJ/mol, - 358.02 ± 3.74 kJ/mol, and -1252.34 ± 10.10 kJ/mol, respectively, whereas from elements, ∆Hfel, for KTaO3, KTa2.2O6 and K6Ta10.8O30 are -1408.96 ± 3.73 kJ/mol, -2790.82 ± 6.06 kJ/mol, and -13393.04 ± 31.15 kJ/mol, respectively. The possible decomposition reactions of K-deficient KTa2.2O6 pyrochlore to KTaO3 perovskite and Ta2O5 (reaction 1) or to TTB K6Ta10.8O30 and Ta2O5 (reaction 2) were proposed, and the enthalpies were calculated to be 308.79 ± 4.41 kJ/mol and 895.79 ± 8.64 kJ/mol for reaction 1 and reaction 2, respectively. The reactions are strongly endothermic, indicating that these decompositions are energetically unfavourable, since it is unlikely that any entropy term could override such a large positive enthalpy. The energetic studies prove that pyrochlore is energetically more stable phase than perovskite at low temperature. Thus, the local order of the amorphous precipitates drives the crystallization into the most favourable structure that is the pyrochlore one with similar local organization; the distance between nearest neighbours in the amorphous or short-range ordered phase is very close to that in pyrochlore. Taking into account the stoichiometric deviation in KTO system, the selection of the most appropriate fabrication / deposition technique in thin films technology is a key issue, especially concerning complex ferroelectric oxides. Chemical solution deposition has been widely reported as a processing method to growth KTO thin films, but classical alkoxide route allows to crystallize perovskite phase at temperatures >800 °C, while the temperature endurance of platinized Si wafers is ~700 °C. Therefore, alternative diol-based routes, with distinct potassium carboxylate precursors, was developed aiming to stabilize the precursor solution, to avoid using toxic solvents and to decrease the crystallization temperature of the perovskite phase. Studies on powders revealed that in the case of KTOac (solution based on potassium acetate), a mixture of perovskite and pyrochlore phases is detected at temperature as low as 450 °C, and gradual transformation into monophasic perovskite structure occurs as temperature increases up to 750 °C, however the desired monophasic KTaO3 perovskite phase is not achieved. In the case of KTOacac (solution with potassium acetylacetonate), a broad peak is detected at temperatures <650 °C, characteristic of amorphous structures, while at higher temperatures diffraction lines from pyrochlore and perovskite phases are visible and a monophasic perovskite KTaO3 is formed at >700 °C. Infrared analysis indicated that the differences are due to a strong deformation of the carbonate-based structures upon heating. A series of thin films of alkali tantalates were spin-coated onto Si-based substrates using diol-based routes. Interestingly, monophasic perovskite KTaO3 films deposited using KTOacac solution were obtained at temperature as low as 650 °C; films were annealed in rapid thermal furnace in oxygen atmosphere for 5 min with heating rate 30 °C/sec. Other compositions of the tantalum based system as LiTaO3 (LTO) and NaTaO3 (NTO), were successfully derived as well, onto Si substrates at 650 °C as well. The ferroelectric character of LTO at room temperature was proved. Some of dielectric properties of KTO could not be measured in parallel capacitor configuration due to either substrate-film or filmelectrode interfaces. Thus, further studies have to be conducted to overcome this issue. Application-oriented studies have also been conducted; two case studies: i) photocatalytic activity of alkali tantalates and niobates for decomposition of pollutant, and ii) bioactivity of alkali tantalate ferroelectric films as functional coatings for bone regeneration. Much attention has been recently paid to develop new type of photocatalytic materials, and tantalum and niobium oxide based compositions have demonstrated to be active photocatalysts for water splitting due to high potential of the conduction bands. Thus, various powders of alkali tantalates and niobates families were tested as catalysts for methylene blue degradation. Results showed promising activities for some of the tested compounds, and KNbO3 is the most active among them, reaching over 50 % degradation of the dye after 7 h under UVA exposure. However further modifications of powders can improve the performance. In the context of bone regeneration, it is important to have platforms that with appropriate stimuli can support the attachment and direct the growth, proliferation and differentiation of the cells. In lieu of this here we exploited an alternative strategy for bone implants or repairs, based on charged mediating signals for bone regeneration. This strategy includes coating metallic 316L-type stainless steel (316L-SST) substrates with charged, functionalized via electrical charging or UV-light irradiation, ferroelectric LiTaO3 layers. It was demonstrated that the formation of surface calcium phosphates and protein adsorption is considerably enhanced for 316L-SST functionalized ferroelectric coatings. Our approach can be viewed as a set of guidelines for the development of platforms electrically functionalized that can stimulate tissue regeneration promoting direct integration of the implant in the host tissue by bone ingrowth and, hence contributing ultimately to reduce implant failure.

Development of a real time Image analysis system for traffic monitoring applications.

Image processing offers unparalleled potential for traffic monitoring and control. For many years engineers have attempted to perfect the art of automatic data abstraction from sequences of video images. This paper outlines a research project undertaken at Napier University by the authors in the field of image processing for automatic traffic analysis. A software based system implementing TRIP algorithms to count cars and measure vehicle speed has been developed by members of the Transport Engineering Research Unit (TERU) at the University. The TRIP algorithm has been ported and evaluated on an IBM PC platform with a view to hardware implementation of the pre-processing routines required for vehicle detection. Results show that a software based traffic counting system is realisable for single window processing. Due to the high volume of data required to be processed for full frames or multiple lanes, system operations in real time are limited. Therefore specific hardware is required to be designed. The paper outlines a hardware design for implementation of inter-frame and background differencing, background updating and shadow removal techniques. Preliminary results showing the processing time and counting accuracy for the routines implemented in software are presented and a real time hardware pre-processing architecture is described.

Structured cases in case-based reasoning: re-using and adapting cases for time-tabling problems

In this paper, we present a case-based reasoning (CBR) approach solving educational time-tabling problems. Following the basic idea behind CBR, the solutions of previously solved problems are employed to aid finding the solutions for new problems. A list of feature-value pairs is insufficient to represent all the necessary information. We show that attribute graphs can represent more information and thus can help to retrieve re-usable cases that have similar structures to the new problems. The case base is organised as a decision tree to store the attribute graphs of solved problems hierarchically. An example is given to illustrate the retrieval, re-use and adaptation of structured cases. The results from our experiments show the effectiveness of the retrieval and adaptation in the proposed method.

Case-Based Reasoning as a Heuristic Selector in a Hyper-Heuristic for Course Timetabling Problems

This paper studies Knowledge Discovery (KD) using Tabu Search and Hill Climbing within Case-Based Reasoning (CBR) as a hyper-heuristic method for course timetabling problems. The aim of the hyper-heuristic is to choose the best heuristic(s) for given timetabling problems according to the knowledge stored in the case base. KD in CBR is a 2-stage iterative process on both case representation and the case base. Experimental results are analysed and related research issues for future work are discussed.

Soft computing based parameter identification in pavements and geomechanical systems

Accurate estimation of road pavement geometry and layer material properties through the use of proper nondestructive testing and sensor technologies is essential for evaluating pavement’s structural condition and determining options for maintenance and rehabilitation. For these purposes, pavement deflection basins produced by the nondestructive Falling Weight Deflectometer (FWD) test data are commonly used. The nondestructive FWD test drops weights on the pavement to simulate traffic loads and measures the created pavement deflection basins. Backcalculation of pavement geometry and layer properties using FWD deflections is a difficult inverse problem, and the solution with conventional mathematical methods is often challenging due to the ill-posed nature of the problem. In this dissertation, a hybrid algorithm was developed to seek robust and fast solutions to this inverse problem. The algorithm is based on soft computing techniques, mainly Artificial Neural Networks (ANNs) and Genetic Algorithms (GAs) as well as the use of numerical analysis techniques to properly simulate the geomechanical system. A widely used pavement layered analysis program ILLI-PAVE was employed in the analyses of flexible pavements of various pavement types; including full-depth asphalt and conventional flexible pavements, were built on either lime stabilized soils or untreated subgrade. Nonlinear properties of the subgrade soil and the base course aggregate as transportation geomaterials were also considered. A computer program, Soft Computing Based System Identifier or SOFTSYS, was developed. In SOFTSYS, ANNs were used as surrogate models to provide faster solutions of the nonlinear finite element program ILLI-PAVE. The deflections obtained from FWD tests in the field were matched with the predictions obtained from the numerical simulations to develop SOFTSYS models. The solution to the inverse problem for multi-layered pavements is computationally hard to achieve and is often not feasible due to field variability and quality of the collected data. The primary difficulty in the analysis arises from the substantial increase in the degree of non-uniqueness of the mapping from the pavement layer parameters to the FWD deflections. The insensitivity of some layer properties lowered SOFTSYS model performances. Still, SOFTSYS models were shown to work effectively with the synthetic data obtained from ILLI-PAVE finite element solutions. In general, SOFTSYS solutions very closely matched the ILLI-PAVE mechanistic pavement analysis results. For SOFTSYS validation, field collected FWD data were successfully used to predict pavement layer thicknesses and layer moduli of in-service flexible pavements. Some of the very promising SOFTSYS results indicated average absolute errors on the order of 2%, 7%, and 4% for the Hot Mix Asphalt (HMA) thickness estimation of full-depth asphalt pavements, full-depth pavements on lime stabilized soils and conventional flexible pavements, respectively. The field validations of SOFTSYS data also produced meaningful results. The thickness data obtained from Ground Penetrating Radar testing matched reasonably well with predictions from SOFTSYS models. The differences observed in the HMA and lime stabilized soil layer thicknesses observed were attributed to deflection data variability from FWD tests. The backcalculated asphalt concrete layer thickness results matched better in the case of full-depth asphalt flexible pavements built on lime stabilized soils compared to conventional flexible pavements. Overall, SOFTSYS was capable of producing reliable thickness estimates despite the variability of field constructed asphalt layer thicknesses.

Evidence and implications of multiple paradigms in accounting knowledge production

This paper uses evidence gathered in two perception studies of Australasian and British accounting academics to reflect on aspects of the knowledge production system within accounting academe. We provide evidence of the representation of multiple paradigms in many journals that are scored by participants as being of high quality. Indeed most of the journals we surveyed are perceived by accounting academics as incorporating research from more than one paradigm. It is argued that this ‘catholic’ approach by journal editors and the willingness of many respondents in our surveys to score journals highly on material they publish from both paradigm categories reflects a balanced acceptance of the multi-paradigmatic state of accounting research. Our analysis is set within an understanding of systems of accounting knowledge production as socially constructed and as playing an important role in the distribution of power and reward in the academy. We explore the impact of our results on concerns emerging from the work of a number of authors who carefully expose localised ‘elites’. The possibilities for a closer relationship between research emerging from a multi-paradigm discipline and policy setting and practice are also discussed. The analysis provides a sense of optimism that the broad constituency of accounting academics operates within an environment conducive for the exchange of ideas. That optimism is dampened by concerns about the impact of local ‘elites’ and the need for more research on their impact on accounting academe.

Modeling relevant legal information for consumer disputes

Accessing relevant legal information found in text excerpts from heterogeneous sources is essential to the decision making process in consumer disputes. The Ontology of Relevant Legal Information in Consumer Disputes (ric) is the domain-independent ontology modeling this relevant legal information comprising rights, their requisites, exceptions, constraints, enforcement procedures, legal sources. Its use is exemplified with one extension thereof, the Air Transport Passenger Incidents Ontology (ric-atpi), representing both the possible incidents triggered by a complaint in the air transport passenger domain and the related legal information that might be applicable. The Ontology models the key provisions found in the hard law, and those in soft law, comprising heterogeneous sources in a structured manner. An ontology-based system provides the knowledge embedded in the legal sources and their relation to the specific scenario.

Autonomous formation flying: unified control and collision avoidance methods for close manoeuvring spacecraft

The idea of spacecraft formations, flying in tight configurations with maximum baselines of a few hundred meters in low-Earth orbits, has generated widespread interest over the last several years. Nevertheless, controlling the movement of spacecraft in formation poses difficulties, such as in-orbit high-computing demand and collision avoidance capabilities, which escalate as the number of units in the formation is increased and complicated nonlinear effects are imposed to the dynamics, together with uncertainty which may arise from the lack of knowledge of system parameters. These requirements have led to the need of reliable linear and nonlinear controllers in terms of relative and absolute dynamics. The objective of this thesis is, therefore, to introduce new control methods to allow spacecraft in formation, with circular/elliptical reference orbits, to efficiently execute safe autonomous manoeuvres. These controllers distinguish from the bulk of literature in that they merge guidance laws never applied before to spacecraft formation flying and collision avoidance capacities into a single control strategy. For this purpose, three control schemes are presented: linear optimal regulation, linear optimal estimation and adaptive nonlinear control. In general terms, the proposed control approaches command the dynamical performance of one or several followers with respect to a leader to asymptotically track a time-varying nominal trajectory (TVNT), while the threat of collision between the followers is reduced by repelling accelerations obtained from the collision avoidance scheme during the periods of closest proximity. Linear optimal regulation is achieved through a Riccati-based tracking controller. Within this control strategy, the controller provides guidance and tracking toward a desired TVNT, optimizing fuel consumption by Riccati procedure using a non-infinite cost function defined in terms of the desired TVNT, while repelling accelerations generated from the CAS will ensure evasive actions between the elements of the formation. The relative dynamics model, suitable for circular and eccentric low-Earth reference orbits, is based on the Tschauner and Hempel equations, and includes a control input and a nonlinear term corresponding to the CAS repelling accelerations. Linear optimal estimation is built on the forward-in-time separation principle. This controller encompasses two stages: regulation and estimation. The first stage requires the design of a full state feedback controller using the state vector reconstructed by means of the estimator. The second stage requires the design of an additional dynamical system, the estimator, to obtain the states which cannot be measured in order to approximately reconstruct the full state vector. Then, the separation principle states that an observer built for a known input can also be used to estimate the state of the system and to generate the control input. This allows the design of the observer and the feedback independently, by exploiting the advantages of linear quadratic regulator theory, in order to estimate the states of a dynamical system with model and sensor uncertainty. The relative dynamics is described with the linear system used in the previous controller, with a control input and nonlinearities entering via the repelling accelerations from the CAS during collision avoidance events. Moreover, sensor uncertainty is added to the control process by considering carrier-phase differential GPS (CDGPS) velocity measurement error. An adaptive control law capable of delivering superior closed-loop performance when compared to the certainty-equivalence (CE) adaptive controllers is finally presented. A novel noncertainty-equivalence controller based on the Immersion and Invariance paradigm for close-manoeuvring spacecraft formation flying in both circular and elliptical low-Earth reference orbits is introduced. The proposed control scheme achieves stabilization by immersing the plant dynamics into a target dynamical system (or manifold) that captures the desired dynamical behaviour. They key feature of this methodology is the addition of a new term to the classical certainty-equivalence control approach that, in conjunction with the parameter update law, is designed to achieve adaptive stabilization. This parameter has the ultimate task of shaping the manifold into which the adaptive system is immersed. The performance of the controller is proven stable via a Lyapunov-based analysis and Barbalat’s lemma. In order to evaluate the design of the controllers, test cases based on the physical and orbital features of the Prototype Research Instruments and Space Mission Technology Advancement (PRISMA) are implemented, extending the number of elements in the formation into scenarios with reconfigurations and on-orbit position switching in elliptical low-Earth reference orbits. An extensive analysis and comparison of the performance of the controllers in terms of total Δv and fuel consumption, with and without the effects of the CAS, is presented. These results show that the three proposed controllers allow the followers to asymptotically track the desired nominal trajectory and, additionally, those simulations including CAS show an effective decrease of collision risk during the performance of the manoeuvre.

Towards ubiquitous city : concept, planning, and experiences in the Republic of Korea

Information and communication technologies (ICTs) had occupied their position on knowledge management and are now evolving towards the era of self-intelligence (Klosterman, 2001). In the 21st century ICTs for urban development and planning are imperative to improve the quality of life and place. This includes the management of traffic, waste, electricity, sewerage and water quality, monitoring fire and crime, conserving renewable resources, and coordinating urban policies and programs for urban planners, civil engineers, and government officers and administrators. The handling of tasks in the field of urban management often requires complex, interdisciplinary knowledge as well as profound technical information. Most of the information has been compiled during the last few years in the form of manuals, reports, databases, and programs. However frequently, the existence of these information and services are either not known or they are not readily available to the people who need them. To provide urban administrators and the public with comprehensive information and services, various ICTs are being developed. In early 1990s Mark Weiser (1993) proposed Ubiquitous Computing project at the Xerox Palo Alto Research Centre in the US. He provides a vision of a built environment which digital networks link individual residents not only to other people but also to goods and services whenever and wherever they need (Mitchell, 1999). Since then the Republic of Korea (ROK) has been continuously developed national strategies for knowledge based urban development (KBUD) through the agenda of Cyber Korea, E-Korea and U-Korea. Among abovementioned agendas particularly the U-Korea agenda aims the convergence of ICTs and urban space for a prosperous urban and economic development. U-Korea strategies create a series of U-cities based on ubiquitous computing and ICTs by a means of providing ubiquitous city (U-city) infrastructure and services in urban space. The goals of U-city development is not only boosting the national economy but also creating value in knowledge based communities. It provides opportunity for both the central and local governments collaborate to U-city project, optimize information utilization, and minimize regional disparities. This chapter introduces the Korean-led U-city concept, planning, design schemes and management policies and discusses the implications of U-city concept in planning for KBUD.

Management: Core concepts and applications

Building on the strengths of its popular previous edition Management: Core Concepts and Applications, 2nd Australasian edition has been thoroughly revised and updated to reflect the three keyaspects of contemporary undergraduate introductory management education: Management theory Concept application Skills development. The text's 16 chapters are presented in a lively and concise mannerideal for the typical 12 or 13 teaching weeks of a semester. Itsflexible framework allows instructors to teach students through the useof interactive tools such as case studies, exercises and projects.These action-oriented learning activities complement the text's solidfoundation of knowledge-based theory material. There is a balanced coverage of both small to medium sizedenterprises and larger multinational organisations operating inAustralia, New Zealand and the Asia-Pacific region. A critical thinkingperspective is integrated throughout the book, asking and encouragingstudents to analyse the theory in light of real-world examples. Each copy of the printed textbook comes with a free copy of the Wiley Desktop Edition:a full electronic version of the text that allows students to easilysearch for key concepts, create their own colour-coded highlights andmake electronic notes in the text for revision. Key themes of the text include: The importance of ethical and socially responsible management Recognition of the continuing need to cater for the increasing diversity of the workforce The importance of managing people, technology, knowledge and quality in achieving organisational goals An appreciation of the challenges and opportunities presented bythe ever changing environment in which contemporary managers operate.

Mapping personal trip OD from probe data

The paper analyses the expected value of OD volumes from probe with fixed error, error that is proportional to zone size and inversely proportional to zone size. To add realism to the analysis, real trip ODs in the Tokyo Metropolitan Region are synthesised. The results show that for small zone coding with average radius of 1.1km, and fixed measurement error of 100m, an accuracy of 70% can be expected. The equivalent accuracy for medium zone coding with average radius of 5km would translate into a fixed error of approximately 300m. As expected small zone coding is more sensitive than medium zone coding as the chances of the probe error envelope falling into adjacent zones are higher. For the same error radii, error proportional to zone size would deliver higher level of accuracy. As over half (54.8%) of the trip ends start or end at zone with equivalent radius of ≤ 1.2 km and only 13% of trips ends occurred at zones with equivalent radius ≥2.5km, measurement error that is proportional to zone size such as mobile phone would deliver higher level of accuracy. The synthesis of real OD with different probe error characteristics have shown that expected value of >85% is difficult to achieve for small zone coding with average radius of 1.1km. For most transport applications, OD matrix at medium zone coding is sufficient for transport management. From this study it can be drawn that GPS with error range between 2 and 5m, and at medium zone coding (average radius of 5km) would provide OD estimates greater than 90% of the expected value. However, for a typical mobile phone operating error range at medium zone coding the expected value would be lower than 85%. This paper assumes transmission of one origin and one destination positions from the probe. However, if multiple positions within the origin and destination zones are transmitted, map matching to transport network could be performed and it would greatly improve the accuracy of the probe data.