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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
81

Dispositifs innovants à pente sous le seuil abrupte : du TEFT au Z²-FET

Wan, Jing 23 July 2012 (has links) (PDF)
Tunnel à effet de champ (TFET) et un nouveau composant MOS à rétroaction que nous avons nommé le Z2-FET.Le Z2-FET est envisagé pour la logique faible consommation et pour les applications mémoire compatibles avecles technologies CMOS avancées. Nous avons étudié de manière systématique des TFETs avec différents oxydesde grille, matériaux et structures de canal, fabriqués sur silicium sur isolant totalement déserté (FDSOI). Lesmesures de bruit à basse fréquence (LFN) sur TFETs montrent la prédominance d'un signal aléatoiretélégraphique (RTS), qui révèle sans ambiguïté le mécanisme d'effet tunnel. Un modèle analytique combinantl'effet tunnel et le transport dans le canal a été développé, montrant un bon accord entre les résultatsexpérimentaux et les simulations.Nous avons conçu et démontré un nouveau dispositif (Z2-FET, pour pente sous le seuil verticale et zéroionisation par impact), qui présente une commutation extrêmement abrupte (moins de 1 mV par décade decourant), avec un rapport ION / IOFF >109, un large effet de hystérésis et un potentiel de miniaturisation jusqu'à 20nm. La simulation TCAD a été utilisée pour confirmer que la commutation électrique du Z2-FET fonctionne parl'intermédiaire de rétroaction entre les flux des électrons et trous et leurs barrières d'injection respectives. LeZ2-FET est idéalement adapté pour des applications mémoire à un transistor. La mémoire DRAM basée sur leZ2-FET montre des performances très bonnes, avec des tensions d'alimentation jusqu'à 1,1 V, des temps derétention jusqu'à 5,5 s et des vitesses d'accès atteignant 1 ns. Une mémoire SRAM utilisant un seul Z²-FET estégalement démontrée sans nécessité de rafraichissement de l'information stockée.Notre travail sur le courant GIDL intervenant dans les MOSFETs de type FDSOI a été combiné avec leTFET afin de proposer une nouvelle structure de TFETs optimisés, basée sur l'amplification bipolaire du couranttunnel. Les simulations de nouveau dispostif à injection tunnel amélioré par effet bipolaire (BET-FET) montrentdes résultats prometteurs, avec des ION supérierus à 4mA/��m et des pentes sous le seuil SS inférieures à 60mV/dec sur plus de sept décades de courant, surpassant tous les TFETs silicium rapportés à ce jour.La thèse se conclut par les directions de recherche futures dans le domaine des dispositifs à pente sous leseuil abrupte.
82

Réalisation et étude des propriétés électriques d'un transistor à effet tunnel 'T-FET' à nanofil Si/SiGe / Design and electrical properties's study of the tunnel field effect transistor ('T-FET' ) based on Si/SiGe nanowires

Brouzet, Virginie 16 December 2015 (has links)
La demande d’objets connectés dans notre société est très importante, au vu du marché florissant des smartphones. Ces nouveaux objets technologiques ont pour avantage de regrouper plusieurs fonctions en un seul objet ultra compact. Cette diversité est possible grâce à l’avènement des systèmes-sur-puce (SoC, System-on-Chip) et à la miniaturisation extrême des composants. Les SoC s’intègrent dans l’approche « More than Moore » et demande une superficie importante des puces. Celle-ci peut-être réduite par l’utilisation d’une autre approche appelée « More Moore » qui fut largement utilisée ces dernières années pour miniaturiser la taille des transistors. Cependant cette approche tend vers ses limites physiques puisque la réduction drastique de la taille des MOSFETs (« Metal Oxide Semicondutor Field Effect Transistor ») ne pourra pas être poursuivie à long terme. En outre, les transistors de taille réduite présentent des effets parasites, liés aux effets de canaux courts et à une mauvaise dissipation de la chaleur dégagée lors du fonctionnement des MOSFETs miniaturisés. Les effets de canaux courts peuvent-être minimisés grâce à de nouvelles architectures, telles que l’utilisation de nanofils, qui permettent d’obtenir une grille totalement enrobante du canal. Mais le problème de la puissance de consommation reste un frein pour le passage au prochain nœud technologique et pour l’augmentation des fonctions dans les appareils nomades. En effet, la puissance de consommation des MOSFETs ne fait qu’augmenter à chaque nouvelle génération, ce qui est en partie dû à l’accroissement des pertes énergétiques induites par la puissance statique de ces transistors. Pour diminuer celle-ci, la communauté scientifique a proposée plusieurs solutions, dont une des plus prometteuses est le transistor à effet tunnel (TFET). Car ce dispositif est peu sensible aux effets de canaux courts, et il peut fonctionner à de faibles tensions de drain et avoir un inverse de pente sous le seuil inférieur à 60mV/dec. L’objectif de la thèse est donc de fabriquer et de caractériser des transistors à effet tunnel à base de nanofil unique en silicium et silicium germanium. Nous présenterons la croissance et l’intégration des nanofils p-i-n en TFET. Puis nous avons étudié l’influence de certains paramètres sur les performances de ces transistors, et en particulier, l’effet du niveau de dopage de la source et du contrôle électrostatique de la grille sera discuté. Ensuite, l’augmentation des performances des TFETs sera montrée grâce à l’utilisation de semiconducteur à petit gap. En effet, nous insérons du germanium dans la matrice de silicium pour en diminuer le gap et garder un matériau compatible avec les techniques de fabrication de l’industrie de la microélectronique. Un modèle de simulation du courant tunnel bande à bande a été réalisé, se basant sur le modèle de Klaassen. Les mesures électriques des dispositifs seront comparées aux résultats obtenus par la simulation, afin d’extraire le paramètre B de la transition tunnel pour chacun des matériaux utilisés. Enfin nous présenterons les améliorations possibles des performances par une intégration verticale des nanofils. / The connected objects demand in our society is very important , given the successfull smartphone market. These newtechnological objects have the advantage to combine several functions in one ultra compact object. This diversity is possibledue to the advent of system-on-chip (SoC) and the components scaling down. The SoCs are into the More than Mooreapproach and require a large chips area, which can be reduced by the use of "More Moore" approach which was widelyused in recent years to scale down the transistors. However, this approach tends to physical limitations since the drasticscaling down of the MOSFETs ("Metal Oxide Field Efect Transistor Semicondutor") can not be continued in the future. Inaddition, the nanoŰMOSFET have parasitic efects, related to short-channel efects and a low heating dissipation. Theshort channel efects can be minimized thanks to new architectures, such as the use of nanowires, which enable a gate allaround of the channel. But the power consumption problem still drag on the transition to the next technology node and theaddition of new functions in mobile devices. Indeed, the MOSFETŠs consumed power increases with each new generation,which is mainly due to the static power increase of these transistors. To reduce it, the scientiĄc community has proposedseveral solutions, and one of the most promising is a tunnel efect transistor (TFET). Because this device exhibit lessshort-channel efects compared to the conventional MOSFET, it can operate at low drain voltages and their subthresholdslope could be lower than 60 mV/dec. The thesis aims are to fabricate and characterize tunneling transistors based onsingle silicon nanowire and silicon germanium. We will present the growth and integration of pŰiŰn nanowires TFET. Thenwe investigated the inĆuence of some parameters on the electrical performance of these transistors, in particular, the efectof the source doping level and the electrostatic gate control will be discussed. In the next part, the increase of TFETsperformance will be shown thanks to the small band-gap semiconductor use. Indeed, we insert germanium in the silicon dieto reduce the bandgap and keep a material compatible with the CMOS manufacturing. A band to band tunneling modelwas used to calculate the device current, based on the model Klaassen. Electrical measurements will be compared to thesimulated results, in order to extract the B parameter of tunnel transition for each materials used. Finally we will presentthe possible performance improvements thanks to the vertical nanowires integration.
83

Integrated nanoscaled detectors of biochemical species

Schütt, Julian 02 October 2020 (has links)
Rapid and reliable diagnostics of a disease represents one of the main focuses of today’s academic and industrial research in the development of new sensor prototypes and improvement of existing technologies. With respect to demographic changes and inhomogeneous distribution of the clinical facilities worldwide, especially in rural regions, a new generation of miniaturized biosensors is highly demanded offering an easy deliverability, low costs and sample preparation and simple usage. This work focuses on the integration of nanosized electronic structures for high-specific sensing applications into adequate microfluidic structures for sample delivery and liquid manipulation. Based on the conjunction of these two technologies, two novel sensor platforms were prototyped, both allowing label-free and optics-less electrochemical detection ranging from molecular species to eukaryotic micron-sized human cells.:Table of Figures List of Tables Abbreviations List of Symbols 1 Introduction 1.1 Motivation 1.2 State of the art 1.3 Scope of this thesis 2 Fundamentals 2.1 Sensors at the nanoscale 2.2 Transistors technology 2.2.1 p-n junction 2.2.3 The MOSFET 2.2.4 The ISFET and BioFET 2.3 Impedance measurements for biodetection 2.3.1 Electrical impedance spectroscopy 2.3.2 Electrical impedance cytometry 2.4 Microfluidics 2.4.1 Definition 2.4.2 Droplet-based microfluidics 2.5 Biomarkers for sensing applications 2.5.1 Peripheral blood mononuclear cells (PBMCs) 2.5.2 Physical parameters 3. Material and methods 3.1 General 3.1.1 Materials and chemicals 3.1.2 Surface cleaning 3.2 Lithography 3.2.1 Electron beam lithography 3.2.2 Laser lithography 3.2.3 UV lithography 3.2.4 Soft lithography 3.3 Thermal deposition of metals 3.4 APTES functionalization 3.4.1 Fluorescent labeling of APTES 3.5 Measurement devices 3.5.1 SiNW FET measurements 3.5.2 Electrical Impedance cytometry measurements 3.6 Bacteria and cell cultivation 3.6.1 PBMC purification and treatment 3.6.2 Bacteria cultivation 4. Compact nanosensors probe microdroplets 4.1 Overview 4.2 Fabrication 4.2.1 SiNW FET fabrication 4.2.2 SiNW FET modification for top-gate sensing 4.3 Electrical characterization 4.4 Flow-focusing droplet generation 4.4.1 Flow-focusing geometry 4.4.2 Flow-focusing droplet characterization 4.4.3 Microfluidic integration 4.5 Deionized water droplet sensing 4.6 Phosphate-buffered saline (PBS) droplet sensing 4.6.1 Influence of the droplet’s ionic concentration 4.6.2 Plateau formation in dependence of the droplet’s settling time 4.6.3 Droplet analysis by their ratio 4.6.4 Dependence on pH value 4.6.5 Long time pH sensing experiment 4.6.6 Dependence on ionic concentration 4.7 Tracking of reaction kinetics in droplets 4.7.1 Principle and setup of the glucose oxidase (GOx) enzymatic test 4.7.2 GOx enzymatic assay 4.8 Stable baseline by conductive carrier phase 5. Impedance-based flow cytometer on a chip 5.1 Overview 5.2 Overview of the fabrication of the sensor device 5.3 COMSOL simulation of sensing area 5.3.1 Prototyping of the sensing geometry 5.3.2 Optimization of the sensing geometry 5.3.3 Evaluation of the working potential 5.3.4. Scaling of the sensing area 5.4 Fabrication of the nanoelectronic sensing structure 5.4.1 Nanofabrication and analysis 5.4.2 Evaluation of the proximity effect 5.5 Microcontacting of nanostructured sensing structures 5.6 Electrical characterization of the sensing structure 5.6.1 Characterization in alternating current 5.6.2 Characterization in direct current (DC) 5.7 Scaling effect of nanostructures in static sensing conditions 5.8 Multi-analyte detection on the sensor 5.9 Microfluidic focusing system 5.9.1 1D focusing using FITC-probed deionized water 5.9.2 2D Focusing using fluorescent microparticles 5.10 Microfluidic integration of the two technologies 5.11 Dynamic SiO2 particle detection 5.11.1 Single particle detection 5.11.2 Scatter plot representation 5.11.3 Effect of the sensing area in dynamic particle detection 5.11.4 Dynamic detection of SiO2 particles with different diameters 5.12 Detection of peripheral blood mononuclear cells (PBMCs) 5.12.1 Overview 5.12.2 PBMC classification detected by impedance cytometry 5.12.3 PBMC Long-time detection 5.13 Detection of acute myeloid leukemia by impedance cytometry 5.13.1 Manual analysis of the output response 5.13.2 Learning algorithm for automatic cell classification 5.14 Exploring the detection limit of the device 6. Summary and outlook Scientific output References Acknowledgements / Rasche und zuverlässige biologische Krankheitsdiagnostik repräsentiert eines der Hauptfokusse heutiger akademischer und industrieller Forschung in der Entwicklung neuer Sensor-Prototypen und Verbesserung existierender Technologien. In bezug auf weltweite demographische Änderungen und hohe Distanzen zu Kliniken, besonders in ländlichen Gegenden, werden zusätzliche Anfordungen an neue miniaturisierte Biosensor-Generationen gestellt, wie zum Beispiel ihre Transportfähigkeit, geringe Kosten und Probenpräparation, sowie einfache Handhabung. Diese Dissertation beschäftigt sich mit der Integration nanoskalierter Strukturen zur Detektion chemischer und biologischer Spezies und mikrofluidischen Kanälen zu deren Transport und zur Manipulation der Ströme. Basierend auf der Verbindung dieser beiden Technologien wurden zwei Sensor-Plattformen entwickelt, die eine markierungsfreie und nicht-optische elektrische Detektion von Molekülen bis zu eukaryotischen menschlichen Zellen erlauben.:Table of Figures List of Tables Abbreviations List of Symbols 1 Introduction 1.1 Motivation 1.2 State of the art 1.3 Scope of this thesis 2 Fundamentals 2.1 Sensors at the nanoscale 2.2 Transistors technology 2.2.1 p-n junction 2.2.3 The MOSFET 2.2.4 The ISFET and BioFET 2.3 Impedance measurements for biodetection 2.3.1 Electrical impedance spectroscopy 2.3.2 Electrical impedance cytometry 2.4 Microfluidics 2.4.1 Definition 2.4.2 Droplet-based microfluidics 2.5 Biomarkers for sensing applications 2.5.1 Peripheral blood mononuclear cells (PBMCs) 2.5.2 Physical parameters 3. Material and methods 3.1 General 3.1.1 Materials and chemicals 3.1.2 Surface cleaning 3.2 Lithography 3.2.1 Electron beam lithography 3.2.2 Laser lithography 3.2.3 UV lithography 3.2.4 Soft lithography 3.3 Thermal deposition of metals 3.4 APTES functionalization 3.4.1 Fluorescent labeling of APTES 3.5 Measurement devices 3.5.1 SiNW FET measurements 3.5.2 Electrical Impedance cytometry measurements 3.6 Bacteria and cell cultivation 3.6.1 PBMC purification and treatment 3.6.2 Bacteria cultivation 4. Compact nanosensors probe microdroplets 4.1 Overview 4.2 Fabrication 4.2.1 SiNW FET fabrication 4.2.2 SiNW FET modification for top-gate sensing 4.3 Electrical characterization 4.4 Flow-focusing droplet generation 4.4.1 Flow-focusing geometry 4.4.2 Flow-focusing droplet characterization 4.4.3 Microfluidic integration 4.5 Deionized water droplet sensing 4.6 Phosphate-buffered saline (PBS) droplet sensing 4.6.1 Influence of the droplet’s ionic concentration 4.6.2 Plateau formation in dependence of the droplet’s settling time 4.6.3 Droplet analysis by their ratio 4.6.4 Dependence on pH value 4.6.5 Long time pH sensing experiment 4.6.6 Dependence on ionic concentration 4.7 Tracking of reaction kinetics in droplets 4.7.1 Principle and setup of the glucose oxidase (GOx) enzymatic test 4.7.2 GOx enzymatic assay 4.8 Stable baseline by conductive carrier phase 5. Impedance-based flow cytometer on a chip 5.1 Overview 5.2 Overview of the fabrication of the sensor device 5.3 COMSOL simulation of sensing area 5.3.1 Prototyping of the sensing geometry 5.3.2 Optimization of the sensing geometry 5.3.3 Evaluation of the working potential 5.3.4. Scaling of the sensing area 5.4 Fabrication of the nanoelectronic sensing structure 5.4.1 Nanofabrication and analysis 5.4.2 Evaluation of the proximity effect 5.5 Microcontacting of nanostructured sensing structures 5.6 Electrical characterization of the sensing structure 5.6.1 Characterization in alternating current 5.6.2 Characterization in direct current (DC) 5.7 Scaling effect of nanostructures in static sensing conditions 5.8 Multi-analyte detection on the sensor 5.9 Microfluidic focusing system 5.9.1 1D focusing using FITC-probed deionized water 5.9.2 2D Focusing using fluorescent microparticles 5.10 Microfluidic integration of the two technologies 5.11 Dynamic SiO2 particle detection 5.11.1 Single particle detection 5.11.2 Scatter plot representation 5.11.3 Effect of the sensing area in dynamic particle detection 5.11.4 Dynamic detection of SiO2 particles with different diameters 5.12 Detection of peripheral blood mononuclear cells (PBMCs) 5.12.1 Overview 5.12.2 PBMC classification detected by impedance cytometry 5.12.3 PBMC Long-time detection 5.13 Detection of acute myeloid leukemia by impedance cytometry 5.13.1 Manual analysis of the output response 5.13.2 Learning algorithm for automatic cell classification 5.14 Exploring the detection limit of the device 6. Summary and outlook Scientific output References Acknowledgements
84

Influence of Size and Interface Effects of Silicon Nanowire and Nanosheet for Ultra-Scaled Next Generation Transistors

Orthi Sikder (9167615) 28 July 2020 (has links)
<div>In this work, we investigate the trade-off between scalability and reliability for next generation logic-transistors i.e. Gate-All-Around (GAA)-FET, Multi-Bridge-Channel (MBC)-FET. First, we analyze the electronic properties (i.e. bandgap and</div><div>quantum conductance) of ultra-thin silicon (Si) channel i.e. nano-wire and nano-sheet based on first principle simulation. In addition, we study the influence of interface</div><div>states (or dangling bonds) at Si-SiO<sub>2</sub> interface. Second, we investigate the impact of bandgap change and interface states on GAA-FETs and MBC-FETs characteristics by</div><div>employing Non-equilibrium Green's Function based device simulation. In addition to that, we calculate the activation energy of Si-H bond dissociation at Si-SiO<sub>2</sub> interface for different Si nano-wire/sheet thickness and different oxide electric-field. Utilizing these thickness dependent activation energies for corresponding oxide electric-field, in conjunction with reaction-diffusion model, we compute the characteristics shift and analyze the negative bias temperature instability in GAA-FET and MBC-FET. Based on our analysis, we estimate the operational voltage of these transistors for a life-time of 10 years and the ON current of the device at iso-OFF-current condition. For example, for channel length of 5 nm and thickness < 5 nm the safe operating voltage needs to be < 0.55V. Furthermore, our analysis suggests that the benefit of Si thickness scaling can potentially be suppressed for obtaining a desired life-time of GAA-FET and MBC-FET.</div>
85

Elektrický pohon s omezením přechodných dějů / The electric drive with current peak limiting

Keller, Karel January 2009 (has links)
My thesis is focused on realization of three inrush current limitors samples. This limiters will be used in ABB´s metal-clad, air-insulated switchgears for medium voltage distribution. On the basis of the results there is chosen the sample with optimal properties suitable for practice in the conclusion.
86

Měnič pro malý 3f asynchronní motor / Frequency inverter for small induction machine

Pavlík, Ondřej January 2013 (has links)
The aim of this diploma thesis is to continue in prototype realization and a final proposition of three-phase frequency transformer pilot projected in scope of my bachelor work. This transformer is outlined for a small unsynchronized engine to 100 watt output and is designed to supply the fan motor. This suggestion was optimalized from the standpoint of bargain low price and technical feasibility. Powerful part of transformer is solved with help of circuit FSB50450 which is fed from compact source MYRRA 47155. Steering system is guaranteed with circuit MC3PHAC. This device is possible to use in less demanding applications where it was resisted by high expensive price of common frequency transformers.
87

Assessment of zebrafish embryo toxicity of environmentally relevant antibiotics

Mastrangeli, Ophelia January 2021 (has links)
Antibiotics are essential drugs in modern medicine. After consumption antibiotics are excreted in unmetabolized form in the urine and reach our sewage treatment plants (STP). STP are not able to degrade all antibiotics leading to release of antibiotics into the aquatic environment. Aquatic animals are thus continuously exposed to antibiotics. This study involved assessment of the toxicity of eight antibiotics previously detected in the river Fyrisån, Uppsala, Sweden, in developing zebrafish (Danio rerio) embryos up to day six of age. The experiments included assessment of embryonal toxicity for the individual antibiotics as well as mixtures of all antibiotics.  The mixtures were based on previously measured concentrations in river Fyrisån and tested in increasing concentrations up to 1000-times higher concentrations. In the toxicity assessment different lethal and sublethal endpoints were observed, such as early movements, heart rate, hatching time and length. These experiments were followed by behaviour study observing the swimming activity during alternating dark-light alternations. Lastly, a bioaccumulation study was performed on mixtures of antibiotics to determine if these antibiotics were bioaccumulative in zebrafish embryos. The results showed that these eight antibiotics, individually and as a mixture did not affect any of the endpoints. As for bioaccumulation, none of the eight antibiotics were bioaccumulating in zebrafish embryos. These antibiotics seem to be non-toxic during fish embryonal development. However, the results cannot determine the long-term effects of antibiotic exposure and thus further studies are needed to assess the potential toxicity of environmentally present antibiotics to fish.
88

The dynamics of coping with policy and practice : mathematics educators' experiences

Mosala, O.L., Junqueira, K.E. January 2013 (has links)
Published Aticle / This article reports on the experiences of Mathematics educators during the implementation of the National Curriculum Statement (NCS) in Grades 10 - 12. The study is contained in five different, but educationally related constructs addressing training, problem areas which challenge or appeal to Mathematics educators, lesson planning, assessment strategies and the effective integration of OBE in the teaching of Mathematics. A mixed methods design was used, with data being collected and collated using questionnaires and semi-structured interviews. The quantitative data employed descriptive data analysis, while the qualitative data was analysed by identifying differences and similarities. The study revealed that educators differed in terms of the problems they encountered with implementing the NCS in Mathematics. They agreed, however, that the implementation was successful and that it contributed to better teaching.
89

The role of critical thinking skills in promoting quality teaching and learning in the further education and training (FET) phase of secondary schools in South Africa / Merinda Felicia Cooper

Cooper, Merinda Felicia January 2010 (has links)
The quality of education in especially the Further Education and Training phase (FET) is recognised as one of the most significant challenges facing the South African government. Low teacher morale, lack of parental involvement, learners' ignorance in taking responsibility for their own learning and other educational problems are all identified as contributing factors. This study was undertaken to investigate how critical thinking skills can contribute to promoting quality teaching and learning in secondary schools with specific reference to the FET phase. The study also sought to make recommendations that will assist teachers to integrate critical thinking skills into the teaching and learning experiences in the FET phase. The nature of quality teaching and learning, the nature of critical thinking skills and the correlation between the concepts to improve the quality of education were researched by means of a literature study. A quantitative research design followed, using questionnaires as research instrument. From the research conducted it was found that learners in the FET phase do not take responsibility for their learning and therefore many of these learners still do not perceive learning as important. However, effective learning could take place if learners are confident, independent, active participants and explore a variety of learning strategies. Teachers, on the other hand, should adopt particular forms of behaviour to foster certain types of learning. The ability to teach critical thinking skills to learners poses a great challenge as many teachers are not trained to do so. This has a great influence on the exposure of an integrated constructivist method of teaching and learning and therefore inflicts on the delivery of quality teaching and learning in the FET phase of secondary schools in South Africa. / MEd, North-West University, Vaal Triangle Campus, 2011
90

Thin film studies of planar transition metal complexes

Whyte, Alex January 2013 (has links)
At present the field of molecular electronics - also known as molecular semiconductors, organic semiconductors, plastic electronics or organic electronics - is dominated by organic materials, both polymeric and molecular, with much less attention being focused on transition metal based complexes despite the advantages they can offer. Such advantages include tuneable frontier orbitals through the ligand/metal interaction and the ability to generate stable paramagnetic species. Devices containing radical materials are particularly interesting in order to examine the interplay between conduction and spin - an effect which is not yet properly understood but can give rise to exotic behaviour. A series of homoleptic, bis-ligand Ni(II) and Cu(II) complexes were prepared using three structurally related phenolic oxime ligands, 2-hydroxy-5-t-octylacetophenone oxime (t-OctsaoH), 2-hydroxy-5-n-propylacetophenone oxime (n-PrsaoH) and 2- hydroxyacetophenone oxime (HsaoH). The complexes were characterised by single-crystal X-ray diffraction, cyclic voltammetry, UV/Vis spectroscopy, field-effect-transistor measurements, DFT/TD-DFT calculations and in the case of the paramagnetic species, EPR and magnetic susceptibility. Variation of the substituent on the ligand from t-octyl to n-propyl to H enabled electronic isolation of the complexes in the crystal structures of M(t-OctsaoH)2, which contrasted with π-stacking interactions observed in the crystal packing of M(n-PrsaoH)2 and of M(HsaoH) (M = Ni, Cu). This was further evidenced by comparing the antiferromagnetic interactions observed in samples of Cu(n-PrsaoH)2 and Cu(HsaoH)2 with the ideal paramagnetic behaviour for Cu(t-OctsaoH)2 down to 1.8 K. Despite isostructural single crystal structures for M(n-PrsaoH)2, thin-film X-ray diffraction and SEM revealed different morphologies depending on the metal and the deposition method employed. However, the complexes of M(n-PrsaoH)2 and M(HsaoH) failed to demonstrate significant charge transport in an FET device despite displaying the ability to form π- stacking structures. A series of planar Ni(II), Cu(II) and Co(II) dibenzotetraaza[14]annulenes (dbtaa) and dinapthotetraaza[14]annulenes (dntaa) were synthesised and studied crystallographically, optically, electrochemically and magnetically. Thin films of each of these complexes have been prepared by vacuum deposition to evaluate the field-effect transistor (FET) performance as well as the morphology and crystallinity of the film formed. Single crystal data revealed that Ni(dbtaa) and Cu(dbtaa) are isomorphous to each other, with Co(dbtaa) displaying a different crystallographic packing. The electrochemistry and UV/Vis absorption studies indicate the materials are redox active and highly coloured, with molar extinction coefficients as large as 80,000 M-1cm-1 in the visible region. The paramagnetic Cu(II) and Co(II) complexes display weak 1-dimensional antiferromagnetic interactions and were fit to the Bonner-Fisher chain model. The data revealed that the Co(II) species possesses much stronger magnetic exchange interactions compared with the Cu(II) complex. Each of the materials formed polycrystalline films when vacuum deposited and all showed ptype field-effect transistor behaviour, with modest charge carrier mobilities in the range of 10-5 to 10-9 cm2 V-1 s-1 . SEM imaging of the substrates indicates that the central metal ion, and its sublimation temperature, has a crucial role in defining the morphology of the resulting film. Structurally related Cu(II) and Ni(II) dithiadiazoletetraaza[14]annulene (dttaa) macrocycles were synthesised and studied in the context of their thin film electrochemical, conducting and morphological properties. Both the Ni(II) and Cu(II) complexes were found to be volatile under reduced pressure, which allowed crystals of both materials to be grown and the single crystal structures solved. Interestingly, the crystal packing of these heterocyclic macrocycles varies depending on whether the central metal ion is Cu(II) or Ni(II), which is in contrast to the analogous dibenzotetrazaannulenes complexes. Soluble Ni(II) analogues containing benzoyl groups on the meso- positions of the macrocycle (dttaaBzOR) were also prepared and contrasted with the insoluble Ni(dttaa) complexes in terms of their solution optical and electrochemical properties. Thin film electrochemical studies of Cu(dttaa) and Ni(dttaa) showed chemically reversible oxidative processes but on scanning to reductive potentials the films disintegrated almost immediately as the bulky counter tetrabutylammonium cation entered the thin film. FET studies undertaken on polycrystalline films of both complexes, using various device configurations and surface treatments, failed to realise any gate effect. Thin film XRD measurements indicate that films of both complexes formed by vacuum deposition are crystalline and contain a mixture of molecular alignments, with molecules aligning “edge on” and “face down” to the substrate. SEM imaging failed to effectively resolve the morphology of the films implying the sizes of the crystallites are small, which may help to explain the lack of FET effect. A series of bis-ligand diimine Ni, Cu and Pd complexes have been synthesised from the ligand 4,5-bis(dodecyloxy)benzene-1,2-diamine (dbdaH2). The same ligand was also used to prepare a series of soluble Cu(II) and Ni(II) tetraaza[14]annulene macrocycles. All the bis-ligand diimine complexes were found to suffer from instability in air due to the ease at which the complexes are oxidised. The Ni complex, Ni(dbda)2, was found to display a NIR transition in the region of 971 to 1024 nm depending on the polarity of the solvent that the molecule is dissolved in. Solution electrochemistry studies of Ni(dbda)2 reaffirmed the facile nature of the first oxidative process, with the HOMO energy calculated at -4 eV by hybrid-DFT. This compound failed to yield semiconducting behaviour in an FET device despite the use of surface treatments aimed at promoting suitable molecular alignment across the conducting channel.

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