Excitonic behaviour in polymeric semiconductors : the effect of morphology and composition in heterostructures

La compréhension des interrelations entre la microstructure et les processus électroniques dans les polymères semi-conducteurs est d’une importance primordiale pour leur utilisation dans des hétérostructures volumiques. Dans cette thèse de doctorat, deux systémes diffèrents sont étudiés ; chacun de ces systèmes représente une approche diffèrente pour optimiser les matériaux en termes de leur microstructure et de leur capacité à se mettre en ordre au niveau moléculaire. Dans le premier système, j’ai effectué une analyse complète des principes de fonctionnement d’une cellule photovoltaïque hybride à base des nanocristaux d’oxyde de zinc (ZnO) et du poly (3-hexylthiophène) (P3HT) par absorption photoinduite en régime quasi-stationnaire (PIA) et la spectroscopie PIA en pompage modulé dépendant de la fréquence. L’interface entre le donneur (le polymère P3HT) et l’accepteur (les nanoparticules de ZnO), où la génération de charges se produit, joue un rôle important dans la performance des cellules photovoltaïques hybrides. Pour améliorer le mécanisme de génération de charges du P3H: ZnO, il est indispensable de modifier l’interface entre ses constituants. Nous avons démontré que la modification d’interface moléculaire avec cis-bis (4, 40 - dicarboxy-2, 20bipyridine) ruthénium (II) (N3-dye) et a-Sexithiophen-2 yl-phosphonique (6TP) a améliorée le photocourant et la performance dans les cellules P3HT: ZnO. Le 6TP et le N3 s’attachent à l’interface du ZnO, en augmentant ainsi l’aire effective de la surface donneur :accepteur, ce qui contribue à une séparation de charge accrue. De plus, le 6TP et le N3 réduisent la densité de pièges dans le ZnO, ce qui réduit le taux de recombinaison des paires de charges. Dans la deuxième partie, jai introduit une matrice hôte polymérique de polystyréne à masse molaire ulra-élevée, qui se comporte comme un solide pour piéger et protéger une solution de poly [2-méthoxy, 5- (2´-éthyl-hexoxy) -1,4-phénylènevinylène- PPV] (MEHPPV) pour utilisation dans des dispositifs optoèlectroniques quantiques. Des travaux antérieurs ont montré que MEH-PPV en solution subit une transition de conformation, d’une conformation enroulé à haute température (phase bleue) à une conformation de chaîne étendue à basse température (phase rouge). La conformation de la chaîne étendue de la solution MEH-PPV favorise les caractéristiques nécessaires à l’amélioration des dispositifs optoélectroniques quantiques, mais la solution ne peut pas être incorporées dans le dispositif. J’ai démontré que la caractéristique de la phase rouge du MEH-PPV en solution se maintient dans une matrice hôte polymérique de polystyrène transformé de masse molaire très élevée, qui se comporte comme un solide (gel de MEH-PPV/UHMW PS), par le biais de la spectroscopie de photoluminescence (PL) dépendant de la température (de 290K à 80 K). La phase rouge du gel MEH-PPV/UHMW PS se manifeste par des largeurs de raie étroites et une intensité augmentée de la transition 0-0 de la progression vibronique dans le spectre de PL ainsi qu’un petit décalage de Stokes entre la PL et le spectre d’absorption à basse température. Ces approches démontrent que la manipulation de la microstructure et des propriétés électroniques des polymères semi-conducteurs ont un impact direct sur la performance de dispositifs pour leurs développements technologiques continus.

What is social innovation? The paradigm shift and its relationship with Social Work

Innovation is a fundamental part of social work. In recent years there has been a shift in the innovation paradigm, making it easier to accept this relationship. National and supranational policies aimed at promoting innovation appear to be specifically guided by this idea. To be able to affirm this hypothesis, it is necessary to review the perception that social workers have of their duties. It is also useful to examine particular cases that show how such social innovation arises.

VLSI design and implementation of 2-D Inverse Discrete Wavelet Transform

This paper proposes a JPEG-2000 compliant architecture capable of computing the 2 -D Inverse Discrete Wavelet Transform. The proposed architecture uses a single processor and a row-based schedule to minimize control and routing complexity and to ensure that processor utilization is kept at 100%. The design incorporates the handling of borders through the use of symmetric extension. The architecture has been implemented on the Xilinx Virtex2 FPGA.

Management of public water supply to reduce energy cost and improve wind power uptake

This paper presents a study on the implementation of Real-Time Pricing (RTP) based Demand Side Management (DSM) of water pumping at a clean water pumping station in Northern Ireland, with the intention of minimising electricity costs and maximising the usage of electricity from wind generation. A Genetic Algorithm (GA) was used to create pumping schedules based on system constraints and electricity tariff scenarios. Implementation of this method would allow the water network operator to make significant savings on electricity costs while also helping to mitigate the variability of wind generation.

Management of public water supply to reduce energy cost and improve wind power uptake

This paper presents a study on the implementation of Real-Time Pricing (RTP) based Demand Side Management (DSM) of water pumping at a clean water pumping station in Northern Ireland, with the intention of minimising electricity costs and maximising the usage of electricity from wind generation. A Genetic Algorithm (GA) was used to create pumping schedules based on system constraints and electricity tariff scenarios. Implementation of this method would allow the water network operator to make significant savings on electricity costs while also helping to mitigate the variability of wind generation.

Design and Flux-Weakening Control of an Interior Permanent Magnet Synchronous Motor for Electric Vehicles

Permanent magnet synchronous motors (PMSMs) provide a competitive technology for EV traction drives owing to their high power density and high efficiency. In this paper, three types of interior PMSMs with different PM arrangements are modeled by the finite element method (FEM). For a given amount of permanent magnet materials, the V-shape interior PMSM is found better than the U-shape and the conventional rotor topologies for EV traction drives. Then the V-shape interior PMSM is further analyzed with the effects of stator slot opening and the permanent magnet pole chamfering on cogging torque and output torque performance. A vector-controlled flux-weakening method is developed and simulated in Matlab to expand the motor speed range for EV drive system. The results show good dynamic and steady-state performance with a capability of expanding speed up to four times of the rated. A prototype of the V-shape interior PMSM is also manufactured and tested to validate the numerical models built by the FEM.

Web-based museum trails on PDAs for university-level design students: Design and evaluation

This paper describes the development and evaluation of web-based museum trails for university-level design students to access on handheld devices in the Victoria and Albert Museum (V&A) in London. The trails offered students a range of ways of exploring the museum environment and collections, some encouraging students to interpret objects and museum spaces in lateral and imaginative ways, others more straightforwardly providing context and extra information. In a three-stage qualitative evaluation programme, student feedback showed that overall the trails enhanced students’ knowledge of, interest in, and closeness to the objects. However, the trails were only partially successful from a technological standpoint due to device and network problems. Broader findings suggest that technology has a key role to play in helping to maintain the museum as a learning space which complements that of universities as well as schools. This research informed my other work in visitor-constructed learning trails in museums, specifically in the theoretical approach to data analysis used, in the research design, and in informing ways to structure visitor experiences in museums. It resulted in a conference presentation, and more broadly informed my subsequent teaching practice.

Designing motivation or motivating design? Exploring Service Design, motivation and behavioural change

Motivation researcher Edward Deci has suggested that if we want behavioural change to be sustainable, we have to move past thinking of motivation as something that we ‘do’ to other people and see it rather as something that we as Service Designers can enable service users to ‘do’ by themselves. In this article, Fergus Bisset explores the ways in which Service Designers can create more motivating services. Dan Lockton then looks at where motivating behaviour via Service Design often starts, with the basic ‘pinball’ and ‘shortcut’ approaches. We conclude by proposing that if services are to be sustainable in the long term, we as Service Designers need to strive to accommodate humans' differing levels of motivation and encourage and support service users' sense of autonomy within the services we design.

“Digital Diagnostics and Communication (DDC) system” Redesigning the Emergency Ambulance

During the development of a new treatment space for the UK emergency ambulance participatory observations with front-line clinicians revealed the need for an integrated patient monitoring, communication and navigation system. The research identified the different information touch-points and requirements through modes of use analysis, day-in-the-life study and simulation workshops with clinicians. Emergency scenario and role-play with paramedics identified 5 distinct ambulance modes of use. Information flow diagrams were created and checked by paramedics and digital User Interface (UI) wireframes were developed and evaluated by clinicians during clinical evaluations. Feedback from clinicians defined UI design specification further leading to a final design proposal. This research was a further development from the 2007 EPSRC funded “Smart Pods” project. The resulting interactive prototype was co-designed in collaboration with ambulance crews and provides a vision of what could be achieved by integrating well-proven IT technologies and protocols into a package relevant in the emergency medicine field. The system has been reviewed by over 40 ambulance crews and is part of a newly co-designed ambulance treatment space.

Investigation of the Nucleation and Growth of Colloidal Indium Phosphide: from Molecular Precursors to Semiconductor Nanocrystals through In37P20(O2CR)51 as a Magic-Size Intermediate

Thesis (Ph.D.)--University of Washington, 2016-06

STRAINING ENGINEERING OF GRAPHENE AND GRAPHENE-BASED NANOSTRUCTURES

Graphene has emerged as an extraordinary material with its capability to accommodate an array of remarkable electronic, mechanical and chemical properties. Extra-large surface-to-volume ratio renders graphene a highly flexible morphology, giving rise to intriguing observations such as ripples, wrinkles and folds as well as the potential to transform into other novel carbon nanostructures. Ultra-thin, mechanically tough, electrically conductive graphene films promise to enable a wealth of possible applications ranging from hydrogen storage scaffolds, electronic transistors, to bottom-up material designs. Enthusiasm for graphene-based applications aside, there are still significant challenges to their realization, largely due to the difficulty of precisely controlling the graphene properties. Controlling the graphene morphology over large areas is crucial in enabling future graphene-based applications and material design. This dissertation aims to shed lights on potential mechanisms to actively manipulate the graphene morphology and properties and therefore enable the material design principle that delivers desirable mechanical and electronic functionalities of graphene and its derivatives.

GOSPEL SINGING IN THE VALLEY: AN INVESTIGATION INTO THE HYMNODY AND CHORAL SINGING OF THE LISU ON THE CHINA-BURMA/MYANMAR BORDER

This dissertation is an ethnomusicological study of contemporary musical practices of the Christian Lisu in Nujiang Prefecture in northwest Yunnan on the China-Myanmar border. Among all the changes that the Nujiang Lisu have experienced since the twentieth century, the spread of Protestant Christianity throughout Nujiang’s mountainous villages has existed for the longest time and had one of the greatest effects. Combining historical investigation and ethnographic description, this study uses the lens of music to examine the impact of this social change on the Lisu living in this impoverished frontier region. The Lisu characteristics have never been vital in the music written by the Christian Lisu in Nujiang. Compared with the practices described in other ethnomusicological writings on Christian music around the world that I have read, this absence of incorporation of indigenous musical elements is unusual. There are probably many other cases similar to that of the Lisu, but few ethnomusicologists have paid attention to them. I aim to elucidate this particular scenario of Lisu Christian music in relation to three social and cultural forces: the missionary legacy of conventions; the government’s identification of the Lisu as a minority nationality and its national policies toward them since the 1950s; and the transnational religious exchange between the Christian Lisu in China and Myanmar since the late 1980s. My examination focuses on two genres which the Lisu use to express their Christian beliefs today: ddoqmuq mutgguat, derived from American northern urban gospel songs, the basis of the Lisu choral singing; and mutgguat ssat, influenced by the Christian pop of the Burmese Lisu, with instrumental accompaniment and daibbit dance and preferred by the young people. Besides studying these two genres in the religious context, I also juxtapose them with other musical traditions in the overall Nujiang music soundscape and look at their role in local social interactions such as those between sacred and secular, and majority and minority. This dissertation demonstrates that the collective performances of shared repertoires have not only created a sense of affinity for the Nujiang Christian Lisu but also have reinforced the formation of Lisu transnational religious networks.

Coupling of magnetic, strain and electric polarization fields in the structure of multiferroic material

The comprehensive study on the coupling of magnetism, electrical polarization and the crystalline lattice with the off-stoichiometric effects in self-doped multiferroic hexagonal h-LuMnxO3±δ (0.92≤x≤1.12) ceramic oxides was carried out for the PhD work. There is a complex coupling of the three ferroic degrees. The cancelation of the magnetic moments of ions in the antiferromagnetic order, electric polarization with specific vortex/antivortex topology and lattice properties have pushed researchers to find out ways to disclose the underlying physics and chemistry of magneto-electric and magneto-elastic couplings of h-RMnO3 multiferroic materials. In this research work, self-doping of Lu-sites or Mn-sites of h-LuMnxO3±δ ceramics prepared via solid state route was done to pave a way for deeper understanding of the antiferromagnetic transition, the weak ferromagnetism often reported in the same crystalline lattices and the ferroelectric properties coupled to the imposed lattice changes. Accordingly to the aim of the PhD thesis, the objectives set for the sintering study in the first chapter on experimental results were two. First, study of sintering off-stoichiometric samples within conditions reported in the bibliography and also extracted from the phase diagrams of the LuMnxO3±δ, with a multiple firings ending with a last high temperature step at 1300ºC for 24 hours. Second, explore longer annealing times of up to 240 hours at the fixed temperature of 1300 ºC in a search for improving the properties of the solid solution under study. All series of LuMnxO3±δ ceramics for each annealing time were characterized to tentatively build a framework enabling comparison of measured properties with results of others available in literature. XRD and Rietveld refinement of data give the evolution the lattice parameters as a function to x. Shrinkage of the lattice parameters with increasing x values was observed, the stability limit of the solid solution being determined by analysis of lattice parameters. The evolution of grain size and presence of secondary phases have been investigated by means of TEM, SEM, EDS and EBSD techniques. The dependencies of grain growth and regression of secondary phases on composition x and time were further characterized. Magnetic susceptibility of samples and magnetic irreversibility were extensively examined in the present work. The dependency of magnetic susceptibility, Neel ordering transition and important magnetic parameters are determined and compared to observation in other multiferroics in the following chapter of the thesis. As a tool of high sensitivity to detect minor traces of the secondary phase hausmannite, magnetic measurements are suggested for cross-checking of phase diagrams. Difficulty of previous studies on interpreting the magnetic anomaly below 43 K in h-RMnO3 oxides was discussed and assigned to the Mn3O4 phase, with supported of the electron microscopy. Magneto-electric coupling where AFM ordering is coupled to dielectric polarization is investigated as a function of x and of sintering condition via frequency and temperature dependent complex dielectric constant measurements in the final chapter of the thesis. Within the limits of solid solubility, the crystalline lattice of off-stoichiometric ceramics was shown to preserve the magneto-electric coupling at TN. It represents the first research work on magneto-electric coupling modified by vacancy doping to author’s knowledge. Studied lattices would reveal distortions at the atomic scale imposed by local changes of x dependent on sintering conditions which were widely inspected by using TEM/STEM methods, complemented with EDS and EELS spectroscopy all together to provide comprehensive information on cross coupling of distortions, inhomogeneity and electronic structure assembled and discussed in a specific chapter. Internal interfaces inside crystalline grains were examined. Qualitative explanations of the measured magnetic and ferroelectric properties were established in relation to observed nanoscale features of h-LuMnxO3±δ ceramics. Ferroelectric domains and topological defects are displayed both in TEM and AFM/PFM images, the later technique being used to look at size, distribution and switching of ferroelectric domains influenced by vacancy doping at the micron scale bridging to complementary TEM studies on the atomic structure of ferroelectric domains. In support to experimental study, DFT simulations using Wien2K code have been carried out in order to interpret the results of EELS spectra of O K-edge and to obtain information on the cation hybridization to oxygen ions. The L3,2 edges of Mn is used to access the oxidation state of the Mn ions inside crystalline grains. In addition, rehybridization driven ferroelectricity is also evaluated by comparing the partial density of states of the orbitals of all ions of the samples, also the polarization was calculated and correlated to the off-stoichiometric effect.

Phobos: The design and implementation of embedded software for a low cost radar warning receiver

This portfolio thesis describes work undertaken by the author under the Engineering Doctorate program of the Institute for System Level Integration. It was carried out in conjunction with the sponsor company Teledyne Defence Limited. A radar warning receiver is a device used to detect and identify the emissions of radars. They were originally developed during the Second World War and are found today on a variety of military platforms as part of the platform’s defensive systems. Teledyne Defence has designed and built components and electronic subsystems for the defence industry since the 1970s. This thesis documents part of the work carried out to create Phobos, Teledyne Defence’s first complete radar warning receiver. Phobos was designed to be the first low cost radar warning receiver. This was made possible by the reuse of existing Teledyne Defence products, commercial off the shelf hardware and advanced UK government algorithms. The challenges of this integration are described and discussed, with detail given of the software architecture and the development of the embedded application. Performance of the embedded system as a whole is described and qualified within the context of a low cost system.

Engineering thin films of magnetic alloys and semiconductor oxides at the nanoscale

The thesis aims to exploit properties of thin films for applications such as spintronics, UV detection and gas sensing. Nanoscale thin films devices have myriad advantages and compatibility with Si-based integrated circuits processes. Two distinct classes of material systems are investigated, namely ferromagnetic thin films and semiconductor oxides. To aid the designing of devices, the surface properties of the thin films were investigated by using electron and photon characterization techniques including Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), grazing incidence X-ray diffraction (GIXRD), and energy-dispersive X-ray spectroscopy (EDS). These are complemented by nanometer resolved local proximal probes such as atomic force microscopy (AFM), magnetic force microscopy (MFM), electric force microscopy (EFM), and scanning tunneling microscopy to elucidate the interplay between stoichiometry, morphology, chemical states, crystallization, magnetism, optical transparency, and electronic properties. Specifically, I studied the effect of annealing on the surface stoichiometry of the CoFeB/Cu system by in-situ AES and discovered that magnetic nanoparticles with controllable areal density can be produced. This is a good alternative for producing nanoparticles using a maskless process. Additionally, I studied the behavior of magnetic domain walls of the low coercivity alloy CoFeB patterned nanowires. MFM measurement with the in-plane magnetic field showed that, compared to their permalloy counterparts, CoFeB nanowires require a much smaller magnetization switching field , making them promising for low-power-consumption domain wall motion based devices. With oxides, I studied CuO nanoparticles on SnO2 based UV photodetectors (PDs), and discovered that they promote the responsivity by facilitating charge transfer with the formed nanoheterojunctions. I also demonstrated UV PDs with spectrally tunable photoresponse with the bandgap engineered ZnMgO. The bandgap of the alloyed ZnMgO thin films was tailored by varying the Mg contents and AES was demonstrated as a surface scientific approach to assess the alloying of ZnMgO. With gas sensors, I discovered the rf-sputtered anatase-TiO2 thin films for a selective and sensitive NO2 detection at room temperature, under UV illumination. The implementation of UV enhances the responsivity, response and recovery rate of the TiO2 sensor towards NO2 significantly. Evident from the high resolution XPS and AFM studies, the surface contamination and morphology of the thin films degrade the gas sensing response. I also demonstrated that surface additive metal nanoparticles on thin films can improve the response and the selectivity of oxide based sensors. I employed nanometer-scale scanning probe microscopy to study a novel gas senor scheme consisting of gallium nitride (GaN) nanowires with functionalizing oxides layer. The results suggested that AFM together with EFM is capable of discriminating low-conductive materials at the nanoscale, providing a nondestructive method to quantitatively relate sensing response to the surface morphology.