abstract: The study of subwavelength behavior of light and nanoscale lasing has broad potential applications in various forms of computation i.e. optical and quantum, as well as in energy engineering. Although this field has been under active research, there has been little work done on describing the behaviors of threshold and saturation. Particularly, how the gain-molecule behavior affects the lasing behavior has yet to be investigated. In this work, the interaction of surface-plasmon-polaritons (SPPs) and molecules is observed in lasing. Various phenomenologies are observed related to the appearance of the threshold and saturation regions. The lasing profile, as a visual delimiter of lasing threshold and saturation, is introduced and used to study various parametrical dependencies of lasing, including the number-density of molecules, the molecular thickness and the frequency detuning between the molecular transition frequency and the SPP resonant frequency. The molecular population distributions are studied in terminal and dynamical methods and are found to contain unexpected and theoretically challenging properties. Using an average dynamical analysis, the simulated spontaneous emission cascade can be clearly seen. Finally, theoretical derivations of simple 1D strands of dipoles are presented in both the exact and mean-field approximation, within the density matrix formalism. Some preliminary findings are presented, detailing the observed behaviors of some simple systems. / Dissertation/Thesis / Masters Thesis Chemical Engineering 2017

Quadratic optimization problems arise in various real world application domains including engineering design, microeconomics, genetic algorithms, integrated circuit chip design, probabilistic graphical models and computer vision. In particular, there are many problems in computer vision that require binary quadratic optimization such as motion segmentation, correspondences, figure-ground segmentation, clustering, grouping, subgraph matching, and digital matting. The objective of an optimization algorithm can be related to the state of a physical system, where the goal is to bring the initial arbitrary state of the system to a state with minimum possible energy. By recognizing that the Hamiltonian of nanomagnets can be expressed in a quadratic form, we exploit the energy minimization aspect of these nanomagnets to solve the quadratic optimization problem in a direct manner. Most hard problems especially in computer vision can be naturally cast as energy minimization problems and solving these using traditional techniques like simulated annealing, graph cuts evidently associate with exorbitant computational efforts. In this dissertation, transcoding the conceptual crossover between the magnetic Hamiltonian and the optimization problem, we envision a nanomagnetic coprocessor with a grid of nanomagnets embracing an optimization heuristic enabling to solve energy minimization in a single clock cycle. We will essentially be solving an optimization problem with each input-and-readout cycle as compared to orders of magnitude more clock cycles that would be needed in a Boolean logic circuit. The dissertation presents results for quadratic minimization problem in the context of perceptual organization of edges in computer vision and compare quality of results using traditional optimization methods and that expected from magnetic computing. The dissertation also presents image processing algorithms for analysis of results produced by actual fabrication of the magnetic systems.

[pt] Neste trabalho foi estudado o mecanismo de deformação de faces polares e não polares do óxido de zinco (ZnO), através da introdução de defeitos mecânicos por nanoindentação. A estrutura cristalina estável do ZnO é do tipo wurtzita, de forte caráter anisotrópico já observado em relação a propriedades como piezoeletricidade e polarização espontânea. O mecanismo de deformação mecânica desses sistemas ainda não está bem esclarecido e são de vital importância na otimização de dispositivos optoeletrônicos. A extensão dos defeitos para cada orientação do cristal foi analisada via microscopia eletrônica de transmissão e correlacionada com o movimento de planos basais {0001} de forma divergente, em faces não polares (1100) e (1120), e ao movimento de planos piramidais {1011} de forma convergente para faces polares (0001) e (0001). A extensão da deformação induzida abaixo da superfície foi avaliada, onde foi possível identificar a formação de discordâncias do tipo parafuso que se propagam através do sistema de escorregamento (1120)(0001), se propagando de forma altamente localizada abaixo da superfície. O início da deformação plástica em monocristais é marcado por eventos plásticos súbitos (pop-ins). Estes eventos foram identificados e analisados em função da força e da extensão da deformação gerada. A topografia e forma das impressões residuais foi analisada usando microscopia de força atômica. Os defeitos observados no plano superficial tenderam a se propagar em direções preferenciais num processo induzido pela formação de zonas de tensão em torno da indentação. A formação de zonas de tensão trativa em uma dada direção aumenta a mobilidade das discordâncias, enquanto zonas de tensão compressiva agem contribuindo para o travamento. Estas zonas foram identificadas e a magnitude desta tensão foi estimada via catodoluminescência. Observamos também que a face polar (0001) apresentou um comportamento reativo, onde defeitos localizados abaixo da superfície foram revelados através do processo de limpeza. / [en] In this work, deformation mechanisms of polar and non-polar zinc oxide (ZnO) were studied by nanoindentation tests. The stable crystal structure of ZnO is the wurtzite with a strong anisotropic character observed in relation to the piezoelectricity and spontaneous polarization properties, for example. The mechanical deformation mechanisms of these sorts of materials are not yet fully understood, being of vital importance for optoelectronic devices optimization.For each ZnO crystallographic orientation, the induced defects damages were analyzed by transmission electron microscopy (TEM) and correlated with the slip of basal planes {0001} in the divergent directions for the both non-polar faces (1100) and (1120), as well as for the both polar faces (0001) and (0001). Screw perfect dislocations were identified by propagating through the slip system (1120)(0001). The beginning of plastic deformation in single crystals is marked by pop-ins events. Such events were identified and analyzed in function of the applied force and size. The residual impressions topography and shape were analyzed by atomic force microscopy (AFM). The observed defects on the surface were propagated in a preferred direction induced by stress components around the indentation. Tensile stress generation in a certain direction increases the dislocations mobility, while compressive stress contributes to pinning regions. Stress components were identified and their magnitudes were estimated by cathode luminescence method. The polar face (0001) showed a reactive behavior; some defects produced underneath the surface were revealed by samples cleaning process.

In most of the tribological experiments studying friction and wear behaviour, the contact interface is hidden. The present work attempts to overcome this hidden-interface problem by carrying out real-time tribological experiments inside Transmission Electron Microscope (TEM). This is achieved by developing an in situ TEM triboprobe which can carry out nanoscale indentation, sliding and reciprocating tests on an electron transparent sample inside TEM. A novel in situ TEM triboprobe is developed by characterising the individual components involved in the development. Coarse positioning of a sharp probe is achieved using inertial sliders. Fine motion of the probe is controlled using a 4-quadrant tube piezoceramic. This triboprobe is capable of carrying out high stiffness tribological experiments inside TEM. The interface is viewed at high resolutions in real time during the experiments using a movie rate CCD camera. In indentation experiments a sharp probe is brought into contact with the sample surface. During indentation of Aluminium alloy tribolayer, it has been observed that the cracks originate from subsurface and propagate to the surface causing delamination-like material removal. Indentation experiments on protruding silicon particle in Aluminium-Silicon (Al-Si) alloy shows that initial deformation is elastic. Once the load is increased, the particle starts indenting the soft aluminum matrix, and results in sinking of the particle into the aluminium matrix. Once the particle starts sinking, the increase in the displacement causes the generation of a crack and the propagation of this crack results in the fracture of the particle. The sliding experiments inside TEM allowed the direct visualization of asperity level interaction during sliding. The preliminary experimental results of nanoscale sliding experiments carried out using an AFM tip as the sample. The adhesive instability is observed as snap-in and snap-out events. The snap-out distance seems to depend on the local geometry of the contact. To simulate reciprocating wear, a sharp diamond probe is brought into contact with Al-Si alloy and reciprocated sinusoidally at 0.5Hz. At lower loads no wear is observed. However, when the normal load is increased, material starts getting removed in thin slivers, and most of the wear debris generated get swept away from the track. Some wear debris get entrapped in between the sliding surfaces; subsequently they join to form larger wear particles. The trapped particles generated during the test act like rollers and a significant increase in the stroke-length is observed accompanying the rolling action of the particle. The phenomena like agglomeration and dissociation of the wear particles has also been observed. Repeated deformation of the trapped particles leads to the formation of tiny liquid drop on some of the wear debris. The liquid consists of gallium which comes from the sample preparation technique. The interaction between the liquid droplets has been studied by carrying out liquid-bridge pulling experiments. Liquid gallium gets cooled with time during tensile pulling of the droplets. A nano-filament is formed between the droplets during pulling. After some time, the droplet gets solidified and coalescence of droplets does not take place. Further frictional heating was necessary to form the bridge again. The in situ TEM triboprobe, which allow the tribological processes to be observed dynamically under high resolutions, is a power full tool in detecting fundamental tribological interactions.

New circuit design techniques that accommodate lower supply voltages necessary for portable systems need to be integrated into the semiconductor intellectual property (IP) core. Systems that once worked at 3.3 V or 2.5 V now need to work at 1.8 V or lower, without causing any performance degradation. Also, the fluctuation of device characteristics caused by process variation in nanometer technologies is seen as design yield loss. The numerous parasitic effects induced by layouts, especially for high-performance and high-speed circuits, pose a problem for IC design. Lack of exact layout information during circuit sizing leads to long design iterations involving time-consuming runs of complex tools. There is a strong need for low-power, high-performance, parasitic-aware and process-variation-tolerant circuit design. This dissertation proposes methodologies and techniques to achieve variability, power, performance, and parasitic-aware circuit designs. Three approaches are proposed: the single iteration automatic approach, the hybrid Monte Carlo and design of experiments (DOE) approach, and the corner-based approach. Widely used mixed-signal circuits such as analog-to-digital converter (ADC), voltage controlled oscillator (VCO), voltage level converter and active pixel sensor (APS) have been designed at nanoscale complementary metal oxide semiconductor (CMOS) and subjected to the proposed methodologies. The effectiveness of the proposed methodologies has been demonstrated through exhaustive simulations. Apart from these methodologies, the application of dual-oxide and dual-threshold techniques at circuit level in order to minimize power and leakage is also explored.

Atomic force microscopy (AFM) is widely used to study material properties and domain heterogeneity of polymers. In both quasi-static force spectroscopy and dynamic AFM, challenging complexities such as the presence of different effective tip-surface forces, surface dynamics, and material viscoelasticity can occur on polymer samples. Many models that attempt to link experimental observables to contact mechanics fail to rigorously account for these complexities. This may lead to inaccurate and unreliable predictions, especially when examining soft polymers. Therefore, having access to rigorous models that can facilitate the understanding of the underlying phenomena during tip-surface interaction, explain the observations, and make reliable and accurate predictions, is of great interest. Among the previously developed models, Attard et al. proposed a novel non-Hertzian-based model that has a versatile ability to systematically incorporate different linear viscoelasticity constitutive models and surface adhesive forces. However, the implementation of Attard’s model into the AFM framework is challenging.<div><br></div><div>In a series of studies, we improve the computational speed and stability of Attard’s viscoelastic contact model and embed it into an AFM framework by proposing algorithms for three AFM operational modes: tapping mode, bimodal, and peak force tapping. For each mode, the results are successfully verified/validated against other reliable AFM codes, FEM simulations, and experiments. The algorithms’ predictions illustrate how viscoelasticity and surface adhesive hysteresis of polymeric samples is reflected in AFM observables. However, since Attard’s model does not lead to a closed-form solution for tip-surface interaction force, using that to quantify the surface mechanical properties based on the AFM observables is not straightforward. Therefore, we utilize the data analytics-based approaches such as linear regression and machine learning algorithms to enable the material viscoelasticity and adhesive parameters estimation based on the provided instrument observables.<br></div><div><br></div><div>The set of results reported in this thesis improves the current knowledge about complex phenomena that occur during tip-surface interactions, especially on soft-viscoelastic-adhesive polymers. The introduced “improved Attard’s model” fulfills the need for a continuum mechanics viscoelasticity contact model that rigorously captures the complexities of such samples. The viscoelasticity contact model and the proposed inverse solution algorithms in this thesis facilitate quantitative measurement and discrimination of the surface adhesive and viscoelastic properties based on the acquired nanoscale AFM maps of polymeric samples.<br></div>

Titanium dioxide (TiO2) is an important semiconducting metal oxide and is expected to play an important role in future applications related to photonic crystals, energy storage, and photocatalysis. Two aspects regarding the combustion synthesis have been investigated; scale-up in laboratory synthesis and advanced nanoparticle synthesis. Concerning the scale-up issue, a novel curved wall-jet (CWJ) burner was designed for flame synthesis. This was achieved by injecting precursors of TiO2 through a central port into different flames zones that were stabilized by supplying fuel/air mixtures as an annular-inward jet over the curved wall. This provides a rapid mixing of precursors in the reaction zone with hot products. In order to increase the contact surface between the precursor and reactants as well as its residence time within the hot products, we proposed two different modifications. The CWJ burner was modified by adding a poppet valve on top of the central port to deliver the precursor tangentially into the recirculating flow upstream within the recirculation zone. Another modification was made by adopting double-slit curved wall-jet (DS-CWJ) configuration, one for the reacting mixture and the other for the precursor instead of the central port. Particle growth of titanium dioxide (TiO2) nanoparticles and their phases were investigated. Ethylene (C2H4), propane (C3H8), and methane (CH4) were used with varying equivalence ratio and Reynolds number and titanium tetraisopropoxide (TTIP) was the precursor. Flow field and flame structure were quantified using particle image velocimetry (PIV) and OH planar laser-induced fluorescence (PLIF) techniques, respectively. TiO2 nanoparticles were characterized using high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Raman Spectroscopy, and BET nitrogen adsorption for surface area analysis. The flow field quantified by PIV consisted of a wall-jet region leading to a recirculation zone, an interaction jet region, followed by a merged-jet region. The modified CWJ burner revealed appreciable mixing characteristics between the precursor and combustion gases within these regions, with a slight increase in the axial velocity due to the precursor injection. This led to more uniformity in particle size distribution of the synthesized nanoparticles with the poppet valve (first modification). The double-slit modification improved the uniformity of generated nanoparticles at a very wide range of stable experimental conditions. Images of OH fluorescence showed that flames are tightly attached to the burner tip and TTIP has no influence on these flames structures. The particle size was slightly affected by the operating conditions. The phase of TiO2 nanoparticles was mainly dependent on the equivalence ratio and fuel type, which impact flame height, heat release rate and high temperature residence time of the precursor vapor. For ethylene and methane flames, the anatase content is proportional to the equivalence ratio, whereas it is inversely proportional in the case of propane flames. The anatase content reduced by 8% as we changed Re between 8,000 and 19,000, implying that the Re has a slight effect on the anatase content. The synthesized TiO2 nanoparticles exhibited high crystallinity and the anatase phase was dominant at high equivalence ratios (φ >1.6) for C2H4, and at low equivalence ratios (φ <1.3) for the C3H8 flame. Concerning advanced nanoparticle synthesis, a multiple diffusion burner and flame spray pyrolysis (FSP) were adopted in this study to investigate the effect of doping/coating on TiO2 nanoparticles. The nanoparticles were characterized by the previously mentioned techniques in addition to thermogravimetric analysis (TGA) for carbon content, X-ray photoelectron spectroscopy (XPS) for surface chemistry, ultraviolet-visible spectroscopy (UV-vis) for light absorbance, inductively coupled plasma (ICP) for metal traces, and superconducting quantum interference device (SQUID) for magnetic properties. Results from multi diffusion burner show that doping TiO2 with vanadium changes the phase from anatase to rutile while doping and coating with carbon or SiO2 does not affect the phase. Doping with iron reduces the band gab of TiO2 particles by reducing the conduction band. FSP results show that iron doping changes the valance band of the nanoparticles and enhances their paramagnetic behavior as well as better light absorption than pure titania, which make these particles good candidates for photocatalytic applications.

京都大学 / 0048 / 新制・課程博士 / 博士(医学) / 甲第22370号 / 医博第4611号 / 新制||医||1043(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 別所 和久, 教授 戸口田 淳也, 教授 妻木 範行 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

Downsizing gears towards nanoscale has opened the possibility to realize nanoscale mechanical machines, which is of great interest in the area of nanorobotics and devices immune to radiation. In this area, there are several crucial issues, such as how to trigger single gear rotation, the ability for interlocked rotation of many gears, and frictional properties during gear rotation on the surface. Here, we are aiming at addressing these three fundamental questions. First, we propose the rotational version of the Anderson-Holstein model within the nonequilibrium Green's function formalism as a possible phenomenological description of single gear rotation by switching between two potential energy surfaces of the highest occupied molecular orbital and lowest unoccupied molecular orbital. Secondly, we exploit the nearly rigid-body approximation for extracting the collective rotational variables of given molecule gears. The analysis of the probability distribution in thermal equilibrium for those variables between two coupled molecular gears has been studied with classical molecular dynamics simulations. This allows us to estimate the interaction potential profile between gears, which is strongly depending on the gear separation distance. Furthermore, we propose a method called locking coefficient diagram to characterize the ability of gear collective rotations under external torque. In comparison, a similar analysis for the case of solid-state gears is also studied, which shows a very robust mechanical transmission behavior. Hence, we have designed a two-digit mechanical pascaline based on these gears, which are feasible for carrying out simple calculations. Finally, the rotational friction for solid-state gears on top of a surface is also studied within classical molecular dynamics simulation. We find a regime of viscous dissipation, which is purely arising from the van-der-Waals interactions. Furthermore, the friction is closely related to the available degrees of freedom in the substrate. By analyzing the velocity distribution for the atoms in the substrate, we find that the rotational dissipation mechanism is largely related to surface phonon excitations. We expect that the results of this thesis will provide some insight for future studies in the area of nanoscale mechanical machines.

abstract: Photocatalytic water splitting over suspended nanoparticles represents a potential solution for achieving CO2-neutral energy generation and storage. To design efficient photocatalysts, a fundamental understanding of the material’s structure, electronic properties, defects, and how these are controlled via synthesis is essential. Both bulk and nanoscale materials characterization, in addition to various performance metrics, can be combined to elucidate functionality at multiple length scales. In this work, two promising visible light harvesting systems are studied in detail: Pt-functionalized graphitic carbon nitrides (g-CNxHys) and TiO2-supported CeO2-x composites. Electron energy-loss spectroscopy (EELS) is used to sense variations in the local concentration of amine moieties (defects believed to facilitate interfacial charge transfer) at the surface of a g-CNxHy flake. Using an aloof-beam configuration, spatial resolution is maximized while minimizing damage thus providing nanoscale vibrational fingerprints similar to infrared absorption spectra. Structural disorder in g-CNxHys is further studied using transmission electron microscopy at low electron fluence rates. In-plane structural fluctuations revealed variations in the local azimuthal orientation of the heptazine building blocks, allowing planar domain sizes to be related to the average polymer chain length. Furthermore, competing factors regulating photocatalytic performance in a series of Pt/g-CNxHys is elucidated. Increased polymer condensation in the g-CNxHy support enhances the rate of charge transfer to reactants owing to higher electronic mobility. However, active site densities are over 3x lower on the most condensed g-CNxHy which ultimately limits its H2 evolution rate (HER). Based on these findings, strategies to improve the cocatalyst configuration on intrinsically active supports are given. In TiO2/CeO2-x photocatalysts, the effect of the support particle size on the bulk/nanoscale properties and photocatalytic performance is investigated. Small anatase supports facilitate highly dispersed CeO2-x species, leading to increased visible light absorption and HERs resulting from a higher density of mixed metal oxide (MMO) interfaces with Ce3+ species. Using monochromated EELS, bandgap states associated with MMO interfaces are detected, revealing electronic transitions from 0.5 eV up to the bulk bandgap onset of anatase. Overall, the electron microscopy/spectroscopy techniques developed and applied herein sheds light onto the relevant defects and limiting processes operating within these photocatalyst systems thus suggesting rational design strategies. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2019