Abstract: Understanding and controlling the ultrafast charge carrier and exciton dynamics at the interface of semiconductor nanocrystals (NCs) offer an excellent opportunity to improve the charge collection and the overall performance of many optoelectronic and energy-based devices. In this dissertation, we study how interfacial engineering of these materials can have a direct influence on controlling the charge transfer and the nonradiative losses in different donor-acceptor systems. The first introductory chapter provides an overview of all the fundamental photophysical processes controlling the interfacial phenomena. Then, the second chapter highlights all the chemicals and synthesis methods employed during this thesis. The subsequent two chapters discuss the detailed experimental studies and observations related to different materials and interfaces. First, it describes how we can dramatically tune the intersystem crossing (ISC) rate, the triplet state lifetime, turn on/off the electron injection at the CdTe-Prophyrin interface via tuning either the quantum dot size or the porphyrin molecular structure. Also, how the intermolecular distances, electronic coupling, and subsequently, the photoinduced charge transfer can be controlled by the interfacial electrostatic interactions at CdTe-Fullerene interfaces. Second, due to the promise that of perovskite NCs holds for improving many solar cell and optoelectronic applications, chapter 3 highlights the tremendous effect that the shape of perovskite nanocrystals has on the rate and the mechanism of charge transfer at the MAPbBr3- TCNE interface. Besides, it demonstrates how the confinement effect brought by changing the dimensionality influence the charge transfer dynamics at the MAPbBr3-BQ interface. Finally, it explains how the effective passivation of the surface defects and the subsequent suppression of the formation of surface nonradiative recombination centers in CsPbCl3 NCs controls the photoluminescence quantum yield and the photodetector performance.

This project deals with the mixed micellar and interfacial properties of mixtures of three surfactants [sodium dodecyl sulphate (SDS), cetyltrimethylammonium bromide (CTAB), and tetraethylene glycol monododecyl ether (C12E4)] with ABA symmetrical triblock copolymer (Pluronic F127), which has many industrial applications. Evidence of F127 micellisation and interaction with surfactants in the aqueous phase is inferred through interfacial tension measurements. The solution containing diluted monomeric F127 showed complex formation with surfactants before the latter self-aggregate as pure micelles. The simultaneous presence of ionic surfactants and micellar F127 in solutions displayed a decrease of interfacial activity and led to the conclusion of F127 micelles disruption. C12E4 was found to interact differently with micellar F127 in forming mixed micelles, and no loss of interfacial activity was recorded. This “association-dissociation” behaviour of F127 and surfactants was leveraged to understand the stability of mineral oil in water emulsions formulated with them in the presence of sodium phosphate (Na3PO4). The mechanisms of emulsions breakdown were found to rely on aggregation behaviour and complex structure of F127 and surfactants mixtures in solution. Laser diffraction showed that unlike SDS and CTAB, mixed-emulsifier systems containing C12E4 are stable to both flocculation, Ostwald ripening and coalescence. Due to electrostatic repulsion between its head group and F127 hydrophilic block, and also because of the combined effect of Ostwald ripening and coalescence, CTAB emulsifier containing systems displayed quicker instability than SDS. SDS containing systems showed a progressive shifting of droplets size distributions to bimodality as SDS concentration was increased and heat exposure pursued, revealing the activity of two distinct population of droplets in the emulsions. More insight on the mechanisms underlying the stability of the three mixed emulsifier systems was gained in performing optical microscopy and rheology measurements; the results were found to be consistent with particle size distribution. / Dissertation (MSc (Applied Science: Chemical Technology))--University of Pretoria, 2020. / Chemical Engineering / MSc (Applied Science: Chemical Technology) / Unrestricted

Le but de ce travail de thèse est d'identifier les mécanismes moléculaires mis en jeu lors du frottement de polymères liquides sur une paroi solide.Dans une première partie, nous avons étudié l'influence de la température T sur le glissement de fondus. Grâce à la technique de vélocimétrie par photoblanchiment, nous avons mesuré la longueur de glissement de PDMS pour plusieurs températures et vérifié l'hypothèse de Navier, qui permet de définir le coefficient de frottement interfacial k comme le rapport entre la viscosité et la longueur de glissement. Loin de la température de transition vitreuse, k augmente exponentiellement avec 1/T, tendance que nous avons vérifiée par une mesure indépendante pour des lentilles de PDMS réticulé. Ainsi, le mécanisme de frottement d'un fondu de polymère est un processus thermiquement activé. La comparaison des énergies d'activation du frottement et de la viscosité prédit le sens de variation de la longueur de glissement avec la température.Le second volet de notre travail s'est focalisé sur l'identification des mécanismes moléculaires du frottement de solutions semi-diluées de polymère. Les expériences de glissement pour des solutions de PS dans le DEP nous ont permis de mettre en évidence un régime transitoire de glissement des solutions, correspondant à une mise en glissement du fluide. Nous avons proposé un modèle de glissement d'un fluide de Maxwell en accord quantitatif avec les expériences.Dans le régime de glissement stationnaire, nous avons étudié l'influence de la fraction volumique φ en polymère sur le frottement des solutions. En régime newtonien, la loi d'échelle mesurée pour k φ en fonction de la fraction volumique met en évidence la dépendance du coefficient de frottement interfacial avec l'écart à la température de transition vitreuse des solutions. Nous attribuons le frottement des solutions de PS dans le DEP au frottement des blobs sur la paroi et non à la formation d'une couche déplétée en polymère.Enfin des expériences de réflectivité de neutrons nous ont permis d'observer directement l'interface solide / solution de polymère. Nous avons mis en évidence l'existence d'une couche adsorbée en polymère. Nous avons mesuré son profil de concentration en fonction de la distance à la paroi. L'interdigitation des chaînes libres et de surface affecte le glissement des solutions. / The aim of this work is to identify the molecular mechanisms driving the friction of liquid polymers on a solid substrate.First, we studied the effect of the temperature T on the slippage properties of PDMS melts. Using a velocimetry technique based on photobleaching, we measured the temperature dependence of the slip length of PDMS and checked the validity of Navier’s hypothesis, which defines the friction coefficient k as the ratio between the bulk viscosity to the slip length. Far above the glass transition temperature, k(T) increases exponentially with 1/T, a result that we confirmed with an independent measurement of k for the friction of crosslinked PDMS lenses. The friction mechanism of melts is a thermally activated process. The comparison of the activation energies for the friction and for the viscosity allows one to predict if the slip length increases or deacreases with temperature.We then focused our work on the identification of the friction mechanisms of semi diluted polymer solutions. Based on slip experiments of PS in DEP solutions, we evidenced a transient onset of slippage regime. Considering the viscoelasticity of the fluid and its friction properties, we developed a mechanical model of friction of a Maxwell-like fluid that well describes our experimental data.In the stationary slippage regime, we studied the influence of the polymer volume fraction φ on the slippage of solutions of polymer. In the Newtonian regime, the measured scaling law for k φ as a function of the volume fraction highlights the dependence of the friction coefficient on the distance to the glass transition temperature of the solution. Thus, the friction of the PS in DEP solutions can be attributed to the friction of blobs on the surface, rather than to the existence of a depletion layer.We directly observed the solid / polymer solution interface thanks to neutron reflectivity: these experiments reveal the formation of an adsorbed polymer layer and we could measure its concentration profile close to the solid wall. The interdigitation between volume and surface polymer chains plays a key role in the slippage of the solutions.

When a sphere or a stream of water hits the surface of a pool of water and enters a crater or air cavity often forms. This topic has been studied, both formally and informally, for a long time. This dissertation investigates four areas of water impact that are still poorly understood using high-speed photography. First, it examines a stream of droplets impacting on a pool of water, similar to a faucet drizzling into a full bucket. For these types of impacts we predict the depth, diameter, velocity, and shape of the cavities that the droplet stream forms. Second, it examines what occurs when a sphere impacts a pool of soapy water, such as a bubble bath or kitchen sink. The minimum velocity for a cavity to form decreases when soap is present. If the water has bubbles on the surface, the sphere will always form a cavity. Third, it examines how different coatings on a sphere (car wax, etc.) affect whether the sphere forms a cavity, and it shows how the coating affect the shape of that cavity. Fourth, when objects impact a water surface they experience a large force, which many people have noticed when participating in cliff jumping, high diving, and belly flop competitions. We show that the force of impact can be reduced by 75% simply by allowing a mass of water to impact in front of the object.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18272号 / 工博第3864号 / 新制||工||1593(附属図書館) / 31130 / 京都大学大学院工学研究科原子核工学専攻 / (主査)教授 功刀 資彰, 教授 中部 主敬, 准教授 横峯 健彦 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21369号 / 工博第4528号 / 新制||工||1705(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 中村 裕之, 教授 安田 秀幸 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21783号 / 工博第4600号 / 新制||工||1717(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 作花 哲夫, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

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