No / Make it connected! 2D close-packed layers of inorganic nanoparticles are interconnected by organic fibrils of oleic acid as clearly visualized by electron holography. These fibrils can be mineralised by PbS to transform an organic-inorganic framework to a completely interconnected inorganic semiconducting 2D array.

The Thermal Radiation Group at Virginia Polytechnic Institute and State University has been working closely with scientists and engineers at NASA's Langley Research Center to develop accurate analytical and numerical models suitable for designing next-generation thin-film thermal radiation detectors for earth radiation budget measurement applications. The current study provides an analytical model of the notional thermal radiation detector that takes into account thermal transport phenomena, such as the contact resistance between the layers of the detector, and is suitable for use in parameter estimation. It was found that the responsivity of the detector can increase significantly due to the presence of contact resistance between the layers of the detector. Also presented is the effect of doping the thermal impedance layer of the detector with conducting particles in order to electrically link the two junctions of the detector. It was found that the responsivity and the time response of the doped detector decrease significantly in this case. The corresponding decrease of the electrical resistance of the doped thermal impedance layer is not sufficient to significantly improve the electrical performance of the detector. Finally, the "roughness effect" is shown to be unable to explain the decrease in the thermal conductivity often reported for thin-film layers / Master of Science

In the pursuit of renewable and sustainable energy sources, this century presents humanity with an imperative driven by the crisis of conventional energy shortages and environmental pollution. Clean electrochemical energy storage and conversion technologies play a pivotal role in shaping the future landscape of power generation and energy utilization. However, the judicious design of the catalysts capable of efficiently and robustly driving electrochemical conversion remains a pressing challenge. In my dissertation, I addressed the critical challenges related to enhancing energy conversion efficiency in zinc-air batteries (ZABs) and electrocatalytic carbon dioxide reduction (CO2RR). These innovations show promise in utilizing renewable electricity to generate power and actively contribute to decarbonization efforts. The core focus of my dissertation revolves around the strategy of interface engineering for materials design and characterization. It is coupled with an in-depth mechanistic investigation of structure-property relationship at the interface level. The construction of a strong metal-support oxide interaction (SMMOI) has been demonstrated in the PdNiMnO porous film and has shown promising results. This interaction significantly enhances the activity of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) through electronic perturbation of Pd, reducing the reliance on precious metals and substantially improving the ZAB performance. On the other hand, my dissertation expands the decarbonization concept of electrocatalytic CO2RR towards value-added chemical production such as CO and formate. By designing bio-inspired tin oxide (SnOx) porous films through multiscale approaches of morphology engineering, surface chemistry, and phase transformation, the CO2RR Faradaic efficiency can be significantly improved. This is achieved by establishing a triple-phase interface and preserving the active phase through controlled pulsed electrochemical potentials during reactions. This innovative approach effectively addresses limitations associated with CO2 capture on the electrode and CO2 solubility issues in the electrolyte. The interface engineering strategies outlined in this dissertation illuminate the path toward next-generation catalyst designs that are highly efficient and tailored for sustainable and renewable energy applications.

In this work, we performed an experimental analysis using a two-dimensional semiconducting transition metal dichalcogenide (TMD), specifically tungsten diselenide (WSe2), for gas sensor applications. Our method entailed building a chemically liquid exfoliated WSe2 gas sensing device with gold (Au) electrodes to measure its reaction and sensitivity to environmental gasses such as CO2 and N2. The 2D thin film was created through a solution processing method and electrically coupled in a two-terminal configuration; photonic curing system along with the hot plate annealing process was used on the thin film for rapid annealing, enhancing particle connectivity, stable crystal structure, and increasing overall electrical conductivity. The inkjet printing technology is used to explore the potential of the 2D thin film fabrication process that defines a well-controlled and scalable additive manufacturing process at the nano level that makes it possible to develop next-generation flexible devices. The additive nano-manufacturing process allowed us to establish the film's structure and chemical properties before measuring the electrical characteristics of the films when exposed to CO2 and N2 gases at room temperature. To explore and validate the sensitivity to human interaction with the gas-sensing device, we carried out further experiments with direct exposure to human breath in an open environmental space which shows a promising landmark for developing a next-generation flexible breath-sensing device.

<p dir="ltr">Multiferroics, which exhibit multiple ferroic orderings within a single material system, have substantial potential for applications in sensors, transducers, memory devices, and energy harvesters. However, the development of single-phase multiferroics that demonstrate roomtemperature properties remains limited by inherent contradictions in d-orbital occupancy between magnetic and ferroelectric materials. This dissertation focuses on addressing this challenge through the exploration of a novel bismuth-based, single-phase multiferroic thin film that features an exotic layered supercell (LSC) structure and displays multiferroic properties at room temperature. The primary aim is to deepen the understanding of LSC materials and advance their applications in practical devices. The dissertation is structured as follows: It begins with an introduction to the fundamental concepts of multiferroics, including their classifications and applications, the specific characteristics and growth mechanism of LSC materials, and other relevant background knowledge. This is followed by a detailed description of the experimental techniques employed. The core of this dissertation comprises four chapters that present a comprehensive study of LSC materials. The first chapter discusses a nanocomposite system combining an LSC material, Bi1.25AlMnO3.25, with Au nanoparticles (NPs), highlighting its tunable microstructure and multifunctional properties influenced by growth temperature. The second chapter explores the integration of Bi2NiMnO6 on a flexible mica substrate, demonstrating the potential of LSC materials for use in flexible electronics, with performance maintained across various bending conditions. The third chapter details the development of freestanding LSC thin films by utilizing a water-soluble sacrificial layer, which are shown to preserve their microstructure and properties after being transferred onto a silicon substrate. Building on this, the fourth chapter investigates the reuse of recycled SrTiO3 substrates for subsequent thin film growth, examining changes in surface strain states and chemistry to guide sustainable practices in complex oxide thin film processing. In summary, this dissertation presents an extensive examination of LSC multiferroics, revealing their significant promise for multifunctional applications and integration into flexible and silicon-based electronics. Additionally, the work explores sustainable methods for substrate reuse, contributing further to the field of material sciences.<br></p>

Electric vehicles aim to carry the torch into a sustainable future. An optimized cooling system is crucial to an Electric Drive Unit (EDU). A smartly designed cooling system will deliver high-performance, efficient and long-lasting EDUs at lower costs. One way to achieve that is to have an integrated cooling system. When the electric motor and transmission share a common oil, the oil returning from the transmission side is aerated due to spraying and splashing. This aeration affects the pump performance and may reduce the cooling performance of the oil. Thus, this thesis is initiated to understand the impact of aeration on heat transfer.     Oil aeration is the presence of air in oil. This aeration depends on the air content and bubble sizes mixed in the oil. Typically, there is also some amount of dissolved air in any oil. Depending on the type of aeration, the oil will appear lighter than its usual colour and have a very foamy texture, showing a change in the properties of the fluid, for example density, viscosity and heat transfer.    An experimental setup is built in order to replicate and study the effect of aeration on local heat transfer. A flat channel with rectangular cross-section is designed with three parts – a bottom plate, a flow spacer channel and a top transparent plate. The oil and air are mixed before they enter the channel and then heated using thin film heaters. A groove within the bottom plate houses an insulating material, the thin film heater, a thermocouple touching the heater and a thermochromic liquid crystal sheet facing the fluid mixture. The thermocouple gives temperature readings from a single point between the heater and the insulating material. Meanwhile, the liquid crystal sheets come in different desired temperature ranges and change in colour from red to blue to show the surface temperatures over an area. So, the surface temperature of the mixed fluid flow can be recorded visually over an area with the thin film heater under it to calculate the heat transfer coefficients accordingly.    The drop in Nusselt number and heat transfer rates with increased aeration in the working fluid is the main highlight and result. The size of the air bubbles in the channel also determine how fast the heat transfer rate drops.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第25303号 / 工博第5262号 / 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 陰山 洋, 教授 作花 哲夫, 教授 田中 勝久 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Within the last decade, organic light-emitting diodes (OLEDs) have evolved to be one of the major players in the display panel market. For instance, in 2023, it is expected that about half of the produced smartphones incorporate an OLED display. This rapid development is based on the high image quality and fast response time of OLEDs compared to the previously dominating technology of liquid crystal displays. Additionally, OLEDs feature interesting properties like mechanical flexibility, areal light emission, and semi-transparency that allow for futuristic device designs in display or lighting applications. One of the major drawbacks of OLEDs is their limited efficiency compared to conventional light-emitting diodes (LEDs). Due to the high refractive index of their active, light-emitting layers, a large portion of the internally generated light is lost because of optical effects like total internal reflection. One promising approach, which increases the amount of outcoupled light, is to align the transition dipole moment (TDM) of the emitter molecules parallel to the interface planes of the device. In the best case, this method can yield an efficiency improvement of more than 50%. This thesis focuses on both the accurate measurement and the exploration of control strategies of the emitter orientation. Furthermore, a software tool is developed, which supports the device design and data evaluation. First, the state-of-the-art emitter orientation measurement technique is analyzed, which is angle-resolved photoluminescence spectroscopy (ARPS). A ray-optics model is developed in order to quantify the impact of experimental deviations from the ideal measurement configuration. In particular, a displacement of the light-emission spot from the rotation center of the measurement setup is investigated. The resulting alteration of the observable angle-resolved emission spectrum is calculated and the impact on the consequent orientation factor is estimated. Based on the optical model, a refined setup structure is proposed, which not only circumvents a part of the identified problems but also yields a ten-times increased signal-to-noise ratio (SNR). Subsequently, it is explored how the emitter orientation can be controlled by external physical parameters during and after processing. Selected phosphorescent organic model systems are exposed to elevated temperatures and electric fields. In the first measurement series, the impact of the substrate temperature during deposition (𝑇sub) is investigated. It is found that the emitter orientation can be tuned from a more horizontal configuration at room temperature (RT) to an isotropic distribution if 𝑇sub approaches the glass transition temperature (𝑇g) of the material. This observation fits well to previous results of glass physics obtained with similar materials. In a second, alternative test series, OLEDs are treated after processing. Here, an emitter system comprising the host material NPB and the emitter Ir(piq)3 is investigated. For a treatment temperature of 125℃ and a simultaneously applied reverse bias of -20V the external quantum efficiency (EQE) of the OLEDs is increased by more than 50%. The effect is observed for two different emitter concentrations of 1 wt% and 10 wt% and OLEDs in the optical minimum and maximum. Finally, the long-term stability of the emitter orientation is experimentally demonstrated over a time frame of 1.5 years and for storage temperatures up to 95% of the host material’s 𝑇g. Preceding the presentation of the experimental results, the software-tool simojio is introduced, which is developed in this thesis. It enables an efficient and convenient workflow throughout the emitter orientation investigations and supports various tasks such as the device and setup design, the processing and visualization of xperimental data, and the extraction of orientation factors from angle-resolved emission spectra. Simojio provides a graphical user interface (GUI), which enables a flexible configuration of input parameters and one-dimensional layer structures. The corresponding numerical and graphical results are neatly arranged in a separate, tab-structured window. The actual calculation and processing algorithms are implemented in custom-made python modules, which can be modified and extended by the users according to their specific needs. Simojio is applied to most of the emitter orientation related simulation and data-processing tasks, which are presented in this thesis. However, due to its flexible, modular architecture, it is not restricted to this use case but may be utilized for highly diverse numerical problems, which are based on the evaluation of generic parameters or one-dimensional structures.

Mesoporous semiconductors such as TiO2 nanoparticles, as well as transparent conducting oxides (TCOs) such as indium tin oxide films are typically employed for setting up the photo-electrode module in variety of photoelectrochemical cells including Dye-Sensitized Solar Cells (DSSCs). In order to exhibit a high performance efficiency, the photo-electrodes in such applications are required to be able to harvest the light and transport the generated electrons effectively. Accordingly mesoporous layers with high values of surface area and well-established pore structure along with highly transparent and conductive TCOs are deposited on suitable substrates through the physical or chemical vapor deposition methods. The processing facilities and materials required to fabricate such high-quality devices with high values of efficiency are complicated and expensive, whereas devices of lower quality do not fulfill the demands. This issue is of particular importance regarding the energy production and developing the solar cell technologies, as it is considered by the concept of “cost per watt”. Thus, a great deal of effort is being carried out globally to enhance the efficiency of affordably-produced solar cells such as low-cost DSSCs. Utilizing the wet chemical techniques such as sol-gel method which provide a considerably more affordable route to synthesize nanoparticles and deposit thin films without the need of applying high temperature or vacuum condition is a widely-used approach to decrease the processing expenses. However, to achieve an acceptable cost-per-watt ratio requires enhancing the obtained efficiency value as well, and therefore, modifying the processing procedures to improve the required features of the products are highly encouraged. This thesis focuses on two individual activities: synthesis of TiO2 nanoparticles, and also thin film deposition of a promising TCO called aluminum-doped zinc oxide (AZO); both obtained through the sol-gel route that is modified to contribute to nanostructures with suitable features for application in photoelectrochemical devices such as DSSC. In the first part, mesoporous anatase nanoparticles were synthesized through the surfactant-mediated sol–gel route. Through changing the refluxing time and water-to-surfactant molar ratio, as-prepared nanocrystals of high density and large and narrowly-distributed pore sizes were obtained, displaying surface area values up to 240 m2·g-1, much higher than the reported values for commercial TiO2-based catalysts. In the second part, sol–gel dip–coating of ZnO thin films doped with 2 at.% of aluminium ions was carried out. By altering the hydrolysis reaction and changing the thermal treatment procedure, thin films of highly c-axis preferred orientation were obtained with optical transmittance of around 80% and resistivity values down to 6 – 15 mΩ·cm, corresponding to sheet resistance of around Rsh ~ 500 Ω/sq. The obtained conductivity values, even though one order magnitude lower than those reported for the AZO thin film prepared via expensive techniques, are in the suitable range to improve the cost per watt ratio in applications such as inkjet printing of low-cost printed electronics and more affordable DSSC devices.

Die vorliegende Arbeit befasst sich mit dem Dünnfilmwachstum der ternären Oxide Na2IrO3, Li2IrO3, Y2Ir2O7 und YBiO3. All diesen oxidischen Materialien ist gemein, dass sie Verwirklichungen sogenannter Topologischer Isolatoren oder Spin-Flüssigkeiten sein könnten. Diese neuartigen Materiezustände versprechen eine zukünftige Anwendung in der Quantencomputation, in magnetischen Speichern und in elektrischen Geräten mit geringer Leistungsaufnahme. Die Herstellung der hier gezeigten Dünnfilme ist daher ein erster Schritt zur Umsetzung dieser Anwendungen in der Zukunft. Alle Dünnfilme werden mittels gepulster Laserplasmaabscheidung auf verschiedenen einkristallinen Substraten hergestellt. Die strukturellen, optischen und elektrischen Eigenschaften der Filme werden mittels etablierter experimenteller Verfahren wie Röntgenbeugung, spektroskopischer Ellipsometrie und elektrischenWiderstandsmessungen untersucht. Die strukturellen Eigenschaften von erstmalig in der Masterarbeit des Authors verwirklichten Na2IrO3-Dünnfilmen können durch Abscheidung einer ZnO-Zwischenschicht deutlich verbessert werden. Einkristalline Li2IrO3-Dünnfilme mit einer definierten Kristallausrichtung werden erstmalig hergestellt. Die Messung der dielektrischen Funktion gibt Einblick in elektronische Anregungen, die gut vergleichbar mit Li2IrO3-Einkristallen und verwandten Iridaten sind. Des Weiteren wird aus den Daten eine optische Energielücke von ungefähr 300 meV bestimmt. In Y2Ir2O7-Dünnfilmen wird eine mögliche (111)-Vorzugsorientierung in Wachstumsrichtung gefunden. Im Vergleich mit der chemischen Lösungsabscheidung zeigen die hier mittels gepulster Laserplasmaabscheidung hergestellten YBiO3-Dünnfilme eine definierte, biaxiale Kristallausrichtung in der Wachstumsebene bei einer deutlich höheren Schichtdicke. Über die gemessene dielektrische Funktion können eine direkte und indirekte Bandlücke bestimmt werden. Deren Größe gibt eine notwendige experimentelle Rückmeldung an theoretische Berechnungen der elektronischen Bandstruktur von YBiO3, welche zur Vorhersage der oben erwähnten, neuartigen Materiezuständen verwendet werden. Nach einer Einleitung und Motivation dieser Arbeit gibt das zweite Kapitel einen Überblick über den gegenwärtigen Forschungsstand der hier untersuchten Materialien. Die folgenden zwei Kapitel beschreiben die Probenherstellung und die verwendeten experimentellen Untersuchungsmethoden. Anschließend werden für jedes Material einzeln die experimentellen Ergebnisse dieser Arbeit diskutiert. Die Arbeit schließt mit einer Zusammenfassung und einem Ausblick. / The present thesis reports on the thin film growth of ternary oxides Na2IrO3, Li2IrO3, Y2Ir2O7 and YBiO3. All of these oxides are candidate materials for the so-called topological insulator and spin liquid, respectively. These states of matter promise future application in quantum computation, and in magnetic memory and low-power electronic devices. The realization of the thin films presented here, thus represents a first step towards these future device applications. All thin films are prepared by means of pulsed laser deposition on various single-crystalline substrates. Their structural, optical and electronic properties are investigated with established experimental methods such as X-ray diffraction, spectroscopic ellipsometry and resistivity measurements. The structural properties of Na2IrO3 thin films, that were previously realized in the author’s M. Sc. thesis for the first time, are improved significantly by deposition of an intermediate ZnO layer. Single-crystalline Li2IrO3 thin films are grown for the first time and exhibit a defined crystal orientation. Measurement of the dielectric function gives insight into electronic excitations that compare well with single crystal samples and related iridates. From the data, an optical energy gap of about 300 meV is obtained. For Y2Ir2O7 thin films, a possible (111) out-of-plane preferential crystal orientation is obtained. Compared to chemical solution deposition, the pulsed laser-deposited YBiO3 thin films presented here exhibit a biaxial in-plane crystal orientation up to a significantly larger film thickness. From the measured dielectric function, a direct and indirect band gap energy is determined. Their magnitude provides necessary experimental feedback for theoretical calculations of the electronic structure of YBiO3, which are used in the prediction of the novel states of matter mentioned above. After the introduction and motivation of this thesis, the second chapter reviews the current state of the science of the studied thin film materials. The following two chapters introduce the sample preparation and the employed experimental methods, respectively. Subsequently, the experimental results of this thesis are discussed for each material individually. The thesis concludes with a summary and an outlook.