Zinc air batteries are among the most promising energy storage devices due to their high energy density, low cost and environmental friendliness. The low mass and cost of zinc air batteries is a result of traditional active materials replacement with a thin gas diffusion layer which allows the battery to use the oxygen directly from the air. Despite the environmental and electronic advantages offered by this system, challenges related to drying the electrolyte and catalyst, determining a high activity bifictional catalyst, and ensuring durability of the gas diffusion layer need to be optimized during the fabrication of rechargeable zinc-air batteries. To date, platinum on carbon (Pt/C) provides the best electrochemical catalytic activity in acidic and alkaline electrolytes. However, the difficult acquisition and high cost of this catalyst mandates investigation into a new composition or synthesis of a bifunctional catalyst. A number of non-precious metal catalyst have been introduced for zinc-air batteries. Nevertheless, their catalytic activities and durability are still too low for commercial rechargeable zinc-air batteries. Thus, it is very important to synthesize a highly active bifunctional catalyst with good durability for long term charge and discharge use. In this study, it is proposed that a manganese-based perovskite oxide nanoparticle combined with nitrogen doped carbon nanotubes willshow promising electrochemical activity with remarkable cycle stability as a bifunctional catalyst for zinc-air batteries. In the first part of this work, nano-sized LaMnO3 and LaMn0.9Co0.1O3 were prepared to research the effectiveness of Co doping into LaMnO3 and its effect on electrochemical catalytic activities. To prepare LaMnO3 and LaMn0.9Co0.1O3, a hydrothermal reaction method was applied to synthesize nanoparticles which can increase the activity of perovskite type oxides. The result shows that while perovskite oxides replacing 10 wt. % of Mn doped with Co metal did not iv change its crystalline structure, the oxygen evolution reaction (OER) performance was increased by 600%. In the second part, a core-corona structured bifunctional catalyst (CCBC) was synthesized by combining LaMn0.9Co0.1O3 nanoparticles with nitrogen doped carbon nanotubes (NCNT). NCNT was chosen because of its large surface area and high catalytic activity for ORR. SEM and TEM analysis show that metal oxide nanoparticles were surrounded with nanotubes. Based on the electrochemical performances, ORR and OER activity is attributed to NCNT and the metal oxide core, respectively, complementing the activities of each other. Furthermore, its unique morphology introduces synergetic activity especially for OER. Electrochemical test results show that the onset potential was enhanced from -0.2 V (in LaMnO3 and LaMn0.9Co0.1O3) to -0.09 V (in CCBC) and the half wave potential was improved from -0.38 V to -0.19 V. In the third part, a single cell zinc-air battery test was performed using CCBC as the bifunctional catalyst for the air electrode. These results were compared with battery performance against a high-performance and expensive Pt/C based air catalyst. The results show that the battery containing catalytic CCBC consumes less energy during charge/discharge. The single cell long-term durability performance was compared, further proving that CCBC provides a more suitable catalyst for zinc-air battery than Pt/C.

Perovskite oxides have the general chemical formula ABO3, where A is a rare-earth or alkali-metal cation and B is a transition metal cation. Perovskite oxides can be formed with a variety of constituent elements and exhibit a wide range of properties ranging from insulators, metals to even superconductors. With the development of growth and characterization techniques, more information on their physical and chemical properties has been revealed, which diversified their technological applications. Perovskite manganites are widely investigated compounds due to the discovery of the colossal magnetoresistance effect in 1994. They have a broad range of structural, electronic, magnetic properties and potential device applications in sensors and spintronics. There is not only the technological importance but also the need to understand the fundamental mechanisms of the unusual magnetic and transport properties that drive enormous attention. Manganites combined with other perovskite oxides are gaining interest due to novel properties especially at the interface, such as interfacial ferromagnetism, exchange bias, interfacial conductivity. Doped manganites exhibit diverse electrical properties as compared to the parent compounds. For instance, hole doped La0.7Sr0.3MnO3 is a ferromagnetic metal, whereas LaMnO3 is an antiferromagnetic insulator. Since manganites are strongly correlated systems, heterojunctions composed of manganites and other perovskite oxides are sunject to complex coupling of the spin, orbit, charge, and lattice degrees of freedom and exhibit unique electronic, magnetic, and transport properties. Electronic reconstructions, O defects, doping, intersite disorder, magnetic proximity, magnetic exchange, and polar catastrophe are some effects to explain these interfacial phenomena. In our work we use first-principles calculations to study the structural, electronic, and magnetic properties of manganite based superlattices. Firstly, we investigate the electronic structure of bulk CaMnO3 and LaNiO3. An onsite Coulomn interaction term U is tested for both the Mn and Ni atoms. G-type antiferromagnetism and insulating properties of CaMnO3 are reproduced with U = 3 eV and ferromagnetic ordering is favorable when CaMnO3 is strained to the substrate lattice constant. This implies that the CaMnO3 magnetism is sensitive to both strain and the U parameter. Antiparallel orientation of the Mn and Ti moments has been found experimentally in the BiMnO3/SrTiO3 superlattice. By introducing O defects at different layers, we find similar patterns when the defect is located in the BiO layer. The structural, electronic and magnetic properties are analysed. Strong hybridization between the d3z2−r2 orbitals of the Mn and Ti atoms near the O defect is found. The effect of uniaxial strain for the formation of a two-dimensional electron gas and the interfacial Ti magnetic moments of the (LaMnO3)2/(SrTiO3)2 superlattice are investigated. By tuning the strain state from compressive to tensile, we predict under which conditions the spin-polarization of the electron gas is enhanced. Since the thickness ratio of the superlattice correlates with the strain state, we also study the structural, electronic and magnetism trends of (LaMnO3)n/(SrTiO3)m superlattices with varying layer thicknesses. The main finding is that half-metallicity will vanish for n, m > 8. Reduction of the minority band gaps with increasing n and m originates mainly from an energetic downshift of the Ti dxy states. Along with these, the interrelation between the interface geometry and the electronic properties of the antiferromagnetic/ferromagnetic superlattice BiFeO3/ La0.7Sr0.3MnO3 is investigated. The magnetic and optical properties are also analysed by first principles calculations. The half-metallic character of bulk La0.7Sr0.3MnO3 is maintained in the superlattice, which implies potential applications on spintronics and memory devices.

abstract: Integrated oxide/semiconductor heterostructures have attracted intense interest for device applications which require sharp interfaces and controlled defects. The research of this dissertation has focused on the characterization of perovskite oxide/oxide and oxide/semiconductor heterostructures, and the analysis of interfaces and defect structures, using scanning transmission electrom microscopy (STEM) and related techniques. The SrTiO3/Si system was initially studied to develop a basic understanding of the integration of perovskite oxides with semiconductors, and successful integration with abrupt interfaces was demonstrated. Defect analysis showed no misfit dislocations but only anti-phase boundaries (APBs) in the SrTiO3 (STO) films. Similar defects were later observed in other perovskite oxide heterostructures. Ferroelectric BaTiO3 (BTO) thin films deposited directly onto STO substrates, or STO buffer layers with Ge substrates, were grown by molecular beam epitaxy (MBE) in order to control the polarization orientation for field-effect transistors (FETs). STEM imaging and elemental mapping by electron energy-loss spectroscopy (EELS) showed structurally and chemically abrupt interfaces, and the BTO films retained the c-axis-oriented tetragonal structure for both BTO/STO and BTO/STO/Ge heterostructures. The polarization displacement in the BTO films of TiN/BTO/STO heterostructures was investigated. The Ti4+ atomic column displacements and lattice parameters were measured directly using HAADF images. A polarization gradient, which switched from upwards to downwards, was observed in the BTO thin film, and evidence was found for positively-charged oxygen vacancies. Heterostructures grown on Ge substrates by atomic layer deposition (ALD) were characterized and compared with MBE-grown samples. A two-step process was needed to overcome interlayer reaction at the beginning of ALD growth. A-site-rich oxide films with thicknesses of at least 2-nm had to be deposited and then crystallized before initiating deposition of the following perovskite oxide layer in order to suppress the formation of amorphous oxide layers on the Ge surface. BTO/STO/Ge, BTO/Ge, SrHfTiO3/Ge and SrZrO3/Ge thin films with excellent crystallinity were grown using this process. Metal-insulator-metal (MIM) heterostructures were fabricated as ferroelectric capacitors and then electrically stressed to the point of breakdown to correlate structural changes with electrical and physical properties. BaTiO3 on Nb:STO was patterned with different top metal electrodes by focused-ion-beam milling, Au/Ni liftoff, and an isolation-defined approach. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2018

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第22451号 / 工博第4712号 / 新制||工||1736(附属図書館) / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 田中 勝久, 教授 田中 功, 教授 陰山 洋 / 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20389号 / 工博第4326号 / 新制||工||1670(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 江口 浩一, 教授 陰山 洋, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

La détection de gaz, qui utilise aujourd'hui principalement des capteurs optiques, des capteurs électrochimiques à base de plomb et des capteurs catalytiques est un marché très porteur (estimé à 3 milliards d'euros) et doté d'une forte croissance (10% par an). La nécessité de développer de nouveaux systèmes d'instrumentation dédiés à la surveillance de la qualité de l'air intérieur et à la détection de substances dangereuses implique l'étude et le développement de nouveaux capteurs élaborés à partir de produits compatibles avec les enjeux environnementaux (RoHs, REACH), et économiques (matériaux à faible coût, techniques de réalisation fiables, durée de vie élevée). Le projet ANR OSPÉGAZ (Oxydes sans plomb pour la détection de gaz) vise à développer des systèmes d'instrumentations intégrés innovants dédiés à la caractérisation des différentes expositions environnementales en lien notamment avec les actions recommandées dans le cadre du PNSE2 pour les impacts sanitaires avérés. Le travail de thèse présenté dans ce manuscrit fait partie du projet OSPÉGAZ. L'objectif du travail a été, d'une part, de mettre au point un nouveau procédé d'élaboration d'encre au sein du laboratoire UDSMM pour l'élaboration et la caractérisation de films épais poreux, et d'autre part, de réaliser des capteurs de gaz à base de ces films. Nous avons choisi d'utiliser le matériau BaTiO₃, bien connu de la littérature, comme matériau de départ afin de mettre au point le procédé d'élaboration de couches épaisses. Par la suite, nous avons choisi le BaSrTiFeO₃ comme matériau sensible au gaz, et nous avons étudié deux compositions correspondant à deux taux de fer : Ba₀.₈₅Sr₀.₁₅Ti₀.₉Fe₀.₁O₃ (BSTF 10%) et Ba₀.₈₅Sr₀.₁₅Ti₀.₉₈Fe₀.₀₂O₃ (BSTF 2%). Ces matériaux ont été caractérisés dans une large gamme de fréquence (100 Hz à 1 MHz) et de température (25°C à 500°C). Les propriétés diélectriques en fonction de la fréquence et de la température ont été étudiées sur deux structures différentes d'électrodes : capacité parallèle (MIM) et capacité interdigitée (CID). Enfin, des démonstrateurs de capteurs de gas basés sur le principe des capteurs semi-conducteurs, ont été réalisés à partir de films épais poreux (BT, BST, BSFT 10% et 2%). Ces démonstrateurs ont été testés dans les locaux de la société SIMTRONICS sous différents gaz comme le monoxyde de carbone CO (200ppm), le sulfure d'hydrogène H₂S (50ppm) et le dioxyde de soufre SO₂ (20ppm) à 400°C et 450°C. Sous H₂S (50ppm), ils ont montré une plus grande sensibilité relative du BSTF (10%) (55.4%) par rapport au BSTF (2%) (48%) à 450°C. La bonne sensibilité relative et la réponse dynamique très intéressante montrent que le matériau BSTF dispose d'un potentiel très intéressant pour la détection de gaz. L'optimisation de la géométrie des capteurs, du taux de fer et de la température de fonctionnement devrait nous permettre d'améliorer les performances de nos démonstrateurs. / Today gas detection, which now mainly uses optical sensors, electrochemical sensors based on lead, and catalytic sensors, is a very promising market (estimated at 3 billion euros) with a strong growth (10% per year). The need for new instrumentation systems dedicated to the monitoring of the air quality and to the detection of hazardous substances, requires the study and development of new sensors compatible with the European environmental standards : Restriction of the use of Hazardous Substances (RoHS) ; Registration, Evaluation and Authorization of Chemicals (REACh). The OSPÉGAZ project aims to develop innovative integrated instrumentations systems for the characterization of different environmental exposures linked to the actions recommended by the PNSE2 for proven health impacts. Our research project aims to develop innovating and cost-effective gas sensors containing lead-free oxides and dedicated to the detection of flammable gases and protection against toxic risks. The works of the thesis presented in this manuscript is a part of this project. The objectives were, firstly, to develop a new process for ink preparation in UDSMM laboratory, for the elaboration, electrical and physicochemical characterizations, of thick porous film, and secondly to make gas sensors based on these films. We chose to use the BaTiO3 (well-known material in literature) material as a first material in order to develop the process of thick film elaboration. After that, we chose the BaSrTiFeO₃ as gas-sensitive material, and we studied two compositions of Ba₁₋ ₓ Sr ₓ Ti₁₋yFeyO₃ with two different concentrations or iron : Ba₀.₈₅Sr₀.₁₅Ti₀.₉Fe₀.₁O₃ (BSTF 10%) and Ba₀.₈₅Sr₀.₁₅Ti₀.₉₈Fe₀.₀₂O₃ (BSTF 2%). Electrical characterizations were made in a wide range of frequency (100 HZ to 1 MHz) and temperature (25° C to 500° C). The dielectric properties as a function of temperature and frequency were studied using two different structures of capacitance : metal-insulator-metal (MIM) and interdigital electrodes (CID). Finally we have developed semi-conductor gas sensors based on BT, BST and BSTF (10% ; 2%) thick films. All our sensors were tested under different gases such as carbon monoxide CO (200ppm), hydrogen sulphide H₂S (50ppm) and sulfur dioxide SO₂ (20ppm), at various temperature, in the laboratory of SIMTRONICS SAS. We have measured the greatest relative sensitivity under H₂S (50ppm) gas ; 55.4% and 48% respectively for BSTF (10%) and BSTF (2%), at 450°C. Good relative sensitivity and very interesting dynamic responsesof BSTF show that the material has a great potential for the detection of gas. The optimization of the sensor geometry, iron rate and operating temperature should allow us to improve the performance of our demonstrators.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第18995号 / 工博第4037号 / 新制||工||1621(附属図書館) / 31946 / 京都大学大学院工学研究科材料化学専攻 / (主査)教授 田中 勝久, 教授 平尾 一之, 教授 三浦 清貴 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

No description available.

Perovskit-Oxide weisen eine große Bandbreite an physikalischen Eigenschaften bei gleichzeitig hoher struktureller Qualität in kleinsten Dimensionen auf. Die dramatischen Veränderungen ihrer Eigenschaften bei nur geringer Variation der stöchiometrischen Zusammensetzung sind sowohl für ein tieferes physikalisches Verständnis als auch für mögliche Anwendungsperspektiven interessant. In der vorliegenden Arbeit wurde der Einfluss von Ladungsübertragung an Grenz- flächen, Anisotropiemodifikation durch Verspannung und Oberflächeneffekte sowie magnetische und strukturelle Kopplung untersucht. Aufgrund ihrer kontrastierenden Eigenschaften im Hinblick auf Ferromagnetismus und Ladungstransport wurden dotiertes Lanthanmanganat und Strontiumruthenat (SRO) für die Untersuchungen ausgewählt. Durch ihre hervorragenden Wachstumseigenschaften mit fehlerlosen Grenzflächen auf atomarer Ebene erlauben sie als Modellsystem die Untersuchung elektronischer, magnetischer und struktureller Kopplung in Perovskit-Oxiden – mit folgenden Ergebnissen: Durch Ladungsübertragung an Grenzflächen wird Ferromagnetismus in Schichten von weniger als vier Einheitszellen in Manganaten stabilisiert. Die mikroskopische Struktur der Systeme kann aus der Analyse der durch die Anisotropie bedingten Symmetrie der winkelabhängigen Magnetotransport- messungen erschlossen werden. Bei abnehmender Schichtdicke verringert sich die intrinsische orthorhombische Symmetrie in SRO zugunsten einer tetragonalen aufgrund der Symmetriebrechung an der Grenzfläche. Die Untersuchungen des anormalen Hall Effekts unterstreichen seine Tensor-Natur und zeigen eine Abhängigkeit des Vorzeichens sowohl von der magnetischen Anisotropie als auch der mikroskopischen Schichtqualität. Die Beobachtung einer Anisotropie oberhalb der Übergangstemperatur von SRO in Manganatschichten einer Dicke von zwei bis sechs Einheitszellen weist auf eine strukturelle Kopplung über die Sauerstoffoktaederrotationen hin. Die komplexe Wechselwirkung zwischen antiferromagnetischer Kopplung und schichtdickenabhängiger Anisotropie und dem magnetischen Moment werden in einem 2-Schichten-Modell beschrieben. Übergitter mit Einzelschichten von weniger als drei Einheitszellen lassen sich nicht mehr mit individuellen Einzelschichten beschreiben sondern stellen einen künstlichen Ferrimagneten dar. / Perovskite oxides show a range of physical properties in combination with high structural quality in small dimensions. The dramatic change of their properties upon small variation in stoichiometry or external influences as pressure/strain are interesting for both a deeper understanding of fundamental condensed matter physics as well as electronic applications. In the present thesis the influence of charge transfer at interfaces, modification of the magnetic anisotropy by strain and surface effects, as well as magnetic and structural coupling was studied. In virtue of their contrasting ferromagnetic and transport properties, charge doped lanthanum manganite and strontium ruthenate (SRO) were chosen for this study. Their superior growth properties allowing atomically flat defect free interfaces make them a model system to study electronic magnetic and structural coupling phenomena in perovskite oxides − with the following findings: Charge transfer at interfaces stabilizes ferromagnetism in single layers of manganites down to one unit cell thickness similar to finite size scaling in ordinary transition metal ferromagnets. The microscopic structure of crystalline layers can be obtained from an analysis of the symmetries present in angle dependent magnetotransport measurements, which are determined by the anisotropy. Upon thickness reduction, the intrinsic orthorhombic symmetry in SRO is reduced in favour of a tetragonal one owing to the symmetry breaking at the interface. Studies on the anomalous Hall effect underline its tensorial nature and show a sign dependence on both magnetic anisotropy and microstructural quality. The observation of an in-plane anisotropy in manganite layers in the thickness range of two to six unit cells indicates a structural coupling via the oxygen octahedra. The complex interplay of antiferromagnetic coupling and layer thickness dependent anisotropy and magnetic moment are described in a bilayer model. Superlattices with individual layers of less than three unit cells cannot be described by the individual layer properties but represent an artificial ferrimagnet.

Ein großes Hindernis für die Anwendbarkeit von oxidischen Perowskiten in elektrotechnischen oder spintronischen Applikationen, ist die Größe der spezifischen Temperaturen, bei der die physikalischen Phänomene, wie Ferromagnetismus oder Hochtemperatur-Supraleitung, beobachtet werden können. Die physikalischen Eigenschaften der Perowskite zeigen eine Abhängigkeit von der Ordnung der verschiedenartigen Metallionen in mehrkomponentigen Systemen. Die Abhängigkeit ergibt sich durch den Einfluss der Metallionen auf die Elektronenkonfiguration und elastischen Verspannung innerhalb des Materials. Man spricht in diesem Zusammenhang auch von der Kontrolle der Füllung und der Bandbreite der elektronischen Bänder im Material durch die Wahl der Metallionen. Die Zielsetzung dieser Arbeit ist die Präparation und Charakterisierung von künstlich A-Platz geordneten schmal- und breitbandigen Manganat Dünnfilmen als auch von natürlich B-Platz geordneten ferro-/ferrimagnetischen doppelperowskitischen Dünnfilmen. Für die Präparation der dünnen Schichten wurde die unkonventionelle Metallorganischen Aerosol Deposition (MAD) verwendet. Es konnte gezeigt werden, dass diverse künstlich oder natürlich Kationengeordnete Perowskite mit der MAD Technologie präpariert werden können. Die lagenweise A-Platz Ordnung in Manganaten führt, über die Modulation der Gitterverspannung und der Elektronenbesetzung im eg-Band der Manganionen, zu modifizierten elektronischen und magnetischen Eigenschaften. In schmalbandigen CMR Manganaten wurde die PS und somit der CMR über die Ordnung beeinflusst, während in breitbandigen CMR Manganaten ein Weg aufgezeigt werden konnte, der zu Übergangstemperaturen TC > 370K führen kann. In geordneten, ferromagnetischen Doppelperowskiten wurde der Einfluss und die Anwesenheit von Antiphasen-Grenzen dargelegt. Über die Einführung einer aktiven Valenz-Kontrolle, konnte die Präparation von halbmetallischen, ferrimagnetischen Doppelperowskiten mit der MAD Technologie ermöglicht werden.