Electronic inhomogeneities play an important role in the definition of physical properties of correlated systems. To study these inhomogeneities one has to use local probe techniques which can distinguish electronic, magnetic and structural variations at the nanoscale. In the present work the high-field electron spin resonance technique (HF-ESR) is used to probe electronic and magnetic inhomogeneities in two transition-metal element based systems with very different properties. The first system is an iron based hightemperature superconductor, namely a member of a so called 1111-family, the (La,Gd)O1−xFxFeAs compound. Our HF-ESR spectroscopy study on Gd3+ ion has revealed that this material exhibits anisotropic interaction between Gd and Fe layers, which is frustrated in the absence of an external magnetic field. Moreover, the study of the superconducting samples has shown a coexistence of a static short range magnetic order with superconductivity up to high doping levels. The second system is a lightly hole doped cubic perovskite LaCoO3. Here, our HF-ESR investigation, complemented with static magnetometry and nuclear magnetic resonance techniques, has established that the hole doping induces a strong interaction between electrons on neighboring Co ions which leads to a collective high-spin state, called a spin-state polaron. These polarons are inhomogeneously distributed in the nonmagnetic matrix. This thesis is organized in three chapters. The first chapter gives basic ideas of magnetism in solids, focusing on the localized picture. The aim of the second chapter is to introduce the method of ESR. The third chapter is dedicated to the study of 1111-type iron arsenide superconductors. In the first part X-band (9.5 GHz) ESR measurements on 2% and 5% Gd-doped LaO1−xFxFeAs are presented. In the second part a combined investigation of the properties of GdO1−xFxFeAs samples by means of thermodynamic, transport and high-field electron spin resonance methods is presented. The last, fourth chapter presents the investigation of the unexpected magnetic properties of lightly hole-doped LaCoO3 cobaltite by means of the electron spin resonance technique complemented by magnetization and nuclear magnetic resonance measurements.

<p> This thesis demonstrates two concepts, one a viable fabrication process for an FeCr alloy supported solid oxide fuel cell (SOFC), and second, the use of CozMn04 (spinel)as the cathode material. Ni/YSZ and YSZ layers were used as anode and electrolyte respectively. The fabrication process consisted of tape casting of iron and chromium oxide powders for the support, dip coating of NiO-YSZ-Fe30 4-Crz03-C and YSZ as anode and electrolyte respectively, synthesis of CozMn04 from Co304 and MnOz as the , cathode material and finally screen printing of the CozMn04 cathode. The support, the anode, and the electrolyte were co-fired at 1350°C in air for 10 hours, then CozMn04 was screen printed and the cell was again fired at 1250°C for 4 hours in air. The complete cell was reduced in pure Hz at 950°C for 10 hours to convert the major part of support into Fe-Cr alloy, leaving approximately 20% unreduced FeCrz04. </p> <p> The fully fabricated cell was tested at 820°C using 7% Hz, 93% Nz as the fuel and air as the oxidant. The Co2MnO4 cathode which reduced to MnO + Co during the final processing stage was recovered in-situ at the start of the test. Pt mesh was used for current collection. The power density was in the range of 80-120 mW/cm2. </p> / Thesis / Master of Applied Science (MASc)

Electronic inhomogeneities play an important role in the definition of physical properties of correlated systems. To study these inhomogeneities one has to use local probe techniques which can distinguish electronic, magnetic and structural variations at the nanoscale. In the present work the high-field electron spin resonance technique (HF-ESR) is used to probe electronic and magnetic inhomogeneities in two transition-metal element based systems with very different properties. The first system is an iron based hightemperature superconductor, namely a member of a so called 1111-family, the (La,Gd)O1−xFxFeAs compound. Our HF-ESR spectroscopy study on Gd3+ ion has revealed that this material exhibits anisotropic interaction between Gd and Fe layers, which is frustrated in the absence of an external magnetic field. Moreover, the study of the superconducting samples has shown a coexistence of a static short range magnetic order with superconductivity up to high doping levels. The second system is a lightly hole doped cubic perovskite LaCoO3. Here, our HF-ESR investigation, complemented with static magnetometry and nuclear magnetic resonance techniques, has established that the hole doping induces a strong interaction between electrons on neighboring Co ions which leads to a collective high-spin state, called a spin-state polaron. These polarons are inhomogeneously distributed in the nonmagnetic matrix. This thesis is organized in three chapters. The first chapter gives basic ideas of magnetism in solids, focusing on the localized picture. The aim of the second chapter is to introduce the method of ESR. The third chapter is dedicated to the study of 1111-type iron arsenide superconductors. In the first part X-band (9.5 GHz) ESR measurements on 2% and 5% Gd-doped LaO1−xFxFeAs are presented. In the second part a combined investigation of the properties of GdO1−xFxFeAs samples by means of thermodynamic, transport and high-field electron spin resonance methods is presented. The last, fourth chapter presents the investigation of the unexpected magnetic properties of lightly hole-doped LaCoO3 cobaltite by means of the electron spin resonance technique complemented by magnetization and nuclear magnetic resonance measurements.

The thermoelectric properties and microstructure of two families of misfit type layered structure cobaltites were investigated for thermoelectric applications. Firstly, Bismuth strontium cobaltite ceramics with the formulations Bi2+xSr2Co2Oy (x=0, 0.1 and 0.2), Bi1.74Sr2Co1.8Oy and Bi2Sr2Co1.8Oy were produced using solid-state reaction (MO) method. The same powders were also used to produce ceramics by Spark Plasma Sintering (SPS) fabrication technique. SEM, high resolution XRD and HRTEM techniques has been employed to characterise the microstructure and crystal structures of the ceramics. Figure of merit (ZT) was also determined from measurement of electrical resistivity, Seebeck coefficient and thermal conductivity. Together with the above, calcium cobaltite of formulation Ca3-xBixCo3O9 (x=0 and 0.3) was also produced via MO and SPS routes. The same characterisation techniques were used for characterisation of calcium cobaltite. For Bi2+xSr2Co2Oy ceramics, it was found that SPS fabrication is essential to obtain high density samples. Excess bismuth has a major role in the adjustment of the microstructure and thermoelectric properties. The room temperature microstructure contains two minor phases with compositions of CoO and Bi0.75Sr0.25O1.26. The crystal structure of the main phase was successfully indexed and refined as misfit type structure having monoclinic symmetry with I2/a space group. A high ZT of 0.12 was achieved in both x=0.1 and 0.2 MO samples. For Bi2Sr2Co1.8Oy ceramics, the microstructure contains only one minor phase, Bi0.75Sr0.25O1.26. A high ZT of 0.16 was obtained at 900 K for this composition. For Bi1.74Sr2Co1.8Oy, it was not possible to obtain high density ceramics by MO route and SPS fabrication was necessary. However, SPS sample showed a low ZT of 0.04 at 900 K.For ceramics of formulation Ca3-xBixCo3O9 (x=0 and 0.3), it was difficult to obtain high density calcium cobaltite ceramics by MO route and SPS fabrication was found to be essential. In addition to improved density, SPS produced textured microstructure. Similar to bismuth strontium cobaltite, excess bismuth played a major role in microstructure development and thermoelectric properties. Single phase and high density Ca3Co4O9 ceramics were obtained by SPS. A minor phase of Bi2Ca2Co2Oy was found in the microstructure of Ca3-xBixCo3O4 (x=0.3) samples. A high ZT of 0.25 was obtained for Ca3Co4O9 SPS samples at 900 K through improvement of power factor. In-situ synchrotron XRD in the temperature range of 300-1223 K was performed on both Bi2Sr2Co2Oy and Ca3Co4O9 to obtain their high temperature structural characteristics. The crystal structure of both compounds remains unchanged till 1223 K. For, Bi2Sr2Co2Oy the CoO and Bi0.75Sr0.25O1.26 minor phases disappear above 1073 K and a new minor phase containing (Bi-Sr-O) or (Bi-Co-O) starts forming. On heating, the lattice volume and coefficient of thermal expansion change linearly for both compounds. Thermal expansion coefficient was found to be 0.0000353-0.0000343 and 0.0000296-0.0000288 K-1 over the temperature range of 300-1223 K for Bi2Sr2Co2Oy and Ca3Co4O9 respectively.

Parmi la grande diversité de composés formant la famille des perovskites hexagonales, les systèmes à base de cobalt sont largement étudiés à cause de leurs propriétés électroniques et magnétiques complexes. Ainsi, l'investigation des systèmes Ba-Co-O-X avec X=F, Cl ou Br a permis de synthétiser de nouvelles phases dont les structures sont caractérisées par des groupements trimères Co3O12 (trois octaèdres CoO6 reliés par une face) ou tétramères Co4O15 (quatre octaèdres CoO6 reliés par une face). De fortes relations structurales ont été mises en évidence entre les formes trimères et tétramères des composés oxydes, oxyfluorures, oxychlorures et oxybromures, notamment l'existence de désordres des atomes d'oxygène ou des transformations de phases à haute température (tétramères -> trimères). Dans tous ces matériaux, la couche d'interface entre blocs élémentaires joue un rôle prépondérant sur la dimensionnalité des structures créées. Par ailleurs, des mesures de susceptibilité magnétique combinées à des expériences de diffraction des neutrons ont permis d'établir l'existence, en l'absence de champ magnétique, d'une mise en ordre antiferromagnétique selon l'axe c à basse température dans les matériaux halogéno-cobaltites. L'évolution des courbes d'aimantation en fonction du champ appliqué montre un comportement magnétique plus complexe pour les matériaux bromés, avec notamment la possibilité d'aligner les moments magnétiques dans le plan (ab) par application d'un champ magnétique. Finalement, ce travail de thèse présente les relations entre structure cristalline, dimensionnalité et propriétés magnétiques de ces nouvelles phases halogéno-cobaltites.

Объектами исследования настоящей работы являются катодные материалы на основе сложного оксида Сa3Co4O9+δ. Цель работы – апробация материалов на основе Сa3Co4O9+δ, которые могут быть использованы в качестве катодов для среднетемпературных твердооксидных топливных элементов с протон-проводящими электролитами BaCe0.5Zr0.3Y0.1Yb0.1O3- и BaCe0.7Zr0.1Y0.1Yb0.1O3-. Методом пиролиза цитрат-солевых композиций проведен синтез сложных оксидов Сa3Co4O9+δ, Ca3Co4-xCuxO9 (х = 0.05; 0.1; 0.15; 0.2), BaCe0.5Zr0.3Y0.1Yb0.1O3-δ и BaCe0.7Zr0.1Y0.1Yb0.1O3-. При помощи комплекса современных методов исследования выполнена фазовая, структурная и микроструктурная аттестация оксидов Сa3Co4O9+δ, Ca3Co4 xCuxO9 (х = 0.05; 0.1; 0.15; 0.2), BaCe0.5Zr0.3Y0.1Yb0.1O3-δ и BaCe0.7Zr0.1Y0.1Yb0.1O3-. Термогравиметрическим методом исследована термическая устойчивость Сa3Co4O9+δ на воздухе и в атмосфере аргона. Термическое расширение оксидов Сa3Co4O9+δ и BaCe0.5Zr0.3Y0.1Yb0.1O3-δ изучено методом дилатометрии, доказана их термическая совместимость. Изучена химическая совместимость оксида Сa3Co4O9+δ с электролитными материалами Ba2In1.8W0.2O5.15, 0.7Ba2In2O5·0.3Ba2InNbO6, Ba3Ca1.18Nb1.82O9 δ, BaCe0.5Zr0.3Y0.1Yb0.1O3 δ, а также материалами коллекторных слоев La0.6Sr0.4MnO3-δ и LaNi0.6Fe0.4О3 δ, установлена оптимальная температура припекания катодного материала Сa3Co4O9+δ к электролиту BaCe0.5Zr0.3Y0.1Yb0.1O3-δ. Исследованы температурные зависимости электропроводности Сa3Co4O9+δ и BaCe0.5Zr0.3Y0.1Yb0.1O3-δ на воздухе. Сформированы электроды на основе композитов с различным массовым содержанием Сa3Co4O9+δ и BaCe0.5Zr0.3Y0.1Yb0.1O3-δ на подложках из BaCe0.5Zr0.3Y0.1Yb0.1O3-δ, а также электроды на основе Ca3Co4-xCuxO9 (х = 0; 0.05; 0.1; 0.15) на подложках из BaCe0.7Zr0.1Y0.1Yb0.1O3-δ. Методом импедансной спектроскопии на симметричных ячейках измерены поляризационные характеристики полученных электродов, а также электродов с оксидным коллектором состава La0.6Sr0.4MnO3-δ+2 масс.% CuO. / The object of study in this work is a cathode material based on the Сa3Co4O9+δ. The aim of the work is to study the electrochemical behavior of electrodes based on the Сa3Co4O9+δ with the electrolyte materials BaCe0.5Zr0.3Y0.1Yb0.1O3- and BaCe0.7Zr0.1Y0.1Yb0.1O3-. The synthesis of the Сa3Co4O9+δ, Ca3Co4-xCuxO9 (х = 0.05; 0.1; 0.15; 0.2), BaCe0.5Zr0.3Y0.1Yb0.1O3-δ and BaCe0.7Zr0.1Y0.1Yb0.1O3- complex oxides was carried out by pyrolysis of citrate-salt compositions. Using a complex of modern research methods, phase, structural and microstructural attestation of the Сa3Co4O9+δ, Ca3Co4-xCuxO9 (х = 0.05; 0.1; 0.15; 0.2), BaCe0.5Zr0.3Y0.1Yb0.1O3-δ and BaCe0.7Zr0.1Y0.1Yb0.1O3- oxides were carried out. The thermal stability of the Сa3Co4O9+δ in air and in the argon atmosphere was studied by the thermo gravimetrical method. The thermal expansion of the Сa3Co4O9+δ and BaCe0.5Zr0.3Y0.1Yb0.1O3-δ oxides was studied by dilatometry, and their thermal compatibility was proved. The chemical compatibility of the Сa3Co4O9+δ oxide with the electrolyte materials Ba2In1.8W0.2O5.15, 0.7Ba2In2O5·0.3Ba2InNbO6, Ba3Ca1.18Nb1.82O9 δ, BaCe0.5Zr0.3Y0.1Yb0.1O3-δ, Lа0.6Sr0.4MnO3-δ and LaNi0.6Fe0.4О3-δ collector materials was studied, the optimal temperature of the cathode material Сa3Co4O9+δ annealing to the BaCe0.5Zr0.3Y0.1Yb0.1O3-δ electrolyte was established. The temperature dependences of the electrical conductivity of the Сa3Co4O9+δ and BaCe0.5Zr0.3Y0.1Yb0.1O3-δ in air were investigated. Electrodes based on composites with different mass contents of Сa3Co4O9+δ and BaCe0.5Zr0.3Y0.1Yb0.1O3-δ on substrates of BaCe0.5Zr0.3Y0.1Yb0.1O3-δ, as well as electrodes based on Ca3Co4-xCuxO9 (х = 0; 0.05; 0.1; 0.15) on substrates of BaCe0.7Zr0.1Y0.1Yb0.1O3  were formed. The polarization characteristics of the obtained electrodes, including those with an La0.6Sr0.4MnO3-δ+2 wt.% CuO oxide collector, were studied by the method of impedance spectroscopy on the symmetric cells.