Rozprawy doktorskie na temat „Manganese perovskites”

The effects of strain on the magnetic phases in perovskites are of interest in the highly active research field of multiferroics. A Monte Carlo program is written to investigate the influence of strain on the low– temperature magnetic phase diagram of the manganese perovskites, RMnO3, where R is a cation in the lanthanide series. A Metropolis simulation scheme is implemented together with parallel tempering to perform computations in a two–dimensional geometry using a conventional nearest–neighbor and next–nearest–neighbor Heisenberg Hamiltonian, extended to include spin–lattice couplings and single–ion anisotropies. The latter two are important to account for structural distortions such as octahedral tilting and the Jahn–Teller effect. It is shown that even weak single–ion anisotropies render incommensurability in the otherwise structurally commensurate E–type ordering, and that the Dzyaloshinskii–Moriya interaction, in combination with single–ion anisotropies, is crucial for the stabilization of previously experimentally observed incommensurate spin spirals. Simulations performed to account for strain in the crystallographic ab–plane show that tensile strain may improve stability of E–type ordering for R elements with small atomic radii and that compressive strain drives the magnetic ordering toward the incommensurate spiral states.
Spänningsinverkan på de magnetiska faserna i perovskiter är av intresse inom den just nu högaktiva forskningen om multiferroiska material. Ett Monte Carlo-program har skrivits för att undersöka effekterna av spän- ning på de magnetiska lågtemperaturfaserna i multiferroiska manganitpe- rovskiter, RMnO3, där R är en katjon i lantanoidserien. En kombination av Metropolisalgoritmen och parallelltemperering har använts för att utföra beräkningar i tvådimensionell geometri med en konventionell Heisenberghamiltonian, utökad till att även inkludera spinn–gitterkopplingar och enkeljonsanisotropier. De senare har visats vara viktiga för att ta i beaktande den strukturella distortion i materialet som följer av t.ex. syreoktahederförskjutning och Jahn–Tellereffekten. Det visas att även svaga anisotropier orsakar inkommensurabilitet i den i övrigt kommensurabla E–typsfasen, och att Dzyaloshinskii-Moriyainteraktionen, i kombination med anisotropitermerna, är avgörande för att kunna stabilisera de sedan tidigare experimentellt bekräftade inkommensurabla spinnspiralsfaserna. Simuleringar som modellerar spänning i materialets kristallografiska ab–plan visar att dragspänning kan förbättra stabiliteten hos E–typsfasen för R–atomer med liten radie och att tryckspänning leder den magnetiska ordningen mot inkommensurabla spiraltillstånd.

A family of oxygen-deficient perovskite phases with compositions, Ca₂Mn_2-xNb_xO_γ has been synthesised and characterised using X-ray Powder Diffraction and Thermogravimetry. Property characterisation has included the study of electrical properties by Impedance Spectroscopy and the investigation of magnetic properties for one composition, x = 1.0. Some compositions were tested for possible application as electrode materials in gas sensors. The Ca₂Mn_2-xNb_xO_γ system 0 ≤ x ≤ 1.2, with variable oxygen content, γ, can accommodate up to 20% vacancies at oxygen sites and Mn occurs in valence states ranging from +2 to +4. Depending on the B-cation ratio and oxygen content, two solid solution form: an extensive GdFeO₃-type solid solution over the entire range of cation content, 0 ≤ x ≤ 1.2, with zero or small oxygen deficiencies and a closely-related, grossly oxygen-deficient solid solution over the range 0.3 ≤ x ≤ 0.8 with a simple cubic perovskite structure. Unit cell volume and orthorhombic GdFeO₃-type distortion vary greatly with Mn valency, oxygen content and B-cation content. The orthorhombic GdFeO₃-type structure of composition x = 1.0 was refined by the Rietveld method. Mn and Nb are disordered over the B-sites. Jahn-Teller activity of Mn³⁺ does not result in cooperative distortions of (Mn,Nb)O₆ octahedra, but it was observed to effect the oxygen stoichiometry. The Nb-rich composition, x = 1.0, can accommodate large amounts of Ca-vacancies (up to 10%). Electrical conductivity varies greatly with the composition. Results suggest that t_2g electrons are responsible for a variation of conductivity and activation energy rather than e_g electrons. Conductivities are believed to depend mainly on the degree of π-orbital overlap between Mn and oxygen and hence, on interatomic distances. At low temperatures, the material exhibits spin glass-like behaviour.

Etude des possibilites d'ecarts a la stoechiometrie sur le sous reseau anionique des perovskites amn::(1-x) fe::(x)o::(3-y) (a=ca, sr, ba) par diffraction x et neutron, microscopie electronique haute resolution, spectre moessbauer et mesures magnetiques. Caracterisation de plusieurs types d'ordre des lacunes oxygene en fonction du cation a et du taux de mn

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Dissertação (Mestrado)
IPEN/D
Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

The 'RMnO3': R = La, Nd, Pr, phases have been synthesised and characterised by a combination of electron probe microanalysis (EPMA), H2-reduction thermogravimetry (TG), x-ray (XRD) and neutron diffraction (ND). RMnO3 forms, at" 1400C, over the ranges: NdMn0, 95Oz to Nd0 88MnOz PrMn0.97O2 to Pr0 88MnOz LaMno 0.90Oz to La0.97MnOz Oxygen contents vary in air over the range 700 to 1400 C and can be varied further, either by high pressure Oz treatment or by reduction in H2. The structure of 'RMnO3' R = Nd, Pr is based on the GdFe03 structure with a Jahn-Teller distortion associated with the high proportion of Mn3+ ions present. The oxygen deficient 'LaMnOz' compositions also exhibit this structure consistent with earlier reports. By combining EPMA, TG, XRD and ND results various defect models describing the stoichiometry and structure of Mn-rich and R-rich, R = Nd, Pr compositions have been summarised. Both R = Nd and Pr systems exhibit very varied defect structures; depending on composition and heat treatment, vacancies can form on any one or any two of the three sublattices, R, Mn and O and the overall Mn oxidation state can include 2+, 3+ and 4+ contributions. For 'RMn03': R = La, Nd, Pr, data on their compositional ranges and defect crystal structures are presented in the form of novel phase diagram-defect structure maps from which the principal defect structure for a given stoichiometry can be easily obtained. The majority of the Pr-Sr-Mn-O pseudotemary phase diagram has been determined. EPMA was used to follow the progress of reaction and the conditions to achieve complete reaction established. Several solid solutions were evidenced, some previously unreported (3 - 6): 1) Pr1.xSrxMnO3 0[Special character omitted]x[Special character omitted]1.0 2) Pr1+xSr2.xMn2O7 0 [Special character omitted]x [Special character omitted] 0.4 3) SrxPr1-xO2 0[Special character omitted]x[Special character omitted]0.16 4) Sr1-xPrO3 0[Special character omitted]x[Special character omitted]0.15 5) Sr2.xMnxO4 6) Sr2.xPrxMnO4 The perovskite-like Pr1-xSrxMnO3 solid solution extends from PrMnOz to SrMnOz. The unit cell symmetry changes from orthorhombic to rhombohedral to tetragonal to cubic and finally to hexagonal as the Sr content increases. The limits of the Ruddlesden Popper (RP) n=2 Pr1+xSr2_xMn2O7 solid solution were determined: 0 [Special character omitted] x [Special character omitted] 0.4 and a tetragonal unit cell observed consistent with the literature. Synthesis of the RP compositions by solid state methods requires long heating times (up to 36 days) to produce homogeneous samples; qualitative EPMA of younger samples indicated an inhomogeneous distribution of Pr and Sr. Contrary to EPMA results, XRD of younger samples indicated that complete reaction had occurred and single phase compositions produced. It is suggested that the SrxPr1-.xO2 solid solution extends over the range 0 [Special character omitted] x [Special character omitted] 0.16 where similarly to the polymorphism of praseodymium oxides, compositions 0.03 [Special character omitted] x [Special character omitted]0.16 exhibit the cubic fluorite-type structure of Pr6O11 and x [Special character omitted] 0.03 is a mixture of cubic SrxPr1-xO2 and hexagonal SrxPr2.xO3. Perovskite-like SrPrO3 exhibits variable cation ratios; the Pr-rich boundary is Sr0.85PrOz. The lower Sr-rich boundary is yet to be identified. Similarly to 'RMnO3': R = La, Nd, Pr, the oxygen content of 'SrPrOz' is expected to vary. Therefore, various possible defect structures describing vacancies on the three sublattices, Sr, Pr and O could exist and charge compensation would be an interesting example of ionic and electronic mechanisms where Pr adopts the +4 and +3 oxidation states. Four layer hexagonal SrMnO3 exhibits variable Sr:Mn ratios but the solid solution limits are not yet known. The unreported Sr2-xPrxMnO4 solid solution has been observed but the solid solution limits are not yet known. The K2NiF4-type structure of Sr2Mn04 is retained at x = 0.75 and is expected to contain Mn3+ as Mn4+ is reduced to compensate Sr24 substitution by Pr3+.

Les nanoparticules seront sans doute les outils diagnostiques et thérapeutiques de demain. Si ellessont magnétiques, elles sont promises à des applications telles que le renforcement du contraste enIRM, la thermothérapie et la libération contrôlée de médicaments. Les nanomatériaux La1-xSrxMnO3ont été sélectionnés car leur température de Curie (TC) peut être ajustée dans la gamme detempérature thérapeutique. Des particules calibrées en taille et désagrégées ont été élaborées par leprocédé glycine-nitrate (GNP). Les caractérisations chimiques et structurales ont permis de mieuxcomprendre les résultats contradictoires de la littérature concernant la soi-disant dépendance de TCavec la taille des nanoparticules. L'adaptabilité de ces nanoparticules pour des applications enhyperthermie ou en IRM a été confirmée. Enfin, la capacité des nanoparticules à s'échauffer a étéutilisée pour réticuler autour d'elles une couronne de macromolécules thermosensibles selon leconcept nouveau de chimie localement stimulée.

Les nanoparticules seront sans doute les outils diagnostiques et thérapeutiques de demain. Si ellessont magnétiques, elles sont promises à des applications telles que le renforcement du contraste enIRM, la thermothérapie et la libération contrôlée de médicaments. Les nanomatériaux La1-xSrxMnO3ont été sélectionnés car leur température de Curie (TC) peut être ajustée dans la gamme detempérature thérapeutique. Des particules calibrées en taille et désagrégées ont été élaborées par leprocédé glycine-nitrate (GNP). Les caractérisations chimiques et structurales ont permis de mieuxcomprendre les résultats contradictoires de la littérature concernant la soi-disant dépendance de TCavec la taille des nanoparticules. L’adaptabilité de ces nanoparticules pour des applications enhyperthermie ou en IRM a été confirmée. Enfin, la capacité des nanoparticules à s’échauffer a étéutilisée pour réticuler autour d’elles une couronne de macromolécules thermosensibles selon leconcept nouveau de chimie localement stimulée
Nanoparticles may be the next generation of diagnostic and therapeutic tools. If they are magnetic,they are dedicated to applications such as MRI contrast agent, thermotherapy and controlled drugrelease. La1-xSrxMnO3 nanoparticles were selected because their Curie temperature (TC) may be tunedwithin the range of therapeutic temperature. Size sorted and disaggregated particles weresynthesized by the Glycine-Nitrate Process. Chemical and structural characterizations allowed abetter understanding of conflicting results found in the literature about the particle size-dependenceof TC. The possibility to use these nanoparticles for hyperthermia and MRI applications has beenconfirmed. Finally, their ability to heat has been used to crosslink thermosensitive macromoleculesall around them according to the new concept of locally stimulated chemistry

Les oxydes pérovskites sont étudiés depuis des décennies pour leurs propriétés magnétiques et plus récemment leurs propriétés électrocatalytiques dans le contexte de la conversion d’énergie, dans les piles à combustibles et les électrolyseurs, notamment. Dans ce travail, nous avons cherché à développer de nouveaux électrocatalyseurs à base de pérovskites opérant en milieu aqueux, en visant des objets nanométriques capables d’interagir avec leur environnement et donc de présenter des propriétés électrocatalytiques dépendant de stimuli extérieurs. Ce travail se situe donc au croisement entre le développement de méthodes de synthèse, la conception de nanomatériaux, l’étude de leurs propriétés électrochimiques et magnétiques et du lien entre ces propriétés. En premier lieu, nous décrivons une stratégie de synthèse adaptée à l’obtention de pérovskites quaternaires en utilisant des milieux sels fondus, un chauffage micro-ondes innovant, et l’ajustement des conditions d’oxo-basicité du milieu fondu. Nous étudions ensuite la relation entre magnétisme et électrocatalyse dans le cas d’école de nanocristaux de La0.7Sr0.3MnO3 obtenus en sels fondus. Nous développons ainsi un diapositif permettant de déclencher des changements de propriétés électrocatalytiques pour la réduction du dioxygène en appliquant un champ magnétique. Nous mettons en avant l’importance de la composition de l’électrolyte pour l’amélioration des propriétés électrocatalytiques sous champ magnétique. Enfin, nous abordons un autre moyen de modifier par un stimulus les propriétés de pérovskites nanométriques, en développant la synthèse de nanocristaux de pérovskite dopées avec divers métaux, puis en déclenchant pour la première fois l’exsolution de ces cations métalliques à la surface des matrices pérovskites nanométriques
Perovskite oxides are studied since decades for their magnetic properties and more recently for their electrocatalytic properties in the context of energy conversion, within fuel cells and water electrolyzers, for instance. In this work, we have aimed at developing new perovskite-based electrocatalysts operating in aqueous media, by targeting nanoscaled perovskites able to interact with their environment and then to exhibit stimuli-dependent electrocatalytic properties. This work was then at crossroad between the development of synthesis strategies, the design of nanomaterials, the study of their electrochemical and magnetic properties and of their interplay. We first describe a synthesis strategy suitable to reach quaternary perovskites by using molten salt media, innovative microwave heating and precise tuning of the oxo-basicity of the melt. We then address the relationship between magnetism and electrocatalysis on the case study of La0.7Sr0.3MnO3 nanocrystals derived from molten salts, through the development of an original set-up enabling triggering changes in the oxygen reduction reaction electrocatalysis by application of a magnetic field. We especially stress out the important of the composition of the electrolyte for magnetic enhancement of electrocatalytic activity. Finally, we address another way to trigger “externally” the properties of nanoscaled perovskite oxides, by developing a synthesis of doped perovskite nanocrystals and then by triggering under reducing conditions the exsolution of the metal cation dopants as metal nanoparticles at the surface of perovskite nanocrystal hosts, for the first time

Dans la première partie de mon travail, j'ai préparé quatre catalyseurs différents à base d'oxydes de manganèse: une perovskite (LaMnO3), par voie sol-gel; un oxide simple (Mn2O3), par méthode rapide et un tamis moléculaire octahedrique (OMS-2) par deux méthodes de préparation différentes, via l'état solide (OMS) et la méthode hydrothermale (OMSh). Les propriétés physicochimiques de ces catalyseurs ont été caractérisées par diffraction des rayons X (DRX), adsorption-désorption de N2, analyses thermogravimétriques (ATD/ATG), analyses chimiques (ICP-OES) et réduction en température programmée (H2-RTP). Leurs performances catalytiques ont été évaluées dans la réaction d’oxydation du toluène. Trois cycles catalytiques consécutifs ont été réalisés pour chaque catalyseur afin de confirmer les performances. Afin d'évaluer la stabilité des catalyseurs dans des conditions réactionnelles, les performances catalytiques ont été étudiées sur des expériences de longue durée à température constante, pendant 24 h à 25% de conversion du toluène. Des tests d'oxydation du toluène sur un catalyseur de référence, type Pd/Al2O3 contenant 0,78% en poids de Pd, ont également été effectués à des fins de comparaison. Les caractéristiques cristallines détectées dans les modèles DRX sont bien compatibles avec la formation des structures désirées. Sur la base de leur surface spécifique et de leur réductibilité à basse température, les catalyseurs ont été classés comme suit : OMSs > Mn2O3 > OMS > LaMnO3. Cette tendance est en bon accord avec les performances observées dans l'élimination catalytique du toluène. Un modèle cinétique a été proposé et un bon accord a été obtenu lors de l'ajustement avec les données expérimentales. Dans la seconde partie de mon travail, des catalyseurs LaMnO3 (LM) avec un rapport molaire acide citrique (CA) sur nitrates métalliques (Mn et La) allant de 0,5 à 2 (LM 0,5 à LM 2) ont été synthétisés par méthode sol-gel citrate, afin d'étudier l'effet du rapport de l'acide citrique sur les propriétés physico-chimiques et les performances catalytiques. Les propriétés physicochimiques de ces catalyseurs ont été caractérisées par diffraction des rayons X (DRX), adsorption-désorption de N2 et par spectroscopie d'émission atomique de plasma à couplage inductif (ICP-AES). Sur des échantillons sélectionnés, des caractérisations supplémentaires par analyse thermogravimétrique et thermique différentielle (ATD/ATG), une réduction programmée en température par de l'hydrogène (H2-TPR) et une spectroscopie de photoélectrons X (XPS) ont été réalisées. Les résultats montrent que le rapport molaire acide citrique sur nitrates métalliques influence significativement le profil obtenu en ATD/ATG des solides non calcinés ainsi que les propriétés physico-chimiques des catalyseurs. Les caractéristiques cristallines détectées par DRX sont bien compatibles avec la formation de la phase perovskite LaMnO3. De petites caractéristiques de Mn2O3 ont été détectées dans les diagrammes de diffraction de tous les catalyseurs LM, à l'exception du rapport molaire élevé des nitrates CA / (Mn + La) (1,9 et 2,0). Inversement, des pics La2O3 sont observés pour des valeurs allant de 1,6 à 2, l'intensité la plus élevée étant détectée au rapport molaire égal à 2. Les performances catalytiques ont été évaluées dans l'oxydation du toluène en réalisant trois cycles catalytiques consécutifs pour atteindre des performances stables. Afin d'évaluer la stabilité des catalyseurs dans des conditions de réaction, des expériences à température constante ont été effectuées pendant 24 h à 17% de conversion du toluène. Les catalyseurs LM1.2, LM1.3 et LM1.5 ont montré les meilleures performances catalytiques en oxydation totale du toluène, tandis que LM1 et LM1.7 présentaient un comportement intermédiaire et LM0.8 était peu actif
In the first part of my work, I have prepared four different catalysts based on manganese oxides: a perovskite (LaMnO3), via sol-gel method; a simple oxide (Mn2O3), by rapid method and an Octahedral Molecular Sieve (OMS-2) by two different preparation methods, via solid state (OMSs) and hydrothermal method (OMSh). The physicochemical properties of these catalysts were characterized by X-ray diffraction (XRD), N2 adsorption–desorption, TGA/DTA, ICP-OES and H2-TPR. Their catalytic performances were evaluated in the oxidation of toluene. Three consecutive catalytic cycles were performed for each catalyst in order to reach steady state performances. In order to assess the stability of the catalysts under reaction conditions, the catalytic performances were studied upon long-term experiments running for 24 h at 25% of toluene conversion. Tests of toluene oxidation over a typical industrial catalyst, such as a commercial Pd/Al2O3 catalyst containing 0.78 wt% Pd, were also performed for comparison purposes. The crystalline features detected in the XRD patterns are well consistent with the formation of the desired structures. Based on their specific surface area and their low-temperature reducibility, the catalysts were ranked as follows: OMSs> Mn2O3> OMSh> LaMnO3. This trend was in good agreement with the performances observed in the catalytic removal of toluene. A kinetic model was proposed and a good agreement was obtained upon fitting with the experimental data. In the second part of my work, LaMnO3 (LM) catalysts with molar ratio of citric acid (CA) to metal nitrates (Mn and La) ranging from 0.5 to 2 (LM 0.5 to LM 2) were synthesized by citrate sol–gel method, in order to study effect of citric acid ratio on the physico-chemical properties and the catalytic performances. The physicochemical properties of these catalysts were characterized by X-ray diffraction (XRD), N2 adsorption–desorption and by inductively coupled plasma atomic emission spectroscopy (ICP-AES). Over selected samples, additional characterizations by thermogravimetric and differential thermal analysis (TGA/DTA), temperature-programmed reduction by hydrogen (H2-TPR) and X-ray photoelectron spectroscopy (XPS) were carried out. The results show that the molar ratio of citric acid to metal nitrates significantly influenced the TGA/DTA profile of gels along with the physico-chemical properties of the catalysts. The crystalline features detected by XRD are well consistent with the formation of LaMnO3 perovskite phase. Small features of Mn2O3 were detected in the diffraction patterns of all LM catalysts except for high CA/Mn+La nitrates molar ratio (1.9 and 2.0). Conversely, La2O3 peaks appeared for values ranging from 1.6 to 2, the highest intensity being detected at molar ratio equal to 2. The catalytic performances were evaluated in the oxidation of toluene, performing three consecutive catalytic cycles in order to reach steady-state performances. In order to assess the stability of the catalysts under reaction conditions, long-term experiments running for 24 h at 17 % of toluene conversion were carried out. The catalysts LM1.2, LM1.3 and LM1.5 showed the best catalytic performances in terms of toluene conversion, LM0.8 was poor performing, while LM1 and LM1.7 exhibited an intermediate behaviour

Intensive research interests in condensed matter physics have been focused at the strongly correlated electron systems. Most of the efforts were devoted in hole-doped manganites with a double exchange interaction between Mn3+/Mn4+. Recently, tetravalent ions substitution has also stimuli much attention as a supplement for the hole-doping. Such electron-doped manganites may be of great potential for the development of all-manganites devices. Manganites are extremely sensitive to external disturbances, such as magnetic fields, electric fields, currents, mechanical strain, and photo illumination, etc. These extraordinary properties make manganites promising for practical applications. In this thesis, the field modulation on physical properties in electron/hole-doped manganites films and heterojunctions were investigated. The effects of tetravalent hafnium doping on the structural, transport, and magnetic properties of polycrystalline La1-xHfxMnO3(LHMO) (0.05 ≤x ≤0.3) were studied systematically. A phase diagram was obtained for the first time through magnetization and resistance measurements in a broad temperature range. An abnormal enhancement of magnetization was observed at about 42 K. It was further confirmed that the second magnetic phase MnO2in LHMO gives rise to such a phenomenon. The dynamic magnetic properties of LHMO, such as relaxation and aging processes, were studied, demonstrating a spin-glass state at low temperature accompanied by a ferromagnetic phase. Heterojunctions composed of n-type SrTiO3-δand p-type GaAs exhibited excellent rectifying behavior from 40K to room temperature. The photocarrier injection effect and a colossal photo-resistance were observed. Strong dependences on both temperature and bias voltage were found as well, which might be under stood by considering the band structure of the formed p-njunction. By employing an ultrathin SrTiO3buffer layer,La0.8Ca0.2MnO3films could be epitaxially grown on GaAs substrates. The heterostructures exhibit good rectifying behavior with a paramagnetic-ferromagnetic transition at ~200K. The variation of diffusion voltage with temperature in these heterostructures could be explained by the effects of the Hund’s rule coupling between the La0.8Ca0.2MnO3and the buffer layer. The effects of the strain induced by ferroelectric poling on the magnetic and electric properties have been investigated by using 0.67Pb(Mg1/3Nb2/3)O3-0.33PbTiO3(PMN-PT) substrates. The polarization of the PMN-PT crystal reduces the biaxial tensile strain in the formed La0.9Hf0.1MnO3layer.It results in a significant decrease in resistance and an enhancement of the phase transition temperature as well as the magnetization. The impact of the lattice strain on the charge/orbital ordering state was also been studied. The modification of charge/orbital ordering phase by the electric fields and ferroelectric polarization suggested that the unstable states in the manganites are sensitive to the strain. Heterojunctions of La1-xHfxMnO3/Nb:SrTiO3 were fabricated and investigated under different fields (electric, magnetic and optic). These heterojunctions exhibited excellent rectifying behavior in a wide temperature range. Their properties could be significantly modulated by magnetic fields. Prominent photovoltaic effect was also observed in the formed junctions.
published_or_final_version
Physics
Doctoral
Doctor of Philosophy

Les manganites ont été particulièrement étudiés ces dernières années pour leurs propriétés de magnétorésistance colossale (CMR) et l'effet magnétocalorique. Ces oxydes de formule chimique T1-xDxMnO3, (T: terre-rare, D: alcalino-terreux) de structure pérovskite ABO3, présentent une valence mixte Mn3+/Mn4+. Les facteurs clés qui contrôlent les propriétés physiques sont le rayon moyen du site A (), le désaccord de taille des cations du site A (quantifié par la variance σ2 et la valence mixte du manganèse. Lors de notre étude, nous nous sommes focalisés sur l'effet du désordre gelé crée par la substitution aléatoire dans le site A de la structure pérovskite. Des échantillons poly-cristallins ont été synthétisés à cette fin. Les systèmes étudiés sont La0,8Pb0,1□0,1MnO3 et La0,8Pb0,1Na0,1MnO3 de composé mère La0,8Pb0,2MnO3 et La0,7Pb0,05Na0,25MnO3 de composé mère La0,7Pb0,3MnO3. Pour les deux premiers matériaux, l'étude structurale magnétique et électrique est présentée par ce manuscrit. Cette étude a permis de montrer l'existence des clusters ferromagnétique à haute température dans le contexte de la formation de la phase de Griffiths. De plus, nous avons mis en évidence l'existence des excitations magnétiques des ondes de spin à très basses température. A partir de la variation dans la température de Curie, la variation de la constante de raideur de l'onde de spin et l'évolution de la phase de Griffiths, nous avons pu montrer que le matériau La0,8Pb0,1□0,1MnO3 présente le rayon le plus faible et σ 2 le plus élevé comparé à La0,8Pb0,1Na0,1MnO3. Cette étude à montrer que le désordre est le mécanisme influençant sur les propriétés physiques de ces matériaux. Pour le système La0,7Pb0,05Na0,25MnO3, qui présente une température de Curie élevée (au dessus de l'ambiante) les propriétés magnétique ne montrent pas un effet considérable du désordre il est considéré régi par le mécanisme du double échange. Dans ce travail, nous nous sommes aussi intéressés à l'influence du désordre sur les exposants critiques et à l'effet magnétocalorique. L'analyse montre que les exposants critiques pour La0,8Pb0,1□0,1MnO3 sont proches à ceux du modèle de Heisenberg à dimension 3, alors qu'ils sont proches de ceux de la théorie du champ moyen pour La0,8Pb0,1Na0,1MnO3. Le désordre est quantifié d'être corrélé à court-distance ou non corrélé. Pour La0,7Pb0,05Na0,25MnO3, les exposants critiques appartiennent à la classe d'universalité de Heisenberg, comme prévu théoriquement. L'étude de l'effet magnétocalorique montre des valeurs intéressantes pour la variation d'entropie magnétique et la puissance relative du froid pour La0,7Pb0,05Na0,25MnO3. De plus, le caractère inhomogène de ces trois composés est affirmé par l'étude de l'exposant locale n qui varie avec le champ magnétique pour toute la gamme de température étudié
Manganites have been extensively studied over the past several years, a result of their displaying a colossal magnetoresistance (CMR) and the magnetocaloric effect (MCE). These materials with a perovskite structure (ABO3) are characterized by the general formula T1- xDxMnO3, (T: rare earth, D: alkaline earth), x being the doping level, the latter causing changes in the valence state of the Mn ions to maintain charge neutrality. The key parameters that control the physical properties of these oxides are the mean radius of the site A (), the size mismatch of cations of the site A (quantified by the variance σ 2) and the mixed valence of manganese. In our study, we focused on the effect of the quenched disorder created by the random substitution in the A site of the perovskite structure. Polycrystalline samples were synthesized for this purpose. The systems studied are La0,8Pb0,1□0,1MnO3 and La0,8Pb0,1Na0,1MnO3 have a parent compound La0,8Pb0,2MnO3 and La0,7Pb0,05Na0,25MnO3 with parent compound La0,7Pb0,3MnO3. For the first two materials, structural, electrical and magnetic studies are presented in this manuscript. These studies reveal the existence of ferromagnetic clusters at high temperature in the context of the formation of the Griffiths phase. In addition, we have demonstrated the existence of magnetic excitations of spin waves at very low temperature. From the variation of the Curie temperature, the variation of the stiffness constant of the spin wave and the evolution of the Griffiths phase, we have shown that the material La0,8Pb0,1□0,1MnO3 has the lowest and highest σ2 compared to La0,8Pb0,1Na0,1MnO3. These studies showed that the disorder is the mechanism influencing the physical properties of these materials. For the system, La0,7Pb0,05Na0,25MnO3, which has a high Curie temperature (above ambient) magnetic properties do not show a significant effect of the disorder, which is considered to be governed by the mechanism of double exchange. In this work, we are also interested in the influence of disorder on the critical exponents and the magnetocaloric effect. The analysis shows that the critical exponents for La0,8Pb0,1□0,1MnO3 are close to those of the Heisenberg model in three dimensions, while they are very close to those of mean field theory La0,8Pb0,1Na0,1MnO3. The disorder is quantified to be correlated with short-range or uncorrelated. For La0,7Pb0,05Na0,25MnO3, the critical exponents belong to the Heisenberg universality class, as expected theoretically. The study of magnetocaloric effect shows interesting values of the magnetic entropy change and the relative cooling power La0,7Pb0,05Na0,25MnO3. In addition, the inhomogeneous nature of these three compounds is confirmed by the study of the local exponent “n” which varies with the magnetic field for the entire temperature range studied

Praca zawiera wyniki termodynamicznych badań kryształów tytanianu ołowiu oraz niobianu sodu – czystych oraz domieszkowanych manganem. Zostały określone wartości entalpii, entropii, energii Gibbs’a, i aktywności chemicznej badanych kryształów. Badania zostały wykonane przy zastosowaniu pomiarów ciepła właściwego kryształów oraz badania produktów odparowanych do fazy gazowej, przy użyciu komórki Knudsena i spektrometrii masowej. Dane termodynamiczne zostały wyprowadzone poprzez zestawienie pomiarów odnoszących się do fazy stałej i gazowej. Zostały zidentyfikowane produkty rozkładu tytanianu ołowiu i niobianu sodu występujące w fazie gazowej, zmierzone ich ciśnienia parcjalne w zależności od temperatury i wyznaczone wartości stałych równowagowych. Określono entalpie ich sublimacji, formowania, reakcji. Wyznaczono zmiany entropii oraz entalpii związane z występującymi przemianami fazowymi. Wykazano długo-czasową stabilność badanych materiałów w warunkach wysokotemperaturowej równowagi termodynamicznej w oparciu o obliczoną niską wartość aktywności chemicznej. Wykazano, że domieszka manganu zmniejsza stabilność badanych kryształów. Pokazano, że jony manganu podstawiają się w miejsce jonów tytanu albo niobu, potwierdzając niektóre wcześniejsze wyniki i rozstrzygając sprzeczności znane z literatury. W oparciu o analizę ciepła właściwego określono w tych materiałach cechy strukturalnych przemian fazowych stowarzyszonych ze zmianą uporządkowania: paraelektrycznego, ferroelektrycznego i antyferroelektrycznego.

With the discovery of appreciable room temperature magnetoresistance (MR) in high Curie temperature (Tc) ferrimagnetic double perovskites such as Sr2FeMoO6, research surrounding other materials of this type has expanded. Most ferrimagnetic double perovskites of the formula A2BB'O6 have non-magnetic A-site cations, such as Sr2+, Ca2+ or Ba2+. Replacing non-magnetic cations with magnetic variants offers further possibilities to tune magnetic effects. This thesis focuses on the substitution of non-magnetic A-site cations with relatively small magnetic Mn2+ cations. This substitution is made possible through the use of high-pressure/temperature (P/T) synthesis, and the characterisation of structural and magnetic properties of new phases discovered through these syntheses. The first of these new phases to be reported herein is Mn2FeReO6, which can be described as the Mn analogue of the well-known ferrimagnetic double perovskite Ca2FeReO6. These materials are well ordered with Fe3+/Re5+ on B-sites and crystallise in a P21/n structure. Mn2FeReO6 shows a high Tc of 520 K due to ferrimagnetic Fe/Re magnetic order above RT, and a large saturated magnetisation of 5.0 μB, which peaks at 75 K. Interestingly, the A-site Mn2+ (3d5) magnetic order has the effect of causing a spin reorientation of the Fe/Re sublattice observed by neutron powder diffraction (NPD) at temperatures below ~75 K. This causes the MR to exhibit the expected negative intergrain tunnelling behaviour above the transition and colossal positive behaviour below. Also reported are a series of perovskite related structures with formulae CaxMn2- xFeReO6 (x = 0.5, 1.0, 1.5). Of particular note among these is CaMnFeReO6, which exhibits 1:1 A-site ordering of Ca/Mn and adopts the P42/n space group. This material belongs to a family of newly discovered 'double double' perovskites, in which Ca/Mn order in columns pointing along the c-axis and Mn has alternating tetrahedral and square planar coordination environments. MR in this material remains negative down to 20 K, potentially due to the presence of Ca disrupting magnetic interactions between Mn2+ cations and suppressing the spin transition. Alternating coordination environments in the double double perovskite structure type were exploited in the synthesis of Ca(Mn0.5Cu0.5)FeReO6. This material also crystallises in the P42/n structure and is well ordered on B-sites, as evidenced by X-ray powder diffraction. Neutron diffraction yields, in addition to columnar order, a slight preference for Cu to occupy the square planar sites and for Mn to occupy tetrahedral sites. This doping of square planar sites with Cu has the effect of enhancing magnetic properties compared to CaMnFeReO6, increasing the saturated magnetisation, raising the ferrimagnetic ordering temperature of the B-sites from 500 to 560 K, and also having a profound effect on the observed MR effects, as a switch in the sign of the MR is observed in this material through a magnetic transition. Finally, B-site substitution has been experimented with in the synthesis of CaMnMnReO6. This also possesses the combined A and B-site orders observed in CaMnFeReO6 and an unusual magnetic structure, with perpendicular A and B-site magnetism due to frustration, deviating greatly from the magnetic structures of materials with B-site Fe/Re. In summary, this thesis compiles the synthesis and analysis of a series of new double perovskites, double double perovskites and a new 'triple double' five-fold cation ordered structure with a general formula of AA'0.5A''0.5BB'O6. These materials show that new types of structural ordering can be used to increase the number of degrees of freedom available for tuning the interplay between many different magnetic cations in different coordination environments.

Les matériaux oxydes possèdent une physique très riche et une large gamme de propriétés qui en font des matériaux très attractifs les applications. Notre but est d'utiliser ces matériaux oxydes pour améliorer les performances de capteurs magnétiques ultrasensibles appelés capteurs mixtes à 77K. Ces capteurs combineraient un transformateur flux champ supraconducteur en YBaCuO fonctionnant à 77K et la magnétorésistance d'une jonction tunnel dont les électrodes sont composées du manganite demi-métallique La0.7Sr0.3MnO3 (LSMO). Durant cette thèse, nous avons développé l'élément clé de ce capteur qu'est la jonction tunnel. Toutes les hétérostructures oxydes ont été déposées par ablation laser. Après avoir vérifié les propriétés de films minces de LSMO et obtenu une couche de référence avec des bicouches LSMO dopé Ru / LSMO, nous avons étudié des jonctions tunnel de type LSMO dopé Ru / LSMO/SrTiO3/LSMO. Sur cet empilement inédit, des magnétorésistances tunnel (TMR) allant jusqu'à 300% ont été mesurés. Le bruit a été caractérisé pour la première fois dans des jonctions tunnel oxydes. Nous nous sommes aussi intéressés au couplage antiferromagnétique à l'interface du LSMO et du SrRuO3 afin de piéger un film de LSMO. Des cycles asymétriques inhabituels ont été observés sur ces bicouches. Des mesures magnétométriques, de réflectivité de neutrons polarisés et des simulations ont alors été combinées pour comprendre le comportement magnétique des bicouches. Cette étude a montré que le couplage antiferromagnétique n'est pas homogène à l'interface entre le LSMO et le SrRuO3

Complex oxides are an intriguing field of solid-state research, as they can exhibit a wide variety of functional properties, such as ferroelasticity, ferroelectricity, ferro- and antiferromagnetism or an even more complicated type of magnetic ordering, the combination or interaction of those ferroic properties (multiferroicity), high spin polarization, or high-temperature superconductivity. Thus they are prospective candidates for future materials in microelectronics. It is a matter of fact that the performance of such oxide-based devices depends mainly on transport properties, which in turn depend on the distribution and density of intrinsic or extrinsic electronic interface states across the device structure. The present thesis focuses on the identification and characterization of such electronic properties by two different photoassisted spectroscopy techniques: surface photovoltage spectroscopy and photoelectron spectroscopy. This work especially deals with perovskite oxides, namely with the model perovskite strontium titanate (SrTiO3) as a substrate and three differently doped lanthanum manganite thin films (10-15 nm thickness) grown by pulsed laser deposition (PLD) on the SrTiO3 substrate(La0.7Sr0.3MnO3, La0.7Ca0.3MnO3, La0.7Ce0.3MnO3). The first part aims at the identification of electronic surface and interface states at the free SrTiO3 surface as well as at the three different lanthanum manganite/SrTiO3 interfaces. For that purpose three different experimental realizations of the surface photovoltage spectroscopy technique were implemented and employed: photoelectron spectroscopy under additional optical excitation, the capacitive detection of the photoinduced displacement current in a parallel-plate capacitor geometry under modulated optical excitation, and the classical Kelvin probe technique. The methods are evaluated comparatively with respect to their suitability to analyze the given oxidic interfaces. The main result of this first part is a map of the energetic positions and relaxation time constants of the surface states at the SrTiO3 surface as well as of the interface states at the lanthanum manganite/SrTiO3 interfaces within the SrTiO3 bandgap. The interface states were classified into film- and substrate-induced states and it could be demonstrated that an appropriate annealing procedure can dramatically decrease their densities. The second part tackles the problem of the manganese valence and the doping type of di- and tetravalent-ion-doped LaMnO3. The question whether the insulating parent compound LaMnO3 becomes an electron-doped semiconductor after doping with tetravalent cations such as Ce4+ - which would be in analogy to the well-established hole doping after partial substitution of La3+ by divalent cations such as Sr2+ or Ca2+ - has been discussed controversially in the literature so far. Due to the physics of the manganite crystal lattice the question can also be formulated in a different way: Can part of the manganese ions be driven from the Mn3+ state towards the Mn2+ state without any crystal instabilities or phase separation phenomena? In order to contribute to the clarification of this question, an extensive X-ray- and UV-photoelectron spectroscopy (XPS/UPS) investigation was performed. The three differently doped lanthanum manganite thin films were comparatively studied considering the exchange splitting of the Mn 3s core level line, which is a linear function of the Mn valence, as measured by XPS and the work function as extracted from UPS. All measurements were performed at different states of deoxygenation after heating in ultrahigh vacuum and reoxidation after heating in a pure oxygen atmosphere. Strong evidence for electron doping of the La0.7Ce0.3MnO3 film after deoxygenation was found. Furthermore, the reversible tunability of the Mn valence by variation of the oxygen content could be demonstrated for both tetravalent- and divalent-ion-doped lanthanum manganite films
Oxidische Komplexverbindungen können eine Vielzahl an funktionellen Eigenschaften, wie z.B. Ferroelastizität, Ferroelektrizität, Ferro- und Antiferromagnetismus sowie kompliziertere magnetische Ordnungen, die Kombination und Interaktion solcher ferroischer Eigenschaften (Multiferroizität), hohe Spinpolarisation oder Hochtemperatursupraleitung aufweisen und gelten daher als aussichtsreiche Materialien für die zukünftige Mikroelektronik. Entscheidend für die Funktionsfähigkeit oxidischer Bauelemente sind deren elektronische Transporteigenschaften, die in äußerst sensibler Weise von der Verteilung und Dichte von ex- oder intrinsischen elektronischen Defektzuständen an Grenz- und Oberflächen innerhalb der Bauelementstruktur abhängen. Die vorliegende Arbeit beschäftigt sich mit der Spektroskopie solcher elektronischer Eigenschaften mittels photonenbasierter Methoden. Im Fokus stehen dabei perowskitische Oxide , speziell das Modellperowskit Strontiumtitanat (SrTiO3) als Substrat und darauf mittels gepulster Laserdeposition (PLD) abgeschiedene dünne Filme (10-15 nm Dicke) dotierter Lanthanmanganate (La0.7Sr0.3MnO, La0.7Ca0.3MnO3, La0.7Ce0.3MnO3). Im Rahmen einer halbleiterphysikalischen Interpretation widmet sich der erste Teilder Identifikation elektronischer Ober- und Grenzflächenzustände an der SrTiO3-Oberfläche sowie an verschiedenen Lanthanmanganat/SrTiO3-Grenzflächen mittels dreier unterschiedlicher experimenteller Methoden zur Vermessung der Oberflächenphotospannung: der Photoelektronenspektroskopie unter zusätzlicher optischer Anregung, einer kapazitiven Detektionsmethode in Plattenkondensatorgeometrie unter modulierter optischer Anregung und der optischen Kelvin-Sonde. Neben einem auf die bei oxidischen Ober- und Grenzflächen auftretenden besonderen Herausforderungen zugeschnittenen Methodenvergleich werden Grenzflächenzustände bezüglich ihrer energetischen Position in der Bandlücke des SrTiO3 und ihres Relaxationsverhaltens analysiert, als substrat- oder filminduziert klassifiziert, und die Verringerung ihrer Dichte nach geeigneter Ausheilprozedur wird nachgewiesen. Der zweite Teil der Arbeit befasst sich mit der in der Literatur bisher kontrovers diskutierten Frage, ob sich die isolierende Stammverbindung LaMnO3 durch Dotierung mit tetravalenten Kationen, wie z.B. Ce4+, in einen elektronendotierten Halbleiter verwandeln lässt - analog zur Herstellung lochdotierter Lanthanmanganate durch Dotierung mit divalenten Kationen, wie z.B. Sr2+ oder Ca2+. Die Frage ist äquivalent zur Betrachtung, ob unter Beibehaltung der Stabilität des Kristallgitters ein Teil der Manganionen vom Mn3+-Zustand in den Mn2+-Zustand übergehen kann. Um einen Beitrag zur Klärung dieses Problems zu leisten, wurden als elektronisch sensitive Methoden die Röntgen- und UV-Photoelektronenspektroskopie (XPS/UPS) gewählt. Die oben genannten Lanthanmanganatfilme wurden dazu hinsichtlich der Austauschaufspaltung der Mangan-3s-Linie im XP-Spektrum, die in linearer Weise von der Manganvalenz abhängt, und der anhand der Breite des UP-Spektrums ermittelten Austrittsarbeit jeweils nach Reinigung der Oberfläche im Ultrahochvakuum (UHV) vergleichend untersucht. Die Messungen wurden nach unterschiedlich starker Desoxidation durch Heizen im UHV und Reoxidierung durch Heizen in Sauerstoffatmosphäre durchgeführt. Es konnte nachgewiesen werden, dass eine Elektronendotierung des La0.7Ce0.3MnO3-Films bei geeigneter Einstellung des Sauerstoffgehalts tatsächlich möglich ist. Außerdem wurde gezeigt, dass sich sowohl in di- als auch in tetravalent dotierten Lanthanmanganatfilmen die Manganvalenz und damit der Dotierungstyp reversibel durchstimmen lässt

Cette thèse porte sur l'étude de la relation entre la microstructure des couches minces de (La,Sr)MnO3 (LSM) et leurs propriétés fonctionnelles dans les dispositifs memristifs. Les mémoires à changement de valence (VCM), qui reposent sur des phénomènes de commutation résistifs, sont des candidats intéressants pour la prochaine génération de mémoires non volatiles car elles offrent une vitesse d'écriture rapide, une densité de stockage élevée et une faible consommation d'énergie. Ces mémoires stockent des données sous la forme d'une résistance accordable, qui peut être modifiée par un champ électrique. Typiquement, la dérive de l'oxygène dans le système provoque une réaction redox qui déclenche le changement de résistance. Cependant, les performances des VCM sont fortement liées aux éléments de la mémoire: le matériau actif, l'électrode et leurs interfaces.Dans cette thèse, la réponse memristive de l'oxyde de pérovskite LSM a été étudiée. Le LSM présente une stœchiométrie d'oxygène flexible grâce au changement de valence de Mn, qui modifie ses propriétés de conduction. Des couches minces de LSM ont été déposées par dépôt chimique en phase vapeur par injection pulsée (PiMOCVD) sur trois substrats pour induire différentes microstructures: des couches épitaxiaux avec une concentration faible et élevée de défauts ont été déposées sur des monocristaux de SrTiO3 (STO) et de LaAlO3 (LAO), respectivement, et des couches polycristallines avec une grande densité de joints de grains (JG) sur des substrats Si3N4. La réponse memristive a été étudiée dans des dispositifs plans microfabriqués Ti/LSMPt. La formation d'une couche de TiOx (x<2) à l'interface Ti/LSM dans des dispositifs vierges a été observée par STEM. Les mesures de spectroscopie d'absorption des rayons X indiquent une forte réduction du Mn sous l'électrode Ti (valence Mn +2,6) alors que le reste de la couche était oxydé (valence +3,5). Ça suggère que, pendant le processus de fabrication, le TiOx est formé à l'interface en piégeant l'oxygène du LSM.Les performances memristives ont été mesurées dans les couches épitaxiaux, pour lesquels il a été prouvé que les performances des dispositifs nanoioniques peuvent être améliorées par l'ingénierie des microstructures. Une commutation résistive de type interface bipolaire a été observée, où la transition vers l'état de haute résistance (HRS) ou RESET a été attribuée à la dérive de l'oxygène du LSM vers l'électrode Ti (l'oxydant), tandis que la réaction redox inverse conduit à une faible résistance état (LRS) ou SET. L'oxydation/réduction progressive peut rendre compte des plusieurs états de résistance mesurés dans ces dispositifs. Le RESET a lieu dans des conditions similaires dans LSM/LAO et LSM/STO, mais le SET dépend fortement de la microstructure du film LSM. La haute qualité cristalline du LSM/STO semble entraver la réincorporation de l'oxygène dans le LSM pendant le SET, et donc, un fonctionnement à tension asymétrique est nécessaire avec HRS/LRS=7. Les dispositifs LSM/LAO où les défauts agissent comme des voies de migration rapides pour réincorporer l'oxygène dans le LSM, le fonctionnement en tension symétrique est possible (HRS/LRS= 23 @± 20 V).Finalement, les dispositifs polycristallins Ti/LSMPt sur LSM/Si3N4 présentent un comportement similaire à celui du LSM/LAO: les capacités multiniveaux sont attribuées à une dérive rapide de l'oxygène le long des JG dans les opérations RESET et SET. Ces dispositifs présentent des fenêtres plus grandes, même à une tension plus faible (HRS/LRS>10 @±14 V). Les résultats obtenus pour les dispositifs polycristallins sont très intéressants car ils sont compatibles avec l'industrie des semi-conducteurs. La miniaturisation de ces dispositifs devrait conduire à une plus grande fenêtre de fonctionnement et à un stockage à plusieurs niveaux, tout en fonctionnant à des tensions plus faibles et ainsi, en réduisant la consommation d'énergie
This PhD thesis focuses on the study of the relationship between (La,Sr)MnO3 (LSM) thin film’s microstructure and their functional properties in memristive devices. Valence Change Memories (VCMs), which rely on resistive switching phenomena, are exciting candidates for the next generation of non-volatile memories as they offer fast writing speed, high storage density and low power consumption. These memories store data in the form of a tunable resistance, which can be varied by an electrical stimuli. Typically, oxygen drift within the system provokes a redox reaction, which triggers the change of resistance. However, the VCMs performance is strongly related to the elements that compose the memory, i.e. active material, electrode and their interfaces.In this thesis, the memristive response of La1-xSrxMnO3 (LSM) perovskite oxide was studied in detail. LSM presents flexible oxygen stoichiometry accommodated through the change of Mn valence, which in turn modifies its electrical conduction properties. LSM thin films were successfully grown by pulsed-injection metal-organic chemical vapor deposition on three substrates to induce different microstructures: epitaxial films with low and high concentration of extended defects were grown on SrTiO3 (STO) and LaAlO3 (LAO) single crystals, respectively, and polycrystalline films with a large density of grain boundaries were grown on Si3N4 substrates. The memristive response was studied in micro-fabricated Ti/LSMPt planar devices. The formation of an oxygen deficient TiOx interlayer at the Ti/LSM interface in pristine devices was observed by STEM. Moreover, X-Ray Absorption Near-Edge Spectroscopy measurements in a pristine device indicate a strong reduction of the Mn under the Ti electrode (Mn valence ca. +2.6) while the rest of the film was oxidized (valence ca. +3.5). The reduction of LSM suggests that, during the fabrication process the TiOx is formed at the interface by scavenging oxygen from LSM.First, the memristive performance was measured in the epitaxial samples, for which it was proven that the performance of the nanoionic devices can be boosted by microstructure engineering. Bipolar interface-type resistive switching was observed, where the transition to the high resistance state (HRS) or RESET was assigned to the drift of oxygen from LSM towards the Ti electrode (oxidizing it), while the reverse redox reaction leads to a low resistance state (LRS) via a SET process. The gradual oxidation/reduction can account for the multilevel resistance states measured in these devices. While the RESET takes place under similar conditions in LSM/LAO and LSM/STO, the SET process greatly depends on the microstructure of the LSM film. The high crystal quality of the LSM/STO epitaxial films seems to hinder the reincorporation of oxygen into LSM during the SET transition, and thus, asymmetric voltage operation is required, reaching a HRS/LRS ratio up to 7. On the other hand, in LSM/LAO devices where the extended defects act as fast migration paths to reincorporate the oxygen into LSM ,symmetric voltage operation is possible up to ±20 V with HRS/LRS up to 23.Finally, polycrystalline Ti/LSMPt devices built on LSM/Si3N4 show similar behavior to that of the LSM/LAO devices, where the multilevel capacities are assigned to fast oxygen drift along the grain boundaries in both directions, i.e. during RESET and SET operation. Hence, these devices present larger operation windows, even at smaller writing voltage, i.e. HRS/LRS>10 for Vwrite=±14 V. The results obtained for polycrystalline devices are very exciting for memory applications as they are compatible with the semiconductor industry. The miniaturization of these devices is expected to lead to larger operating window and multilevel storage, while operating at lower voltages and thus, reducing power consumption

Ce manuscrit présente l?étude par diffusion de neutrons aux petits angles des inhomogénéités magnétiques de l?échelle nanométrique à l?échelle mésoscopique à basse température dans les composés manganites à effet CMR de la série Pr1-xCaxMnO3, x proche de 1/3, et son évolution sous champ magnétique appliqué.
Ces systèmes montrent une séparation de phase à grande échelle entre une phase ferromagnétique isolante (FI) et une phase antiferromagnétique isolante (AFI) correspondant à deux phases cristallines distinctes. Ils se transforment en une troisième phase cristalline, ferromagnétique métallique (FM), sous l?effet du champ magnétique. Nous avons tenté de comprendre par quel mécanisme.
Nous avons mis en évidence l?existence d?inhomogénéités magnétiques nanométriques dans chacune des phases FI et AFI. Notre étude sous champ révèle l?apparition d?un fort signal de diffusion dû à une nucléation de clusters de phase FM mésoscopiques (quelques centaines de nanomètres) lors de la transition I-M induite par le champ, faisant ainsi disparaître la diffusion par les objets nanométriques. L?effet CMR n?est donc pas dû à une nucléation à l?échelle nanométrique mais mésoscopique.

La réfrigération magnétique attire beaucoup d’attention ces dernières années parce qu’elle est considérée comme une technologie respectueuse de l’environnement et énergétiquement économique. Aujourd’hui, cette technologie avancée est encore en phase de recherche que des dispositifs de réfrigérations magnétiques soient déjà opérationnels. Ce travail de thèse consiste à étudier la potentialité de résistance à la corrosion de différents types de matériaux magnétocaloriques (Gd6Co1.67Si3, Ni2Mn0.75Cu0.25Ga et Pr0.66Sr0.34MnO3) en contact avec un fluide caloporteur. Afin de comprendre les propriétés magnétocaloriques des matériaux, nos recherches se sont aussi focalisées sur les relations entre la transition magnéto-structurales d’alliages Heusler Ni2Mn0.75Cu0.25Ga et (i) la distribution cationique au sein de la structure cristalline et/ou (ii) la microstructure. Finalement, le diagramme de phase magnétique et nucléaire en lien avec les effets magnétocalorique obtenu grâce à la diffraction de neutrons et de pérovskite Pr1-xSrxMnO3 (0.25≤x≤0.45) est également présenté
Magnetic refrigeration has gained lot of importance and attention as they are highlighted to be environmental friendly, energy efficient. Presently, though at research stage, the magnetic refrigerators are pushed towards realization in domestic application with extensive work on materials and with few working models. One critical issue, the potential resistance to corrosion in case of different class of magnetocaloric materials (Gd6Co1.67Si3, Ni2Mn0.75Cu0.25Ga and Pr0.66Sr0.34MnO3) against the heat transport fluid is addressed. To better understand and improve the observed magnetocaloric properties in Heulser alloys Ni2Mn0.75Cu0.25Ga and to elaborate the same with the magneto-structural relation, studies on (i) cation distribution with in crystal structure and/or (ii) microstructural dependence are presented. Nuclear and magnetic phase diagram based on detailed neutron diffraction and magnetism studies for magnetocaloric perovskite oxide Pr1-xSrxMnO3 (0.25≤x≤0.45) is also presented

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
Este trabalho teve como objetivo otimizar rotas de síntese de diferentes métodos de materiais cerâmicos monofásicos e estudar propriedades cristalográficas e magnéticas de manganitas destes materiais. Foram utilizados os métodos da reação no estado sólido, método da reação de combustão e o método hidrotérmico. Após otimização, foram sintetizadas pelo método da reação de combustão amostras com composição nominal Bi1-xMxMn2O5, onde (M= Eu, Er e x = 0,10). Para obter as fases desejadas, os materiais sintetizados pelo método da combustão foram tratados termicamente a diferentes temperaturas de 600°C, 700°C e 800°C para amostras de composição BiMn2O5, e a 900°C para as amostras com substituições de Eu e Er. Já, as amostras obtidas pelo método da reação no estado sólido foram tratadas a 700, 750 e 800°C por 24 horas em cada temperatura. Para o estudo da das fases cristalográficas formadas nos materiais foi utilizada a difração de raios X, seguida do refinamento estrutural pelo método de Rietveld. Os métodos de síntese, por combustão com ureia e de reação no estado sólido, permitiram obter amostras monofásicas para o material com composição nominal BiMn2O5, que apresentaram estrutura perovisquita do tipo mulita e grupo espacial Pbam, a reação de combustão com ureia permitiu também obter amostras monofásicas para a composição nominal Bi1-xMxMn2O5, na qual (M = Eu e x = 0,10), onde foi observada a formação de um material monofásico com a mesma estrutura e grupo espacial do BiMn2O5 (ICSD-026806), que sugere a substituição do sítio do Bi+3 por cátions Eu+3, para as composições nominais onde x = 0,1. A microscopia eletrônica de varredura indicou que o material sintetizado pelo método de combustão por ureia apresentou uma boa distribuição de partículas da ordem de 300 nm, enquanto que o método da reação no estado sólido permitiu obter amostras da ordem de 1 µm. No estudo do comportamento magnético das amostras foram realizadas medidas magnéticas em função da temperatura em procedimento ZFC (medida de magnetização com resfriamento sem campo magnético aplicado) e FC (medida de magnetização com resfriamento com campo magnético aplicado) na faixa de temperaturas de 2 a 300 K, para campos magnéticos aplicados de 100 Oe, para as amostras obtidas pelo método do estado sólido, que apresentaram comportamento típico antiferromagnético nas duas curvas (TN ~ 40 K). As medidas de magnetização em função da temperatura, obtidas pelo procedimento ZFC-FC, indicaram que as amostras com composição BiMn2O5, obtidas pelos métodos da reação por combustão apresentam uma resposta típica antiferromagnética com TN ~ 40 K nas curvas medidas em modo ZFC. Tal resposta se deve a ocupação dos cátions de Mn+3 nos sítios pirâmide tetragonal e Mn+4 nos sítios octaédricos da estrutura perovisquita do tipo mulita. Por fim, as amostras com composição nominal Bi0,9Eu0,1Mn2O5 apresentam um aumento na magnetização do material trazendo uma componente ferromagnética para o mesmo observada na sua curva FC com TC em 44,3 K. Isto ocorre devido a o momento magnético não nulo dos íons Eu3+, que ocupam os sítios octaedrais do bismuto.
The objective of this work is to optimize different methods of routes for synthesis of monophasic ceramic materials, and to study the crystallographic as well as its manganites magnetic properties. The reaction methods to be analyzed were the solid state reaction method, the combustion reaction method and the hidrothermic method. After optimization, the samples with nominal composition of Bi1-xMxMn2O5 (M= Eu, Er e x = 0.10) were synthesized using the combustion reaction method. With the aim of obtaining the desired phases, the synthesized materials using the combustion reaction method were then treated thermally at 600, 700 and 800oC for the samples presenting composition BiMn2O5, and 900oC for the samples containing substitutions Eu and Er. The samples obtained by the solid state reaction method were treated at 700, 750 and 800oC for 24 hours for each temperature. The X-ray diffraction using the Rietveld method for structural refining was used to study the crystallographic phases formed in the studied materials. The synthesis methods for combustion with urea as well as solid state allowed to obtain monophasic samples for the materials with nominal composition of BiMn2O5. They presented perovskite-like mullite-type structure with special group Pbam. The combustion reaction method with urea also allowed to obtain monophasic samples with nominal composition Bi1-xMxMn2O5, (M = Eu e x = 0.10), where it was possible to observe the formation of a monophasic material with the same structure and space group of BiMn2O5 (ICSD-026806). This result suggests the substitution of the Bi3+ site for Eu3+ cations for the nominal compositions with x = 0.1. The scanning electron microscopy indicated that the materials synthesized for combustion with urea presented a good particle distribution in the order of 300 nm, while the materials synthesized for solid state allowed to obtain samples in the order of 1 µm. The studies involving the magnetic behavior of the samples were performed through magnetic measurements as a function of temperature with ZFC (zero field cooled), as well as FC (field cooled). The measurements were performed in the range of temperatures from 2 to 300 K for the applied magnetic fields of 100 Oe when used samples obtained by the solid state reaction method. They presented typical antiferromagnetic behavior in the two curves (TN ~ 40 K). The measurements of magnetization as a function of temperature obtained through the ZFC-FC procedures indicated that the samples with composition BiMn2O5 obtained by the combustion reaction method presented a typical antiferromagnetic response with TN ~ 40 K in the curves measured in ZFC mode. Such a response is due to the occupation of Mn3+ cation in the tetragonal pyramid sites and Mn4+ in the octaedric sites for the perovskite structure mullite-type. Lastly, the samples with nominal composition Bi0,9Eu0,1Mn2O5 presented an increase in the material magnetization bringing a ferromagnetic component to the same observed in its FC curve with TC ~ 44,3 K. The last happens due to a not null magnetic moment of the Eu3+ ions that occupy the octaedric sites of bismuth.
CAPES: 8965/11-0

Ce travail a été effectué dans le cadre de la mise au point de procédés cataliques efficaces pour réduire la pollution atmosphérique induite par les oxydes d'azote (NOx), à partir de sources fixes. La réduction catalique sélective est le procédé le plus couramment utili¬sé sur site industriel. Il s'agit d'employer un réducteur approprié, l'ammoniac, pour réduire les NOx en présence d'oxygène. Cependant, l'utilisation de ce réactif présente un inconvénient majeur en raison de sa toxicité. L'originalité de ce travail est de proposer une réaction de dénitrification (DeN0x) propre, sans pollution induite, en utilisant le carbone comme agent réducteur (celui-ci est soit alimenté directement sous forme de noir de carbone, soit généré in situ sur le catalyseur, à l'aide d'un hydrocarbure) et un catalyseur appartenant à la famille des pérovskites. Les manganites au lanthane substituées par du cuivre en site B (Lao,8 Sro,2Mn1 Cuy03>; Oy(l) ont montré leur efficacité pour une telle réaction. La mise en forme du catalyseur, étape indispensable pour un usage industriel qui ne permet pas l'utilisation de solides pulvérulents, a été étudiée. Celle-ci a consisté à déposer le catalyseur sur un support céramique de type éponge, lui-même préalablement recouvert d'un wash-coat Ce02. Comme l'alimentation en noir de carbone et le contact entre le catalyseur et le noir de carbone sont particulièrement délicats, la génération de réactifs réducteurs carbonés a été réalisée par alimentation en propène sur un catalyseur fabriqué spécialement, constitué de pérovskite et d'alumine dopée au lanthane. De bonnes performances cataliques ont été obtenues grâce à ce catalyseur bifonctionnel.

La thermothérapie consiste à soigner un tissu cancéreux par la chaleur, par destruction directe de la tumeur (thermoablation) ou amélioration de traitements radiothérapeutiques ou chimiothérapeutiques (hyperthermie). Une des voies les plus prometteuses de thermothérapie consiste à utiliser l'échauffement de nanoparticules magnétiques La0. 75Sr0. 25MnO3 ont été synthétisées par voie Pechini. Ces nanoparticules présentent un échauffement magnétique autorégulé, c'est-à-dire que lorsque la température du milieu s'approche de leur température de Curie, les nanoparticules perdent leur capacité d'échauffement, empêchant tout risque de chauffage excessif. L'influence des conditions de synthèse de ces particules, ainsi que de la fréquence et de l'amplitude du champ magnétique sur l'échauffement de ces particules a été étudiée. L'appareil d'induction multifréquence, construit au cours de cette thèse, devrait à court terme permettre de mieux comprendre les phénomènes d'échauffement magnétique de ces particules. Les nanoparticules La0. 75Sr0. 25MnO3 ont été encapsulées dans de la silice par voie Stöber puis aminées par ajout d'aminosilanes : cette modification de surface ouvre de nombreuses possibilités (furtivité des nanoparticules vis-àvis dusysthème immunitaire par greffage de polyoxyéthylène, ciblage de cellules-cibles par greffage de ligands appropriés, etc. ). Un polymère thermosensible à base de poloxamers, capable de piéger des molécules-tests à "basse" température et de les libérer sous l'effet de l'échauffement magnétique, a été synthétisé et les premiers tests de libération de colorant sous l'effet de l'échauffement magnétique de nanoparticules La0. 75Sr0. 25MnO3 piégées dans ce gel se sont révélés très prometteurs.

L’objet de ce travail est l’étude des propriétés structurales et physiques des manganites La₀.₆₇Ba₀.₃₃Mn₁₋ₓTiₓO₃, préparés par la méthode céramique solide- solide et par des techniques de chimie douce (citrate modifié) et des manganites La0.6Sr0.4-d/dMnO3 préparés par la méthode céramique.L’utilisation de la méthode de citrate modifié montre plusieurs avantages (la simplicité, la rapidité et la pureté chimique des matériaux obtenus) alors que les résultats expérimentaux restent similaires pour les deux méthodes. La diffraction des RX et des neutrons montre que les échantillons La₀.₆₇Ba₀.₃₃Mn₁₋ₓTiₓO₃ sont monophasés. L’étude magnétique montre que les échantillons La₀.₆₇Ba₀.₃₃Mn₁₋ₓTiₓO₃ présente une transition paramagnétique-ferromagnétique pour un taux de Ti £ 10% alors qu’un comportement type verre de spin est observé au delà de ces taux. L’étude de la variation de résistante en fonction de la température faite pour La₀.₆₇Ba₀.₃₃Mn₁₋ₓTiₓO₃ (x = 0.05, 0.1) a montré que l’échantillon La(0.67)Ba(0.33)Mn(0.95)Ti(0.05)O(3) présente une transition métal – semi-conducteur alors qu’au dessus de 10% ces manganites présentent uniquement un comportement semi-conducteur.L’étude des échantillons La(0.6)Sr(0.4-d/d)MnO(3) a montré essentiellement que le taux nominal de lacunes, d, n’est pas atteint. La composition chimique résultante se décale vers celle du système La(1-x)Sr(x)MnO(3) par formation d’une seconde phase minoritaire Mn(3)O(4). L’étude de la relation structure cristalline et propriétés magnétiques a montré que la diminution de TC est due au renforcement des interactions de super- échange en augmentant le taux de Mn3+ dans nos échantillons
This work focuses on the study of structural and physical properties of manganites La₀.₆₇Ba₀.₃₃Mn₁₋ₓTiₓO₃, prepared by the ceramic method and soft chemistry routes (modified citrate) and manganites La0.6Sr0.4-ddMnO3 prepared by ceramic route.The use of the modified citrate-gel method shows several advantages (simplicity, speed and the chemical purity of the materials obtained) while the experimental results are similar for both methods. The X-ray and neutron diffraction show that the samples La₀.₆₇Ba₀.₃₃Mn₁₋ₓTiₓO₃ are single phased. The magnetic study shows that the samples present a paramagnetic-ferromagnetic transition for a rate of Ti £ 10% while a spin glass-type behavior is observed beyond these rates. The study of the variation in resistance with temperature made for La₀.₆₇Ba₀.₃₃Mn₁₋ₓTiₓO₃ (x = 0.05, 0.1) showed that the sample has a metallic-semiconductor transition while above 10% for Ti rate these manganites exhibit only a semiconducting behavior.The studied samples La0.6Sr0.4-ddMnO3 showed essentially that nominal vacancies, δ, cannot generally be achieved. The resulting chemical composition shifts toward the system La1-xSrxMnO3 by forming a second Mn3O4 minority phase. The study of the relationship between the crystalline structure and the magnetic properties showed that the decrease of TC is due to the strengthening of super-exchange interactions by increasing the rate of Mn3+ in our samples

Les manganites a valence mixte presentent une variete de transitions magnetiques, electroniques et structurales, leur comprehension etant encore un defi pour les physiciens de l'etat solide. La premiere partie de cette these est consacree a l'etude detaillee de la magnetoresistance extrinseque liee au transport dependant du spin a travers les interfaces. La mise en uvre d'une nouvelle chambre d'ablation laser a permis de developper un systeme modele a base des couches de la 2 / 3ca 1 / 3mno 3 deposees sur des substrats non-accordes de mgo (001). La conduction granulaire a ete caracterisee soigneusement et interpretee a partir des mesures de transport tunnel dependant du spin a travers d'interfaces non completement saturees ferromagnetiquement. Nous avons verifie nos hypotheses en developpant un autre systeme a base de joints des grains induits mecaniquement. Le role de la contrainte epitaxiale a ete etudie dans des couches de la 2 / 3ca 1 / 3mno 3 sur srtio 3 (001) et la modification des proprietes magnetiques et de transport a ete discutee et liee a la deformation structurale induite par la croissance epitaxiale. La deuxieme partie de cette these est dediee a l'etude des manganites a l'etat massif presentant des phenomenes d'ordre orbital et/ou de charge, ainsi que de segregation de phase. La diffraction de neutrons et de rayons x synchrotron, la relaxation des muons au champ nul, ainsi que la caracterisation magnetique et de transport ont ete utilisees pour etudier la migration electronique dans les planes ayant un ordre orbital tipe d x 2 - y 2 (pr 1 / 2sr 1 / 2mno 3), l'ordre de charge (pr 1 / 2ca 1 / 2mno 3 et bi 1 / 2ca 1 / 2mno 3) ainsi que la separation electronique de phase (pr 2 / 3ca 1 / 3mno 3) ou l'existence

Dans les multiferroïques coexistent au moins deux ordres ferroïques différents (ferromagnétique, ferroélectrique, ferroélasticité et ferrotoroïdicité) ou anti-ferroïques. Ces différentes propriétés peuvent être couplées ou non. Parmi ces matériaux, les plus étudiés sont ceux présentant un ordre magnétique et un ordre ferroélectrique. La présence d’un couplage magnétoélectrique entre ces deux ordres, permet de contrôler la polarisation par l’application d’un champ magnétique et inversement. Cependant très peu de ces matériaux ont des températures de transition supérieures à la température ambiante. Ces matériaux multiferoïques peuvent être séparés en deux catégories : la première regroupe les matériaux où les transitions des deux ordres sont indépendantes ; la deuxième regroupe les matériaux dont la transition ferroélectrique est liée à la mise en ordre magnétique. Dans cette thèse nous nous sommes intéressés à deux types d’oxyde multiferroïques dont l’un appartient à la première catégorie (YMnO3) et l’autre à la deuxième (RCrO3)
In multiferroics, at least two different ferroic orders coexist (ferromagnetic, ferroelectric, ferroelastici and ferrotoroidici) or anti-ferroic. These different properties can be coupled or not. Among these materials, the most studied are those with magnetic and ferroelectric orders. The presence of magnetoelectric coupling between these two orders, allows one to control the polarization by the application of a magnetic field and vice versa. However very few of these materials have transition temperatures above room temperature. These multiferoics materials can be separated into two categories : the first one includes the materials where the transitions of both orders are independent ; the second comprises the materials the ferroelectric transition of which is related to magnetic ordering. In this thesis we have studied two types of multiferroic oxides, one belongs to the first category (YMnO3) and the other to the second (RCrO3 )

Finding luminescent materials with narrow-band emissions, high stability, and high photoluminescence quantum yield (PLQY), yet relatively fast radiative decay rates, has been an outstanding research challenge. This thesis aims to develop different luminescent materials and examine their structural and optical properties for light-emitting applications. The first part of this thesis covers the controversy regarding the origin of emission in zerodimensional perovskites (0D), Cs4PbBr6 and Cs4PbI6, through a comparative analysis between 0D and three-dimensional (3D) perovskites. A series of optical studies excluded the 3D phases as the origin of emission in these materials. In parallel, the results from the DFT proposed the defects as a possible origin of emission. The second part of the thesis addresses the shortcoming of lead-based perovskites in terms of toxicity and stability, motivated by the high demand for sustainable materials with analogous electrical and structural properties. Thus, a series of solid-state Zn-based and Mn-based ternary compounds were investigated with and without doping. The compounds' photoluminescence peaks were between 520 nm – 525 nm, with PLQY between 34% -60%. Finally, CsMnBr3 NCs were synthesized revealing an intense red PL peak centered at 650 nm and a PLQY as high as 54% along with a remarkable excitation spectrum and surprisingly short lifetimes. The single crystals of this composition were also reported with a PL peak at 640 nm and a relatively high PLQY of 6.7% under the excitation at 360 nm. Further, a combination of structural and optical analysis attributed the green and red luminescence to the tetrahedral and octahedral environment of Mn2+, respectively. These materials represent a milestone towards lead-free luminescent materials with interesting optical properties. This dissertation aims at engineering different materials to address critical aspects in the field including stability and good luminescence properties while simultaneously examining the photophysics and mechanisms of the corresponding properties. This work paves the way for finding sustainable light-emitting materials for the next generation of light-emitting applications.

碩士
國立臺灣海洋大學
材料工程研究所
101
This study successful synthesizes (La,Sr)MnO3 (LSMO)-ZnO on e-dimensional (1D) heterostructures on cross-linked ZnO nano structures by RF sputtering. The high-temperature annealing procedure in oxygen-rich ambient at 800℃~950℃ enhanced the saturation magnetization and Curie temperature of the LSMO-ZnO 1D heterostructures. On the other hand, RF sputtering wa s used to synthesize LSMO nanolayers on the sapphire substra te with and without In2O3 epitaxial buffering. LSMO nanolaye r with In2O3 epitaxial buffering has a high degree of nanosc ale disordered regions and subgrain boundaries and incoheren t heterointerfaces. These structural inhomogeneities caused a low degree of ferromagnetic ordering in LSMO with In2O3 ep itaxial buffering, which leads to a lower saturation magneti zation value, Curie temperature, and higher coercivity.

碩士
淡江大學
物理學系碩士班
93
The half-doped manganese oxide Pr0.5Ba0.5MnO3 exhibits anomalous magnetic and transport properties with changing the amounts of A-site randomness. There are two kinds of structure distortion related to the fraction of the A-site randomness which arise from size-mismatch and structural stretching effect. The long-range A-type antiferromagnetic ordering is suppressed by the A-site randomness. The structure distortion might be the main factor of the second-order magnetic phase transition in the A-site totally ordered Pr0.5Ba0.5MnO3. The cooperative bond length fluctuation due to magnetic phase segregation introduces a random field that suppresses the magnetic phase transition in the samples with mixed phase. In addition, the stepwise behavior is only observed at low temperatures in the samples with mixed phase. The bond length fluctuation between separated AFM and FM phases makes the interaction of spin moments be dipole-dipole interaction which introduces a strain acting on a pair of antiparallel spins. As the stress is released at the threshold magnetic field Hthreshold, FM regions abruptly precipitate in the AFM clusters instead of gradually growing at the expense of the AFM clusters, giving rise to the extraordinarily sharp steps in magnetization and resistivity.

Oxides of ABO3 composition (A = alkali, alkaline earth or rare earth metal in general, B = transition metal) constitute a large family of metal oxides of current interest to solid state and materials chemistry. Among the several structure types exhibited by ABO3 oxides (ilmenite, LiNbO3, perovskite, YAIO3/YMnO3, KSbO3, pyrochlore, among others), the perovskite structure is probably the most well known and widely investigated. The ideal perovskite structure consists of a three-dimensional (3D) framework of corner-sharing BO6 octahedra in which the A cation resides in the dodecahedral site surrounded by twelve oxide ions. The ideal cubic structure occurs when the Gold Schmidt’s tolerance factor, t = (rA + ro)/{V2 (rB + ro)}, adopts a value of unity and the A-O and B-O bond distances are perfectly matched. The flexibility of the perovskite structure towards a wide variety of substitutions at both A and B sites gives rise to a very large number (several hundreds) of perovskite derivatives with subtle variations in structure. The perovskite structure can also tolerate vacancies at both the A and O sites giving ordered superstructures. Members of y4BO3 oxides have numerous properties that find technological application, such as nonlinear optical response (LiNbO3), Ferro electricity (BaTiO3), piezoelectricity (PbZn_xTixO3), magneto ferroelectricity (YMnO3), superconductivity (Bai_xKxBi03)5 colossal magnetoresistance (La^xCaxMnO3) and ionic conductivity [(Lil_a)TiO3] Ordering of cations at the A and B sites of the perovskite structure is an important phenomenon. Ordering of B site cations in double (/42BB'O6) and multiple (/43BB'2Og) perovskites gives rise to newer and interesting materials properties For example, 1*1 ordered Sr2FeMoO6 and Sr2FeReO6 are half-metallic ferrimagnets; Pb3MgNb2O9 is a relaxor ferroelectric; Ba3ZnTa2O9 is a low loss dielectric used in telecommunication and, last but not least, Ba3CoNb2O9 is a visible light driven photocatalyst. Realization of these properties in these materials depends crucially on the ordering/or otherwise of the B site cat ions in the perovskite structure. Furthermore, ordering of not only the metal atoms but also the oxygen/oxygen vacancies in the perovskite structure is equally important for the occurrence of superconductivity in the cuprate superconductor, YBa2Cu3O7. The ideal perovskite structure gives way to hexagonal YMnO3/YAIO3 structure for smaller A cations (tolerance factor, t < 1). Oxides of this structure are attracting current attention for the realization of multiple magnetoferroic properties. On the other hand, for larger A cations (tolerance factor, t > 1), various perovskite polytypic structures are formed. For example, BaNiO3 forms a 2H polytypic structure, SrMnO3 and BaRuO3 adopts a 4H and 9R structures respectively, where the SO6 octahedra share faces or faces and corners. Besides the foregoing 3D perovskites, a number of layered variants of the perovskite structure are also known. The most common layered perovskites are the Aurivillius phases, (Bi2O2)[A»-iBnO3n+iL the Ruddlesden-Popper phases, /4'2|7ln_iBnO3n+1], and the Dion-Jacobson phases, A[An^BnOzn+-\]' The two-dimensional (2D) perovskite unit, [^n-iBnOsn+i], which could be visualized as formed by slicing the 3D perovskite structure along <001>p is common for all the three layered perovskite series. The perovskite slabs are stacked alternately with various charge-balancing units, for example, with [Bi2O2]2+ in the Aurivillius phases and two alkali/alkaline earth cations (A+JA2+) in the Ruddlesden-Popper phases etc. Members of the layered perovskites are also important from the point of view of materials properties. For example, 2D magnetism (K2NiF4), superconductivity (La2-xSrxCuO4), ion exchange, Bronsted acidity, intercalation, exfoliation (K2La2Ti3Oio and CsCa2Nb3O10), photo catalysis (Rb2La2Ti30io) are some of the important materials properties found in layered perovskites. The high Tc-superconductors, Bi2Sr2CaCu2O8+XJ TI2Ba2Ca2Cu3Oi0, TIBa2Ca2Cu3O9 and HgBa2Ca2Cu3O8+x, also belong to the family of layered perovskites where the defective perovskite cuprate sheets are interleaved by other 2D entities like (Bi2O2), (TI2O2), (TIO) or (HgOx). In addition, Aurivillius phases, such as Bi2SrTa209 and Bi325Lao75Ti3Oi2, in thin film geometry are candidate materials for non-volatile ferroelectric memory devices. Synthesis plays a key role in realizing new structures and materials properties for ABO3 oxides. The conventional synthetic methods (ceramic method) involve mixing and heating of solid reactants at elevated temperatures. Although this approach continues to be employed to synthesize new materials, it is often limited by the fact that it yields thermodynamically stable phases. Since many of the perovskite oxides showing useful materials properties are metastable in nature and are required in the form of fine particles (free-standing / monodisperse / submicron or nanometer dimensions) for application, the ceramic methods are of no avail for this purpose. Therefore, materials chemists constantly endeavor to develop alternate synthetic routes that enable them to synthesize novel oxides under mild conditions. Typical examples of metastable perovskites are: the super conducting cuprates (e.g. TlosPbosS^CaC^Og) and perovskite based lithium ion conductors (La2/3-xLi3XDi/3-2xTiO3). Also the control of oxidation states in double perovskites, such as Sr2FeMoO6 and Sr2FeRe06 and pyrochlores such as Pb2MnReC>6, cannot be achieved by conventional means. Therefore, the synthesis of such metastable phases requires special synthetic strategies that involve soft chemistry (chimie douce) methods where mild reactions/reaction conditions are employed to access metastable phases. The present thesis is mainly devoted to an investigation of perovskite related oxides towards developing new synthetic strategies and materials as well as exploring hydrogen insertion - a novel materials property - in certain members of this family. Solid-state metathesis (SSM) reactions provide a convenient route for the synthesis of a wide variety of non-oxide ceramic materials such as, bondes, carbides, silicides, pnictides and chalcogenides. A typical metathesis reaction, for example, M0CI5 + 5/2 Na2S -» MoS2 + 5 NaCI + 1/2 S (1) involves exchange of atoms/ions between the reactants and is accompanied by a large enthalpy change (AHm = - 890 kJ mol"1) and high adiabatic reaction temperature (Tm = 1413 °C). The reactions are often self-propagating and believed to be driven by the formation of stable salt byproducts such as alkali halides with high lattice energy. In our laboratory we have developed a different kind of metathesis reaction for the synthesis of perovskite related oxides, a typical example being, K2La2Ti30io + 2 BiOCI -* [Bi2O2]La2Ti3O10 + 2 KCI. A major difference between metathesis reactions (1) and (2) is that unlike (1), reaction (2) is not self-propagating, requiring longer duration. In this study, we have investigated metathesis reactions of the second kind at some length for the synthesis of perovskite related oxides. We found that rocksalt oxides such as UMO2 (M = Mn, Co) and Li2TiO3 constitute convenient precursors for the formation of v4BO3 perovskite oxides in metathesis reactions with appropriate reaction partners such as halides, oxyhalides or sulphates, LiCoO2 + LaOCl -» LaCoO3 + LiCt (3) LiMnO2 + LaOCl + x/2 O2 -> LaMnO3+x + LiCI (4) Li2TiO3 + PbSO4 -» PbTiO3 + Li2SO4. (5) We could synthesize not only well known ABO3 oxides but also functional perovskites such as PbZr0 4sTio 52O3 (PZT), La2/3Cai/3MnO3 as well as superconducting BaPbo75Bio2s03 by this method. We could also synthesize La2CuO4 and its superconducting analogues, La185^oi5Cu04 (A = Sr, Ba), by the same method using Li2CuO2 and LaOCl. For the synthesis of double perovskites A2BB%OQ by this method however, appropriate lithium containing rocksalt precursor oxides are not known in the literature. Therefore, we first synthesized rocksalt precursor oxides of the general formula Li4MWO6 (M = Mg, Mn, Fe, Ni) and established their identity. Using these precursor oxides, we could synthesize the double perovskite oxides Sr2MWO6 (M = Mg, Mn, Fe, Ni) in the metathesis reaction Li4MWO6 + 2 SrCI2 -» Sr2MWO6 + 4 LiC Significantly, the double perovskites are formed with an ordered structure at relatively low temperatures (750 - 800 °C) as compared to the high temperatures (up to 1400 °C) usually employed for the synthesis of these materials by conventional ceramic approach. Next, we investigated ABO$ compositions corresponding to the formula for 6 = Cu and Ni, where we could obtain a YAIO3 superstructure consisting of triangular Cu clusters for 6 = Cu, whereas a perovskite phase for B = Ni. Moreover, the Cu-phase appears to be a unique line phase formed around LasCi^VOg composition, whereas a continuous series of GdFeO3-like perovskite oxides are formed for LaNii»xVxO3 (0 < x < 1/3)forS = Ni. Considering the current interest in bringing different transition metal ions (d°/dn electronic configuration) in the same perovskite related structure towards developing multiferroic materials, we investigated the substitution of aliovalent cations in a typical Aurivillius phase, Bi2Sr2Nb2TiOi2. We have characterized new aliovalent cation substituted Aurivillius phases, Bi2SrNaNb2TaOi2, Bi2Sr2Nb2Zr012J Bi2Sr2Nb2 5Feo50i2 and Bi2Sr2Nb2 ezZno 33O12. Lastly, we investigated the interaction of hydrogen with perovskite oxides, /\MnO3 (A = Ca, Sr, Ba) in an attempt to characterize possible existence of hydrogen-inserted oxide materials. An oxide-hydride of the formula LaSrCoO3H07 has recently been reported in the literature. Conventionally, the interaction of hydrogen with perovskite related oxides is known to result in either anion deficient phases (e.g. CaMnO3 -> Ca2Mn205), or hydrogen inserted materials, 'hydrogen bronzes', (e. g. HXWO3, HxBaRuO3), where hydrogen acts as an electron donor (H -^ H+ + e). We have characterized a new mode of hydrogen incorporation in Pt dispersed BaMnO3 and SrMnO3. Detailed investigation of the hydrogen sorption behaviour of 1 atom % Pt dispersed materials showed that about 1.25 mass % of hydrogen is inserted per mole of BaMnO3/Pt, corresponding to an insertion of - 3 hydrogen atoms giving 'BaMnOsHs'. While the exact nature of inserted hydrogen is yet to be established unambiguously, our results suggest that the inserted hydrogen is unlikely to be protonic (H+) in the hydrogen insertion product, BaMnO3H3. The results of these investigations are presented in the thesis consisting of seven chapters. Chapter 1 gives an overview of perovskite related oxides - structure, properties and synthesis. Chapter 2 presents metathesis as a general route for the synthesis of ABO3 oxides and illustrates the method by transforming several rocksalt oxides such as LiCoO2, Li2Mn03 and Li2Ti03 to corresponding ABO3 oxides, LaCoO3, /\MnO3 and ATiO3 (A = Ca, Sr, Ba). Uniformly in all the cases, the perovskite oxides are obtained in the form of loosely connected submicron sized particles at considerably lower temperatures than those usually employed for their synthesis by ceramic methods. Thermodynamic calculations have also been carried out to probe into the driving force of metathesis reactions involved in the synthesis. Chapter 3 describes an extension of the metathesis route for the synthesis of double perovskites, Sr2MWO6 (M = Mg, Mn, Fe, Ni). For this purpose, first we synthesized new rocksalt oxides of the general formula, Li4MWO6 (M = Mg, Mn, Fe, Ni). The oxides adopt rocksalt superstructures related to Li4MgReO6 (for M = Mg, Mn, Ni) and U4WO5 (for M = Fe). Metathesis reaction between Li4MWO6 and SrCi2 at 750 - 800 °C yields the corresponding double perovskites where the octahedral site M and W are ordered in the long range. Formation of ordered perovskite oxides at relatively low temperatures (750 - 800 °C) by the metathesis route is a significant result, considering that synthesis of these oxides by conventional ceramic method requires much higher temperatures (1300 - 1400 °C) and prolonged annealing. Synthesis of La2CuO4, Nd2CuO4 and super conducting La-j 85>4oi5Cu04 (A = Sr, Ba) by the metathesis route is described in Chapter 4. Chapter 5 deals with synthesis, structure and magnetic properties of mixed-metal oxides of ABO3 composition in the La-6-V-O (6 = Ni, Cu) systems. While the B = Ni oxides adopt GdFeO3-like perovskite structure containing disordered nickel and vanadium at the octahedral B site, La3Cu2VO9 crystallizes in a YAIO3-type structure. A detailed investigation of the superstructure of nominal La3Cu2VO9 by WDS analysis and Rietveld refinement of powder XRD data reveals that the likely composition of the phase is Lai3Cu9V4O38 5, where the Cu and V atoms are ordered in a Vi3ah (ah = hexagonal a parameter of YAlCMike subcell) superstructure. Magnetic susceptibility data support the proposed superstructure consisting of triangular Cu3 clusters. The present work reveals the contrasting behaviour of La-Cu-V-O and La-Ni-V-0 systems, while a unique line-phase related to YAIO3 structure is formed around La3Cu2VO9 composition in the copper system, a continuous series of perovskite-GdFeO3 solid solutions, LaNi1.0CVxO3 for 0 < x < 1/3 seems to obtain in the nickel system. The chapter also describes the formation of a new transparent Cu(l) oxide, Lai4V6CuO365, and its characterization. This oxide was obtained during attempts to grow single crystals of LasC^VOg. Single crystal structure determination of Lai4V6CuO36 5 showed that the structure contains isolated VO43" tetrahedra and [OCuO]3" sticks dispersed in a lanthanum oxide network. Films of Lai4V6CuO36 5 were grown on R-plane sapphire by using pulsed laser deposition. Rutherford backscattering spectroscopic and X-ray diffraction analyses of the films showed oriented growth of the title phase, with an optical band gap of -~ 5 eV and n-type conductivity Chapter 6 presents the work on the flexibility of the Aurivillius structures for substitution of aliovalent/isovalent cations at both A and 6 sites of the perovskite slabs. For example, in a typical n = 3 member, Bi2Sr2Nb2TiOi2, substitution of both Sr and Na at the A site and Ta at the B site has enabled us to synthesize a new n = 3 member, Bi2SrNaNb2Ta0i2, where we see a preference of Nb for the terminal octahedral sheets. Similarly, aliovalent substitution only at the B site of the perovskite slabs of Bi2Sr2Nb2TiOi2 has yielded new members for specific compositions, Bi2Sr2Nb2ZrOi2, Bi2Sr2Nb2 5Feo50i2 and Bi2Sr2Nb2 67Zno33012 that tend to be oxygen-stoichiometric. The latter phases again show a preference of Nb for the terminal octahedral sites that are strongly distorted as compared to the middle octahedral site. This chapter also describes substitution of La3+ for Bi3+ in the perovskite slabs of Bi4Nb30i5 stabilizing a new series of n = 1/ n = 2 intergrowth Aurivillius phases of the formulas, Bi4LnNb3Oi5 (Ln = La, Pr, Nd) and Bi4LaTa30i5. The present work suggests that replacement of Bi3+: 6s2 lone pair ion by non-6s2 cations such as Sr2"* and La3+ in the perovskite slabs of Aurivillius phases tends to render the structure Centro symmetric and the materials lose NLOSHG response. Chapter 7 describes our investigation of the interaction of hydrogen with alkaline earth manganites (IV) >AMnO3 (>A = Ca, Sr, Ba) dispersed with 1 atom % Pt. The result shows an unprecedented uptake of hydrogen by BaMnO3/Pt to the extent of - 1.25 mass % at moderate temperatures (190 - 260 °C) and ambient pressure. Gravimetric sorption isotherms and mass spectrometric analysis of the desorption products indicate that approximately three hydrogen atoms per mole of BaMnCVPt is inserted reversibly. The nature of hydrogen in the insertion product, BaMnO3H3, is discussed in the light of the structure of BaMnC>3. The work presented in the thesis is carried out by the candidate as a part of the Ph. D. training programme and most of it has been published in the literature. He hopes that the studies reported here will constitute a worthwhile contribution to the materials chemistry of ABO3 oxides in general.

Oxides of ABO3 composition (A = alkali, alkaline earth or rare earth metal in general, B = transition metal) constitute a large family of metal oxides of current interest to solid state and materials chemistry. Among the several structure types exhibited by ABO3 oxides (ilmenite, LiNbO3, perovskite, YAIO3/YMnO3, KSbO3, pyrochlore, among others), the perovskite structure is probably the most well known and widely investigated. The ideal perovskite structure consists of a three-dimensional (3D) framework of corner-sharing BO6 octahedra in which the A cation resides in the dodecahedral site surrounded by twelve oxide ions. The ideal cubic structure occurs when the Gold Schmidt’s tolerance factor, t = (rA + ro)/{V2 (rB + ro)}, adopts a value of unity and the A-O and B-O bond distances are perfectly matched. The flexibility of the perovskite structure towards a wide variety of substitutions at both A and B sites gives rise to a very large number (several hundreds) of perovskite derivatives with subtle variations in structure. The perovskite structure can also tolerate vacancies at both the A and O sites giving ordered superstructures. Members of y4BO3 oxides have numerous properties that find technological application, such as nonlinear optical response (LiNbO3), Ferro electricity (BaTiO3), piezoelectricity (PbZn_xTixO3), magneto ferroelectricity (YMnO3), superconductivity (Bai_xKxBi03)5 colossal magnetoresistance (La^xCaxMnO3) and ionic conductivity [(Lil_a)TiO3] Ordering of cations at the A and B sites of the perovskite structure is an important phenomenon. Ordering of B site cations in double (/42BB'O6) and multiple (/43BB'2Og) perovskites gives rise to newer and interesting materials properties For example, 1*1 ordered Sr2FeMoO6 and Sr2FeReO6 are half-metallic ferrimagnets; Pb3MgNb2O9 is a relaxor ferroelectric; Ba3ZnTa2O9 is a low loss dielectric used in telecommunication and, last but not least, Ba3CoNb2O9 is a visible light driven photocatalyst. Realization of these properties in these materials depends crucially on the ordering/or otherwise of the B site cat ions in the perovskite structure. Furthermore, ordering of not only the metal atoms but also the oxygen/oxygen vacancies in the perovskite structure is equally important for the occurrence of superconductivity in the cuprate superconductor, YBa2Cu3O7. The ideal perovskite structure gives way to hexagonal YMnO3/YAIO3 structure for smaller A cations (tolerance factor, t < 1). Oxides of this structure are attracting current attention for the realization of multiple magnetoferroic properties. On the other hand, for larger A cations (tolerance factor, t > 1), various perovskite polytypic structures are formed. For example, BaNiO3 forms a 2H polytypic structure, SrMnO3 and BaRuO3 adopts a 4H and 9R structures respectively, where the SO6 octahedra share faces or faces and corners. Besides the foregoing 3D perovskites, a number of layered variants of the perovskite structure are also known. The most common layered perovskites are the Aurivillius phases, (Bi2O2)[A»-iBnO3n+iL the Ruddlesden-Popper phases, /4'2|7ln_iBnO3n+1], and the Dion-Jacobson phases, A[An^BnOzn+-\]' The two-dimensional (2D) perovskite unit, [^n-iBnOsn+i], which could be visualized as formed by slicing the 3D perovskite structure along <001>p is common for all the three layered perovskite series. The perovskite slabs are stacked alternately with various charge-balancing units, for example, with [Bi2O2]2+ in the Aurivillius phases and two alkali/alkaline earth cations (A+JA2+) in the Ruddlesden-Popper phases etc. Members of the layered perovskites are also important from the point of view of materials properties. For example, 2D magnetism (K2NiF4), superconductivity (La2-xSrxCuO4), ion exchange, Bronsted acidity, intercalation, exfoliation (K2La2Ti3Oio and CsCa2Nb3O10), photo catalysis (Rb2La2Ti30io) are some of the important materials properties found in layered perovskites. The high Tc-superconductors, Bi2Sr2CaCu2O8+XJ TI2Ba2Ca2Cu3Oi0, TIBa2Ca2Cu3O9 and HgBa2Ca2Cu3O8+x, also belong to the family of layered perovskites where the defective perovskite cuprate sheets are interleaved by other 2D entities like (Bi2O2), (TI2O2), (TIO) or (HgOx). In addition, Aurivillius phases, such as Bi2SrTa209 and Bi325Lao75Ti3Oi2, in thin film geometry are candidate materials for non-volatile ferroelectric memory devices. Synthesis plays a key role in realizing new structures and materials properties for ABO3 oxides. The conventional synthetic methods (ceramic method) involve mixing and heating of solid reactants at elevated temperatures. Although this approach continues to be employed to synthesize new materials, it is often limited by the fact that it yields thermodynamically stable phases. Since many of the perovskite oxides showing useful materials properties are metastable in nature and are required in the form of fine particles (free-standing / monodisperse / submicron or nanometer dimensions) for application, the ceramic methods are of no avail for this purpose. Therefore, materials chemists constantly endeavor to develop alternate synthetic routes that enable them to synthesize novel oxides under mild conditions. Typical examples of metastable perovskites are: the super conducting cuprates (e.g. TlosPbosS^CaC^Og) and perovskite based lithium ion conductors (La2/3-xLi3XDi/3-2xTiO3). Also the control of oxidation states in double perovskites, such as Sr2FeMoO6 and Sr2FeRe06 and pyrochlores such as Pb2MnReC>6, cannot be achieved by conventional means. Therefore, the synthesis of such metastable phases requires special synthetic strategies that involve soft chemistry (chimie douce) methods where mild reactions/reaction conditions are employed to access metastable phases. The present thesis is mainly devoted to an investigation of perovskite related oxides towards developing new synthetic strategies and materials as well as exploring hydrogen insertion - a novel materials property - in certain members of this family. Solid-state metathesis (SSM) reactions provide a convenient route for the synthesis of a wide variety of non-oxide ceramic materials such as, bondes, carbides, silicides, pnictides and chalcogenides. A typical metathesis reaction, for example, M0CI5 + 5/2 Na2S -» MoS2 + 5 NaCI + 1/2 S (1) involves exchange of atoms/ions between the reactants and is accompanied by a large enthalpy change (AHm = - 890 kJ mol"1) and high adiabatic reaction temperature (Tm = 1413 °C). The reactions are often self-propagating and believed to be driven by the formation of stable salt byproducts such as alkali halides with high lattice energy. In our laboratory we have developed a different kind of metathesis reaction for the synthesis of perovskite related oxides, a typical example being, K2La2Ti30io + 2 BiOCI -* [Bi2O2]La2Ti3O10 + 2 KCI. A major difference between metathesis reactions (1) and (2) is that unlike (1), reaction (2) is not self-propagating, requiring longer duration. In this study, we have investigated metathesis reactions of the second kind at some length for the synthesis of perovskite related oxides. We found that rocksalt oxides such as UMO2 (M = Mn, Co) and Li2TiO3 constitute convenient precursors for the formation of v4BO3 perovskite oxides in metathesis reactions with appropriate reaction partners such as halides, oxyhalides or sulphates, LiCoO2 + LaOCl -» LaCoO3 + LiCt (3) LiMnO2 + LaOCl + x/2 O2 -> LaMnO3+x + LiCI (4) Li2TiO3 + PbSO4 -» PbTiO3 + Li2SO4. (5) We could synthesize not only well known ABO3 oxides but also functional perovskites such as PbZr0 4sTio 52O3 (PZT), La2/3Cai/3MnO3 as well as superconducting BaPbo75Bio2s03 by this method. We could also synthesize La2CuO4 and its superconducting analogues, La185^oi5Cu04 (A = Sr, Ba), by the same method using Li2CuO2 and LaOCl. For the synthesis of double perovskites A2BB%OQ by this method however, appropriate lithium containing rocksalt precursor oxides are not known in the literature. Therefore, we first synthesized rocksalt precursor oxides of the general formula Li4MWO6 (M = Mg, Mn, Fe, Ni) and established their identity. Using these precursor oxides, we could synthesize the double perovskite oxides Sr2MWO6 (M = Mg, Mn, Fe, Ni) in the metathesis reaction Li4MWO6 + 2 SrCI2 -» Sr2MWO6 + 4 LiC Significantly, the double perovskites are formed with an ordered structure at relatively low temperatures (750 - 800 °C) as compared to the high temperatures (up to 1400 °C) usually employed for the synthesis of these materials by conventional ceramic approach. Next, we investigated ABO$ compositions corresponding to the formula for 6 = Cu and Ni, where we could obtain a YAIO3 superstructure consisting of triangular Cu clusters for 6 = Cu, whereas a perovskite phase for B = Ni. Moreover, the Cu-phase appears to be a unique line phase formed around LasCi^VOg composition, whereas a continuous series of GdFeO3-like perovskite oxides are formed for LaNii»xVxO3 (0 < x < 1/3)forS = Ni. Considering the current interest in bringing different transition metal ions (d°/dn electronic configuration) in the same perovskite related structure towards developing multiferroic materials, we investigated the substitution of aliovalent cations in a typical Aurivillius phase, Bi2Sr2Nb2TiOi2. We have characterized new aliovalent cation substituted Aurivillius phases, Bi2SrNaNb2TaOi2, Bi2Sr2Nb2Zr012J Bi2Sr2Nb2 5Feo50i2 and Bi2Sr2Nb2 ezZno 33O12. Lastly, we investigated the interaction of hydrogen with perovskite oxides, /\MnO3 (A = Ca, Sr, Ba) in an attempt to characterize possible existence of hydrogen-inserted oxide materials. An oxide-hydride of the formula LaSrCoO3H07 has recently been reported in the literature. Conventionally, the interaction of hydrogen with perovskite related oxides is known to result in either anion deficient phases (e.g. CaMnO3 -> Ca2Mn205), or hydrogen inserted materials, 'hydrogen bronzes', (e. g. HXWO3, HxBaRuO3), where hydrogen acts as an electron donor (H -^ H+ + e). We have characterized a new mode of hydrogen incorporation in Pt dispersed BaMnO3 and SrMnO3. Detailed investigation of the hydrogen sorption behaviour of 1 atom % Pt dispersed materials showed that about 1.25 mass % of hydrogen is inserted per mole of BaMnO3/Pt, corresponding to an insertion of - 3 hydrogen atoms giving 'BaMnOsHs'. While the exact nature of inserted hydrogen is yet to be established unambiguously, our results suggest that the inserted hydrogen is unlikely to be protonic (H+) in the hydrogen insertion product, BaMnO3H3. The results of these investigations are presented in the thesis consisting of seven chapters. Chapter 1 gives an overview of perovskite related oxides - structure, properties and synthesis. Chapter 2 presents metathesis as a general route for the synthesis of ABO3 oxides and illustrates the method by transforming several rocksalt oxides such as LiCoO2, Li2Mn03 and Li2Ti03 to corresponding ABO3 oxides, LaCoO3, /\MnO3 and ATiO3 (A = Ca, Sr, Ba). Uniformly in all the cases, the perovskite oxides are obtained in the form of loosely connected submicron sized particles at considerably lower temperatures than those usually employed for their synthesis by ceramic methods. Thermodynamic calculations have also been carried out to probe into the driving force of metathesis reactions involved in the synthesis. Chapter 3 describes an extension of the metathesis route for the synthesis of double perovskites, Sr2MWO6 (M = Mg, Mn, Fe, Ni). For this purpose, first we synthesized new rocksalt oxides of the general formula, Li4MWO6 (M = Mg, Mn, Fe, Ni). The oxides adopt rocksalt superstructures related to Li4MgReO6 (for M = Mg, Mn, Ni) and U4WO5 (for M = Fe). Metathesis reaction between Li4MWO6 and SrCi2 at 750 - 800 °C yields the corresponding double perovskites where the octahedral site M and W are ordered in the long range. Formation of ordered perovskite oxides at relatively low temperatures (750 - 800 °C) by the metathesis route is a significant result, considering that synthesis of these oxides by conventional ceramic method requires much higher temperatures (1300 - 1400 °C) and prolonged annealing. Synthesis of La2CuO4, Nd2CuO4 and super conducting La-j 85>4oi5Cu04 (A = Sr, Ba) by the metathesis route is described in Chapter 4. Chapter 5 deals with synthesis, structure and magnetic properties of mixed-metal oxides of ABO3 composition in the La-6-V-O (6 = Ni, Cu) systems. While the B = Ni oxides adopt GdFeO3-like perovskite structure containing disordered nickel and vanadium at the octahedral B site, La3Cu2VO9 crystallizes in a YAIO3-type structure. A detailed investigation of the superstructure of nominal La3Cu2VO9 by WDS analysis and Rietveld refinement of powder XRD data reveals that the likely composition of the phase is Lai3Cu9V4O38 5, where the Cu and V atoms are ordered in a Vi3ah (ah = hexagonal a parameter of YAlCMike subcell) superstructure. Magnetic susceptibility data support the proposed superstructure consisting of triangular Cu3 clusters. The present work reveals the contrasting behaviour of La-Cu-V-O and La-Ni-V-0 systems, while a unique line-phase related to YAIO3 structure is formed around La3Cu2VO9 composition in the copper system, a continuous series of perovskite-GdFeO3 solid solutions, LaNi1.0CVxO3 for 0 < x < 1/3 seems to obtain in the nickel system. The chapter also describes the formation of a new transparent Cu(l) oxide, Lai4V6CuO365, and its characterization. This oxide was obtained during attempts to grow single crystals of LasC^VOg. Single crystal structure determination of Lai4V6CuO36 5 showed that the structure contains isolated VO43" tetrahedra and [OCuO]3" sticks dispersed in a lanthanum oxide network. Films of Lai4V6CuO36 5 were grown on R-plane sapphire by using pulsed laser deposition. Rutherford backscattering spectroscopic and X-ray diffraction analyses of the films showed oriented growth of the title phase, with an optical band gap of -~ 5 eV and n-type conductivity Chapter 6 presents the work on the flexibility of the Aurivillius structures for substitution of aliovalent/isovalent cations at both A and 6 sites of the perovskite slabs. For example, in a typical n = 3 member, Bi2Sr2Nb2TiOi2, substitution of both Sr and Na at the A site and Ta at the B site has enabled us to synthesize a new n = 3 member, Bi2SrNaNb2Ta0i2, where we see a preference of Nb for the terminal octahedral sheets. Similarly, aliovalent substitution only at the B site of the perovskite slabs of Bi2Sr2Nb2TiOi2 has yielded new members for specific compositions, Bi2Sr2Nb2ZrOi2, Bi2Sr2Nb2 5Feo50i2 and Bi2Sr2Nb2 67Zno33012 that tend to be oxygen-stoichiometric. The latter phases again show a preference of Nb for the terminal octahedral sites that are strongly distorted as compared to the middle octahedral site. This chapter also describes substitution of La3+ for Bi3+ in the perovskite slabs of Bi4Nb30i5 stabilizing a new series of n = 1/ n = 2 intergrowth Aurivillius phases of the formulas, Bi4LnNb3Oi5 (Ln = La, Pr, Nd) and Bi4LaTa30i5. The present work suggests that replacement of Bi3+: 6s2 lone pair ion by non-6s2 cations such as Sr2"* and La3+ in the perovskite slabs of Aurivillius phases tends to render the structure Centro symmetric and the materials lose NLOSHG response. Chapter 7 describes our investigation of the interaction of hydrogen with alkaline earth manganites (IV) >AMnO3 (>A = Ca, Sr, Ba) dispersed with 1 atom % Pt. The result shows an unprecedented uptake of hydrogen by BaMnO3/Pt to the extent of - 1.25 mass % at moderate temperatures (190 - 260 °C) and ambient pressure. Gravimetric sorption isotherms and mass spectrometric analysis of the desorption products indicate that approximately three hydrogen atoms per mole of BaMnCVPt is inserted reversibly. The nature of hydrogen in the insertion product, BaMnO3H3, is discussed in the light of the structure of BaMnC>3. The work presented in the thesis is carried out by the candidate as a part of the Ph. D. training programme and most of it has been published in the literature. He hopes that the studies reported here will constitute a worthwhile contribution to the materials chemistry of ABO3 oxides in general.

by Tsai Yau Moon = 錳氧化物的金屬-絶緣體轉變 : 多層薄膜及異構結 / 蔡友滿.
Thesis (M.Phil.)--Chinese University of Hong Kong, 2006.
Includes bibliographical references.
Text in English; abstracts in English and Chinese.
by Tsai Yau Moon = Meng yang hua wu de jin shu-jue yuan ti zhuan bian : duo ceng bo mo ji yi gou jie / Cai Youman.
Abstract
論文摘要
Acknowledgements
Table of Contents
List of Figures
List of Tables
Chapter Chapter 1 --- Introduction
Chapter 1.1 --- Perovskite-type structure
Chapter 1.2 --- Metal-insulator transition
Chapter 1.3 --- Magnetoresistance
Chapter 1.3.1 --- Giant magnetoresistance (GMR)
Chapter 1.3.2.1 --- Colossal magnetoresistance (CMR) in perovskite manganites
Chapter 1.3.2.2 --- Possible origin of CMR
Chapter 1.4 --- Brief review of p-n junction between perovskite manganites and STON (001)
Chapter 1.5 --- Our project
Chapter 1.6 --- Scope of this thesis work
References
Chapter Chapter 2 --- Preparation and characterization of manganite thin films
Chapter 2.1 --- Thin film deposition
Chapter 2.1.1 --- Facing-target sputtering (FTS)
Chapter 2.1.2 --- Vacuum system
Chapter 2.1.3 --- Deposition procedure
Chapter 2.1.4 --- Deposition conditions
Chapter 2.1.5 --- Oxygen annealing system
Chapter 2.1.6 --- Silver electrode coating system
Chapter 2.2 --- Characterization
Chapter 2.2.1 --- Alpha step profilometer
Chapter 2.2.2 --- X-ray diffraction (XRD)
Chapter 2.2.3 --- Transport property measurement
References
Chapter Chapter 3 --- [LCSMO/PCMO] multilayers
Chapter 3.1 --- [LCSMO (100 A)/PCMO (X A)] multilayers
Chapter 3.1.1 --- Sample preparation
Chapter 3.1.2 --- Results and discussion
Chapter 3.1.2.1 --- Structural analysis
Chapter 3.1.2.2 --- Transport properties
Chapter 3.2 --- [LCSMO (50 A)/PCMO (X A)] multilayers
Chapter 3.2.1 --- Sample preparation
Chapter 3.2.2 --- Results and discussion
Chapter 3.2.2.1 --- Structural analysis
Chapter 3.2.2.2 --- Transport properties
References
Chapter Chapter 4 --- [LSMO/PCMO] multilayers and LSMO/STON p-n junction
Chapter 4.1 --- [LSMO/PCMO] multilayers
Chapter 4.1.1 --- Sample preparation
Chapter 4.1.2 --- Results and discussion
Chapter 4.1.2.1 --- Structural analysis
Chapter 4.1.2.2 --- Magnetization
Chapter 4.2 --- LSMO/STON heterojunction
Chapter 4.2.1 --- Sample preparation
Chapter 4.2.2 --- Results and discussion
Chapter 4.2.2.1 --- Structural analysis
Chapter 4.2.2.2 --- Metal insulator transition of LSMO revealed by four point I-V measurement
Chapter 4.3 --- Conclusion
References
Chapter 5 Conclusion
Chapter 5.1 --- Conclusion
Chapter 5.2 --- Future outlook

Multifunctional materials with novel magnetic and electric properties have attracted intense research interest due to prospects in technological applications as well as understanding of fundamental physics. Perovskite materials with ABO3 structure belong to one of the most interesting and vastly studied families by virtue of their rich magnetic and electrical properties. In the present thesis, efforts have been made to investigate the magnetic, electrical, and structural properties of A and B-site doped perovskites. In the beginning, a general introduction to basic concepts of various physical phenomena are discussed. This is followed by a brief description of the various experimental methods employed including sample synthesis and single crystal growth. Fe3+ and Mn3+ have the same ionic radii in oxygen octahedra. However, Mn3+ is Jahn–Teller active, and the magnetic ground states of RFeO3 and RMnO3 are completely different. The evolution of structural and electrical properties with doping of Mn3+ ion in RFeO3 was investigated on a series of NdFe1-xMnxO3 (0≤x≤1) compounds. Despite similar ionic radii in Mn3+ and Fe3+, a large variation in the lattice parameters and a crossover from dynamic to static Jahn– Teller distortion were discernible. The magnitude of Fe/Mn–O–Fe/Mn bond angle on ab plane and activation energy corresponding to transport and dielectric relaxation (deduced by assuming the small polaron hopping (SPH) model) vary with doping in a characteristic manner which was attributed to changes in magnetic interaction. Effects of size mismatch at B-site were investigated by doping Mn-site with Ni cations in Ho2NiMnO6 compound. This induces B-site ordering which leads to double perovskite structure and ferromagnetic ordering at TC = 86 K. Ideal Curie–Weiss law fails to provide a reasonable fit in the paramagnetic region which follows a modified Curie–Weiss law. Such a deviation occurs due to presence of heavy rare earth element Ho. Griffiths phase pertaining to the Ni/Mn subsystem was ascertained. Two dielectric relaxations due to phononic and Maxwell–Wagner mechanisms were observed. The system has also been shown to be a potential magnetocaloric refrigerant. A solid solution of RFeO3 and RMnO3 offer much prospects due to its vastly different magnetic properties. A single crystalline phase is essential for such studies, and we were successful in growing single crystals of ErFe0.55Mn0.45O3 which order antiferromagnetically at 365 K with spin canting-induced weak ferromagnetic moment along c axis. Upon cooling, magnetization along c axis passes through zero at 266.4 K and becomes negative below this temperature and a spin reorientation occurs from Γ4(Gx, Ay, Fz) to Γ1(Ax, Gy, Cz) configuration in the temperature window of 255 to 258 K. Magnetic behavior is explained with spin configuration and interplay between net magnetization of individual Er and Fe/Mn sublattices which are oppositely coupled and have different temperature evolution. To observe the effect of A-site doping on RFeO3 perovskites, Ho0.5Dy0.5FeO3 single crystals were grown. Two spin reorientations of Fe magnetic sublattice were evident viz. Γ4(Gx, Ay, Fz) → Γ1(Ax, Gy, Cz) → Γ2(Fx, Cy, Gz) at temperatures of 49 and 26 K. As magnetic field along c axis increases, the sample resumes Γ4 state in place of Γ1 state. Along c axis, field- induced transition from Γ1 to Γ4 is feasible. Studies on hybrid organic-inorganic perovskite compounds have also been carried out on heterometallic [(CH3)2NH2]Mn0.5Ni0.5(HCOO)3 and [(CH3)2 NH2]Co0.5Ni0.5(HCOO)3 which were found to crystallize in trigonal space group R-3c at room temperature and order antiferromagnetically with weak ferromagnetism induced by spin canting at 17 and 8 K, respectively. Hydrogen bond ordering leads to spontaneous polarization and structural transition occurs from R-3c to Cc through mixed phase. This is reflected in impedance data also. Highlights of major findings in different chapters and a general conclusion to this study are presented at the end.

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.