Orientador: Annette Gorenstein / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-08-05T23:58:57Z (GMT). No. of bitstreams: 1 SouzaJunior_EdvaldoAlvesde_D.pdf: 2701192 bytes, checksum: 949e8dd1afc482f52e573f2b9fbca63a (MD5) Previous issue date: 2006 / Resumo: O pentóxido de vanádio é um dos compostos de intercalação mais conhecidos na área de baterias de lítio. Dada sua estrutura lamelar, íons de lítio podem ser inseridos e extraídos de forma reversível, o que torna o pentóxido de vanádio promissor para uso como catodo. No entanto, o armadilhamento de parte dos íons de lítio a cada ciclo de carga e descarga provoca a perda gradativa da capacidade. A incorporação de íons metálicos na estrutura do V2 >O5 é uma das alternativas para melhorar seu desempenho nos ciclos de carga e descarga. Por outro lado, foi demonstrado que o óxido de cobre nanoparticulado é capaz de fornecer alta capacidade de carga em processos reversíveis de inserção e extração de íons lítio. Esta tese se propõe estudar a inserção/extração de íons de lítio em filmes finos de óxidos de cobre-vanádio objetivando sua aplicação em catodos de microbaterias. Um conjunto de amostras foi obtido iniciando-se com o pentóxido de vanádio, e através de acréscimos de cobre e decréscimos de vanádio, atingindo o óxido de cobre II. Óxidos bronzes, complexos, mistos e puros foram obtidos. As amostras foram depositadas através da técnica de sputtering. Na caracterização das amostras foram utilizadas técnicas de difração de raios-X, retroespalhamento Rutherford, emissão de fotoelétrons de raios-X, absorção de raios-X (XANES) e microscopia de força atômica. A inserção de íons de lítio foi realizada através da cronopotenciometria. Cada classe de óxidos apresentou características eletroquímicas próprias. Óxidos de cobre apresentaram uma capacidade de inserção de carga quatros vezes maior que a capacidade do pentóxido de vanádio (109 µAh/cm 2-µm). Bronzes de vanádio apresentaram maior estabilidade entre todos óxidos, e melhor capacidade, quando comparado com o V2 O5. A introdução de átomos de vanádio na matriz CuO permitiu a formação de óxidos mistos com maior estabilidade eletroquímica quando comparados à filmes CuO / Abstract: In the field of lithium batteries, vanadium pentoxide is one of the most studied intercalation compound. Due to its lamellar structure, lithium ions can be reversibly inserted and extracted, and the material is a promising candidate for use as a cathode. However, trapping of part of the lithium ions in each charge/discharge cycle causes a gradative loss of capacity. The incorporation of metallic ions in the V22O5host structure is one of the alternatives to improve its cycling behavior. On the other hand, it was recently demonstrated that nanosized copper oxide is capable of providing high charge capacity in reversible lithium insertion/extraction processes. The aim of the present work is to study the insertion/extraction of lithium ions in thin films of copper-vanadium oxides for application as cathode in microbatteries. A range of samples was produced, starting from pure vanadium pentoxide. By increasing the amounts of copper and decreasing the amount of vanadium in the film, the copper oxide II composition was attained. Different classes of oxides, such as bronzes, complex oxides, mixed oxides and the pure oxides were obtained. The samples were deposited by sputtering. The characterization was performed using X-Ray diffraction, Rutherford Backscattering spectrometry, X-Ray Photoemission Spectroscopy, X-Ray Absorption Spectroscopy (mainly XANES) and Atomic Force Microscopy. The electrochemical behavior was analyzed mainly by chronopotentiometry. Each class of oxides presented distinct electrochemical properties. Copper oxide films presented an insertion capacity four times greater than the capacity of the vanadium pentoxide films (109 µAh/cm 2-µm). Vanadium bronzes presented the best stability among all of the investigated materials, and a higher capacity in comparison to vanadium pentoxide. The insertion of vanadium atoms in the CuO structure allowed the obtention of mixed oxides films with higher electrochemical stability if compared to pure CuO films / Doutorado / Superfícies e Interfaces ; Peliculas e Filamentos / Doutor em Ciências

Die eingereichte Dissertation befasst sich mit Übergangsmetalloxid-Nanostrukturen, wobei quasi-eindimensionale Materialien im Mittelpunkt stehen, z.B. Nanoröhren und Nanostäbe. Mittels Suszeptibilitäts- bzw. EELS-Messungen wurden magnetische und elektronische Eigenschaften verschiedener Nanoverbindungen untersucht. Zur weiteren Charakterisierung der Proben wurden außerdem Magnetisierungsmessungen (VSM, Pulsfeld), optische Spektroskopie, AC-Suszeptibilitätsmessungen, Messungen der spezifischen Wärme sowie NMR- und ESR-Experimente durchgeführt. Ein Schwerpunkt dieser Arbeit sind Vanadiumoxid-Verbindungen, wobei Vanadiumoxid-Nanoröhren (VOxNT) aufgrund ihrer besonderen Morphologie eine Sonderstellung unter den vorgestellten Materialien besitzen. Suszeptibilitätsmessungen an den VOxNT offenbaren aktiviertes Verhalten bei Temperaturen T > 100 K, was auf V4+-Spindimere zurückgeführt werden kann. Zudem existieren quasi-freie V4+-Momente sowie längere Spinkettenfragmente, z.B. Trimere. Elektronische Anregungen im Valenzband können wahrscheinlich dem Platzwechsel von 3d-Elektronen zwischen V4+- und V5+-Plätzen innerhalb der gemischtvalenten V-O-Ebenen zugeschrieben werden. Durch Dotierung mit Alkalimetallen ist es möglich, die V 3d-Niveaus mit zusätzlichen Elektronen zu besetzen und dadurch die Vanadiumvalenz zu beeinflussen (V5+ -> V4+ -> V3+). Die dabei auftretenden stärkeren Coulombabstoßungen zwischen den V 3d-Elektronen beeinträchtigen die Mobilität der Ladungsträger. Ebenso wurde gezeigt, dass sich durch die Dotierung mit Ammoniak und anderen Übergangsmetallionen die Vanadiumvalenz sowie der Magnetismus der VOxNT beeinflussen lassen. Die Ergebnisse von weiteren Vanadiumoxid-Nanostrukturen - Co0.33V2O5, alpha-NaV2O5, VO2(B) sowie V3O7·H2O-Nanokristallen - zeigen, dass sehr unterschiedliches magnetisches Verhalten wie Paarbildung zwischen V4+-Spins, antiferromagnetisch gekoppelte Spinketten oder ein Phasenübergang zwischen zwei paramagnetischen Temperaturbereichen auf Nanoebene realisiert werden kann. Die magnetischen Eigenschaften von MnO2-Nanostäben sind durch starke Kopplungen und Frustration zwischen den Mn-Spins gekennzeichnet. Außerdem zeigt die Verbindung Merkmale eines Spinglases. Durch Dotierung mit Elektronen lässt sich bei diesem Material die Mn-Valenz verändern. Schließlich zeigen erste Charakterisierungsmessungen an übergangsmetalldotierten MoO3-Nanobändern paramagnetisches Verhalten dieser Systeme.

Defects in materials significantly influence their properties and enhance functionality. Hybrid functionals like HSE06, though effective for describing defects, face challenges in geometry optimization for large supercells. The r2SCAN+rVV10+U+Ud method provides a computationally efficient alternative. By selecting appropriate U and Ud values for the d orbitals of host and defect atoms, this method accurately describes defects in materials. Our study on small polaron defects in layered transition-metal oxides demonstrates this. Using literature values for U and Ud, we investigated birnessite (KnMnO2, n = 0.03) and KnNiO2, n = 0.03. With one K atom intercalated in a supercell, both materials show a localized eg polaronic state on the transition metal ion reduced by the K atom, when the geometry is calculated using published U values. The expected Jahn-Teller distortion is not observed when U=Ud=0. In layered cobalt oxide with additional potassium ions (KnCoO2, n = 1.03), a single extra K atom in the supercell leads to four localized electrons in the band gap, using standard U values, and even for U=Ud=0. Monolayer MoS2 exhibits intriguing properties and potential technological applications when subjected to strain. A recent experimental study reported that the bandgap of monolayer MoS2 on a mildly curved graphite surface decreases by 400 meV/% strain under biaxial strain with a Poisson’s ratio of 0.44. We conducted density functional theory (DFT) calculations on a free-standing MoS2 monolayer using the generalized gradient approximation (GGA) PBE, the hybrid functional HSE06, and many-body perturbation theory with the GW approximation using PBE wavefunctions (G0W0@PBE). Our findings indicate that under biaxial strain with the experimental Poisson’s ratio, the bandgap decreases at rates of 63 meV/% strain (PBE), 73 meV/% strain (HSE06), and 43 meV/% strain (G0W0@PBE), which are significantly lower than the experimental rate. Additionally, PBE predicts a reduction rate of 90 meV/% strain for a Poisson’s ratio of 0.25. Spin-orbit correction (SOC) has minimal impact on the bandgap or its strain dependence. We also observed a semiconductor-to-metal transition at 10% tensile biaxial strain and a shift from a direct to an indirect bandgap, aligning with previous theoretical studies. / Physics

Electronic structure of transition metal oxides has been a subject of intense research since decades due to the wide spectrum of properties that they exhibit, like high temperature superconductivity, metal-insulator transitions (MIT), phase separation etc. Among these, colossal magnetoresistance (CMR), i.e. a sharp drop in the electrical resistance by the application of an external magnetic field, is a property of fundamental and technological importance. In the present study we investigate several of these interesting properties ranging from colossal magnetoresistance, metal-insulator transitions and phase separation phenomena on a wide range of magnetoresistive systems. All these properties originate in transition metal oxides due to a competition between the strong inter-atomic Coulomb interaction strength within the transition metal d electrons and a large hopping interaction strength between the metal d and oxygen 2p states. In this thesis we report the investigation of the electronic and magnetic structures of some magnetoresistive oxides, including various double perovskites and manganites, using various high energy spectroscopies in conjunction with various theoretical approaches. The samples for the present experimental investigation were prepared by different synthetic routes, such as solid state reaction, nitrate method, d.c arc melting and float zone method, and were characterized by x-ray diffraction, four probe resistivity, magnetic susceptibility, optical absorption and energy dispersive analysis of x-rays while some of the samples were supplied by our collaborators. Various spectroscopic techniques like x-ray photoemission spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS) , bremsstrahlung isochromat spectroscopy (BIS), x-ray absorption spectroscopy (XAS), x-ray magnetic circular dichroism spectroscopy (XMCD) , electron energy loss spectroscopy (EELS), spatially resolved photoelectron spectroscopy and M¨ ossbauer spectroscopy were used to probe the samples. Theoretical methods include configuration interaction cluster approach to fit the XAS and XMCD spectra while ab initio band structure calculations along with the least-square fitting procedure was used to fit some of the valence and conduction bands. Following a general introduction in Chapter 1, the details of various experimental and theoretical techniques are discussed in Chapter 2 of this thesis. Recently, a double perovskite, Sr2FeMoO6, belonging to a general family of halfmetallic ferromagnetic oxides, has shown a spectacularly large magnetoresistance even at the room temperature and at relatively small applied magnetic fields compared to the extensively investigated class of magnetoresistive manganites. Physical properties of this compound is strongly influenced by the Fe -Mo ordering. We hence synthesized Sr2FeMoO6 sample, both with high and low degree of Fe/Mo ordering. Spectroscopic investigations of these samples suggest the presence of Fe rich and Mo rich domains of the type Sr2Fe1+xMo1−xO6 in disordered Sr2FeMoO6 at times. This prompted us to prepare bulk samples of Sr2Fe1+xMo1−xO6. In Chapter 3 we address various issues related to Fe/Mo ordering like saturation magnetization, variation of TC, and CMR as well as oxidation state of Fe and Mo in Sr2FeMoO6using this new series, ”Sr2Fe1+xMo1−xO6” as it offers a better control on the Fe/Mo bonds by controlling x. On the basis of the electron spectroscopic studies in conjunction with a configuration interaction cluster calculation model coupled with the conduction band, we claim that Fe remains in 3+oxidation state throughout the series, where as Mo changes its valency to maintain the charge neutrality. An analysis of the magnetic momentas a function of x suggests that Fe at the ”wrong” crystallographic site is coupled anti-parallel to the Fe moments at the ”correct” site. Additionally, Mo depolarizes to the extend proportional to the number of Mo sites in the near-neighbor co-ordination shell. Continuing with the double perovskites in Chapter 4 we investigate the electronic and magnetic structure of Sr2FeMoO6, Ca2FeMoO6 and Ba2FeMoO6using XAS and XMCD studies. We find that the conventional XAS and XMCD calculations based on configuration interaction of a typical fragment, FeO6in this case, is insufficient to reproduce the experimental spectrum as the compounds considered here are metallic. In order to include the non local charge transfer, we coupled FeO6 octahedra to a conduction band which mimics the Mo band. Within this model we obtained a good fit to the experimental spectrum. Chapter 5 deals with another series of double perovskite (Sr1−yCay)2FeReO6which exhibits a rich phase diagram since it undergoes a metal insulator transition (MIT) with composition at low temperatures. This system becomes more interesting due to the presence of a temperature driven MIT for higher y compositions. We find that the MIT is not related to the change in valency of Fe and Re. Analysis of the near Fermi edge valence band spectra suggests opening up of a soft gap. The main reason for MIT in this system is most likely the presence of strong electron-electron correlation between multiple electrons at the Re site, which is caused by the mismatch of the Re ionic radius and change in the crystal structure across MIT. Another issue which has been extensively investigated in this thesis is phase separation in manganites presented in Chapter 6. We use a spatially resolved, direct spectroscopic probe for electronic structure with an additional unique sensitivity to chemical compositions, to investigate high quality single crystal samples of La1/4Pr3/8Ca3/8MnO3 in the first section. This unique probe establishes the formation of distinct insulating domains embedded in the metallic host at low temperatures, significantly in the absence of any perceptible chemical inhomogeneity, with the domain-size at least an order of magnitude larger than the previous largest estimate. We also provide compelling evidence of memory effects in such domain formation and morphology, suggesting an intimate connection between these electronic domains and long-range strains, often thought to be an important ingredient in the physics of doped manganites. In second part of this chapter we discuss another system namely Eu0.5Y0.5MnO3 which undergoes a chemical phase separation forming alternate stripes of Eu rich (Y deficient) orthorhombic phase and Y rich (Eu deficient) hexagonal phases. These stripes are amazingly straight and run parallel over millimeters. One more system that we investigated is a mixture of ferromagnetic La5/8Sr3/8MnO3and insulating ferroelectric LuMnO3 taken in ratio 3:7, here too the attempt to make a single crystal resulted into a chemical phase separation forming strips of metallic La5/8Sr3/8MnO3and insulating LuMnO3 throughout the sample surface. Preliminary studies suggests that strain between the chemically and crystallographically different species may result into such interesting morphology. In Chapter 7 we study pseudo-one dimensional compounds Sr3CuIrO6 and Sr3ZnIrO6 using photo electron spectroscopy. The experimental results were fitted using band structure calculations with Full Potential Linearized Augmented Plane Wave (FP-LAPW) method.

This thesis presents the investigation of magnetism in a selection of low-dimensional systems and its relation to other physical properties, such as superconductivity. The techniques employed are muon spin rotation and pulsed magnetic field magnetisation. The ability of muons to directly probe the local field is used to study SrFeAsF, which is a parent compound of the high-temperature superconducting pnictides. This revealed that the magnetic and structural transitions are separated in this system. I then demon- strate the coexistence of magnetism and superconductivity in NaFeAs for the first time. This discovery is of great interest since the interplay between magnetism and supercon- ductivity is thought to play an important role for high-temperature superconductivity. I further investigate the effect of partially replacing Fe with Co in NaFeAs. I study the ordering and spin reorientation in the Mott insulator Sr₂IrO₄, which has been suggested as a possible high-temperature superconductor. The complex magnetism observed in this system is contrasted to that in related iridates Ca₄IrO₆, Ca₅Ir₃O₁₂ and Sr₃Ir₂O₇. By combining pulsed-field magnetization and low magnetic field experiments with μSR on a series of coordination polymers. I am able to determine the size and direction of the magnetic exchange interaction. I demonstrate how it is possible to adjust the in- teractions by altering the molecular architecture of these Cu-based spin- 1 2 compounds. This is a significant contribution since it will lead to the targeted design of magnetic systems that can be utilized to experimentally test fundamental theories of magnetism.

Transition metal oxides adopt a wide variety of crystal structures and display a diverse range of physical phenomena from Mott insulating states to electron-nematics to unconventional superconductivity. Detailed understanding of these states and how they may be manipulated by structural modifications requires both precise structural knowledge and in-depth physical property measurements using as many techniques over as wide a range of phase space as possible. In the work described in this thesis a range of transition metal oxides were studied using high-resolution powder neutron diffraction and detailed low-temperature physical property measurements. The quaternary barium orthotellurates Ba₂NiTeO₆, Ba₂CuTeO₆ and Ba₂ZnTeO₆ belong to an almost unstudied family of materials. The development of procedures for synthesizing large single crystals has facilitated the investigation of interesting new anisotropic magnetic states in the Cu and Ni systems and the existence of a possible structural phase transition in the Zn-based compound. YMnO₃ is a multiferroic with improper ferrielectricity. The study of the high-temperature structural phases described in this thesis has led to the identification both of the transition path to the ferrielectric state and the identification of an isostructural phase transition within the ferrielectric phase. BiFe₀.₇Mn₀.₃O₃ is also a multiferroic material but with proper ferroelectricity. The investigation of the structural phases of this compound have provided confirmation of the high-temperature phases with the reassignment of the symmetry of the highest-temperature phase which is intriguingly different to that of the unsubstituted material. Finally, an investigation of the electronic structures of the high conductivity delafossites PdCoO₂ and PdCrO₂ using micro-cantilever torque magnetometry measurements of quantum oscillations is described. This has resolved the warping of the Fermi surface of PdCoO₂ and given insights into the complicated Fermi surface of the itinerant antiferromagnet PdCrO₂.

A reação de redução de oxigênio (RRO) foi estudada em eletrocatalisadores formados por nanopartículas de óxidos puros e mistos de metais de transição de Mn, Co e Ni, além de estrutura tipo espinel, e por nanopartículas de Ag, Au e Ag3M (M= Au, Pt, Pd e Cu) suportadas em carbono Vulcan, em eletrólito alcalino. Os óxidos de metais de transição foram sintetizados por decomposição térmica de seus respectivos nitratos e as nanopartículas a base de prata e ouro foram sintetizadas por redução química com borohidreto. Os eletrocatalisadores foram caracterizados por Difratometria e Espectroscopia de Absorção de Raios X (somente para os óxidos de transição). Os materiais a base de óxidos de manganês, mostraram-se com alta atividade para a RRO, para os quais os resultados espectroscópicos in situ evidenciaram a ocorrência da redução do Mn(IV) para Mn(III), na região de início da RRO. Assim, as atividades eletrocatalíticas foram associadas à ocorrência da transferência de elétrons do Mn(III) para o O2. Entretanto, apresentaram forte desativação após ciclagem potenciodinâmica, o que foi associado à formação da fase Mn3O4, conforme indicado por difratometria de Raios X, após os experimentos eletroquímicos, que é eletroquimicamente inativa. Já o material formado pela estrutura do tipo espinel de MnCo2O4 apresentou alta atividade e estabilidade frente à ciclagem e à RRO. A alta atividade eletrocatalítica foi relacionada a ocorrência do par redox CoII/CoIII em maiores valores de potencial em relação ao CoOx e MnOx, devido a interações entre os átomos de Co e Mn no reticulo espinélico. Contrariamente ao observado nos óxidos com maior quantidade de manganês, o espinel mostrou-se altamente estável, o que foi associada à não alteração de sua estrutura no intervalo de potenciais que a RRO ocorre. Para os materiais bimetálicos a base de prata e ouro, os experimentos eletroquímicos indicaram maior atividade eletrocatalítica para o material de Ag3Au/C. Neste caso, a alta atividade foi associada a dois efeitos principais: (i) a um efeito sinergético, no qual os átomos de ouro atuam na região de ativação, favorecendo a adição de hidrogênio e os átomos vizinhos de prata proporcionam a quebra da ligação O-O, conduzindo a RRO pelo caminho de quatro elétrons por molécula de O2; (ii) ao aumento força da ligação Ag-O, devido à interação da Ag com o Au, resultando em maior atividade para a quebra da ligação O-O, aumentando a atividade da Ag para a RRO, em relação à atividade da Ag pura. Assim, a RRO apresentou menor sobrepotencial e maior número de elétrons em Ag3Au/C, quando comparado com as demais nanopartículas bimetálicas. / The oxygen reduction reaction (ORR) was studied on electrocatalysts composed by pure and mixed transition metal oxides of Mn, Co, and Ni, including spinel-like structures, and by Ag, Au, and Ag3M/C (M= Au, Pt, Pd e Cu) bimetallic nanoparticles, in alkaline electrolyte. The transition metal oxides were synthesized by thermal decomposition of their nitrates, and the silver and gold-based nanoparticles by chemical reduction using borohydride. The electrocatalysts were characterized by X-Ray Diffraction and X-Ray Absorption Spectroscopy (in the case of the metal oxides). The manganese-based oxide materials showed high activity for the ORR, in which the in situ spectroscopic results evidenced the Mn(IV) to Mn(III) reduction, in the range of the ORR onset. In this case, the electrocatalytic activities were correlated to the transfer of electron from Mn(III) to O2. However, they presented strong deactivation after several potentiodynamic cycles, which was ascribed to the formation of the electrochemically inactive phase of Mn3O4, as indicated by the XRD results, after the electrochemical experiments. On the other hand, the MnCo2O4 spinel-like material showed high activity and stability for the ORR. Its high electocatalytic activity was attributed to the CoII/CoIII redox pair, taking place at higher potentials, in relation to that of the CoOx e MnOx pure phases, due to the Co and Mn interactions in the spinel lattice. Contrarily to the behavior observed for the manganese-based materials, the spinel oxide presented high stability, which was ascribed to the non alteration of its crystallographic structure in the range of potentials tha the ORR takes place. For the Au and Ag-based materials, the electrochemical experiments indicated higher electrocatalytic activities for Ag3Au/C. In this case, its higher activity as associated to two main aspects: (i) to a synergetic effect, in which the gold atoms act in the activation region, facilitating the hydrogen addition, and the neighboring Ag atoms promoting the O-O bond breaking, leading the ORR to the 4-electrons pathway; (ii) to the increased Ag-O bond strength, due to the electronic interaction between Ag and the Au atoms, resulting in a faster O-O bond breaking, enhancing the electrocatalytic activity of the Ag atoms in the Ag3Au/C nanoparticle, in relation to that on the pure Ag. Therefore, the ORR presented lower overpotential and higher number of electrons in the Ag3Au/C electrocatalyst, when compared to the other investigated bimetallic nanoparticles.

Materials chemistry is essentially concerned with the design/synthesis of new solids endowed with functional properties that could be of relevance to today’s materials technology. Among the large variety of solid materials that attract attention, metal oxides continue to contribute significantly to current materials chemistry. A wide variety of oxide materials (based on rocksalt, spinel, corundum, perovskite, garnet, pyrochlore and other structures) and their properties have been investigated over the years. Most of these oxides are derived from the transition metals. Transition metal oxides with structures derived from metal-oxygen (MO6) octahedra, in particular, display an array of exotic properties with potential or proven technological application. While it is traditionally believed that the partially filled d shell (dn : 0 < n < 10) of the transition metal atoms plays a crucial role in deciding the electronic properties, the significance of d0 metal atoms for the properties (and structure) of transition metal oxides is not fully recognized. Magnetism (SrRuO3, Fe3O4), metallicity (ReO3, LaNiO3), colossal magnetoresistance (La1-xCaxMnO3) and superconductivity (La2xSrxCuO4, Sr2RuO4) are some of the properties that can be traced to the presence of partially filled d shell, while properties like ferroelectricity (BaTiO3), piezoelectricity (PbZr1-xTixO3) and nonlinear optical response (LiNbO3) could be traced to the presence of transition metals (TiIV, ZrIV, NbV) with d0 electronic configuration. The empty d orbitals on the metal atoms constitute the low lying unoccupied states (LUMO) that mix with the highest occupied states (HOMO) of the ligand atoms (oxygen) through special chemical bonding effects (second order Jahn-Teller effect, SOJT). This mixing results, among others, in out-of-centre distortion(s) of the MO6 octahedra and this distortion is at the heart of several properties mentioned above. Among the transition metal oxide structures based on MO6 octahedra, three structures are noteworthy: the perovskite, the pyrochlore and the rutile. The AMO3 perovskite structure consists of a three-dimensional framework of corner sharing MO6 octahedra in which the A cation occupies the dodecahedral site surrounded by twelve oxide ions. The perovskite structure can accommodate a large variety of substitutions at both the A and the M sites as well as vacancies at the A/O sites, giving a large number of derivatives. Several variants of the perovskite structure are also known, for instance, the layered perovskites and ordered perovskites. Many nonperovskite structures are also known for the composition AMO3 : hexagonal YMnO3 is an alternative structure for AMO3 composition where manganese exists as MnO5 trigonal bipyramids. The A2M2O7 pyrochlore structure is also based on a corner-connected network of MO6 octahedra which interpenetrates an A2O network. The rutile (TiO2) is a well-known structure consisting of chains of edge-sharing MO6 octahedra, which are connected through corners to adjacent chains. A large number of oxide materials based on the above three structure types have been reported : for example, perovskite [Ba3ZnTa2O9 (microwave telecommunication ceramic), Pb3MgNb2O9 (relaxor ferroelectric), Bi4Ti3O12 (high temperature ferroelectric)], pyrochlore [Nd2Mo2O7 (metallic ferromagnet), AOs2O6 for A = K, Rb, Cs (superconductor)] and rutile [TiO2 (photocatalyst), CrO2 (metallic ferromagnet), VO2 (insulator-metal transition)]. Considering the current interest in oxide materials of these three structure types which continue to generate new variants and novel properties, we undertook the present research project to synthesize new derivatives of these structure types, and characterize their structures and relevant electronic properties. In doing so, we recognized that synthesis based on an understanding of the reactivity of the constituents and crystal chemistry of the expected products plays a crucial role in this effort. Accordingly, we tailored several new compositions of AMO3, A2M2O7 and MO2 stoichiometries and adopted appropriate methodologies for their synthesis. We have characterized the structures and properties of the solid products by means of state-of-the-art methods available to us. There are two main approaches to the synthesis of nonmolecular inorganic solids: conventional ceramic route and chimie douce / soft chemistry routes. In the ceramic route, solid reactants are heated at elevated temperatures for long durations with intermittent mixing/grinding until the reaction is complete. Chimie douce routes, on the other hand, utilize gentle reactions such as dehydration, decomposition, intercalation, ion exchange, and so on to synthesize the desired phases. The ceramic route generally provides access to the thermodynamically controlled product(s), while chimie douce routes allow access to metastable phases (kinetically controlled product(s)). Disadvantages notwithstanding, the ceramic route has been the mainstay of materials chemistry and several important materials continue to be discovered / synthesized by this route. The choice of the synthetic route based on an understanding of the crystal chemical preferences and the reactivities of the constituents involved is often crucial to achieve the desired final products. The present thesis is devoted to the synthesis and investigation of MO6 octahedra-based oxides belonging to the perovskite, pyrochlore and rutile structure types wherein we have explored alternate synthetic strategies (perovskite-based Ba3MM'2O9 telecommunication ceramics and a solution route for the synthesis of ruthenium-based pyrochlores) and probed structure-property relations of perovskite oxides (Ba3MM'M''O9 oxides for various M/M'/M'' atoms) as well as formation of new derivatives of layered Aurivillius phases. In addition, we have also synthesized new noncentrosymmetric oxides possessing the YMnO3 structure. Our investigation of rutile based oxides has resulted in the discovery of a new lead-free relaxor ferroelectric material, FeTiTaO6. Given that the lone pair PbII:6s2 plays a crucial role in the ferroelectric properties of Pb-based perovskite oxides, we have also investigated members of the Pb1-xLix/2Lax/2TiO3 system for their structure and dielectric response. The present thesis describes the results of these investigations in eight chapters. Chapter 1 provides a general introduction to oxides of the perovskite, pyrochlore and rutile structures. In Chapter 2, we describe a new one-pot metathesis strategy for the synthesis of dielectric ceramics Ba3MM'2O9 (M = Mg, Ni, Zn; M' = Nb, Ta). Rietveld refinement of X-ray diffraction data shows near-complete ordering of M-site ions in many cases. The dielectric properties of the products synthesized are found to be in reasonable agreement with reported data. The synthesis of ordered materials at lower temperatures (~1100 °C) than that employed in the conventional ceramic route (~1500 °C) is a significant result of this work. Chapter 3 presents a study of Ba3MIIMIVWO9 (MII = Ca, Zn; MIV = Ti, Zr) perovskite oxides for the purpose of synthesizing new dielectric ceramic materials and to gain understanding of the factors that stabilize 3C vs. 6H structures. In general, a 1:2-ordered 6H perovskite structure is stabilized at high temperatures (1300 °C) for all of the Ba3MIITiWO9 oxides investigated. An intermediate phase possessing a partially ordered 1:1 double perovskite (3C) structure with the cation distribution, Ba2(Zn2/3Ti1/3)(W2/3Ti1/3)O6, is obtained at 1200 °C for Ba3ZnTiWO9. A metastable perovskite, Ba3CaZrWO9, that adopts the 1:1 3C structure has also been synthesized by a low-temperature metathesis route. Besides yielding several new perovskite oxides that may be useful as dielectric ceramics, the investigation provides new insights into the complex interplay of crystal chemistry (tolerance factor) and chemical bonding (anion polarization and d0-induced distortion of metaloxygen octahedra) in the stabilization of 6H versus 3C perovskite structures for the Ba3MIIMIVWO9 series. In Chapter 4, we describe the synthesis and investigation of the structure and dielectric properties of Ba3MIIITiMVO9 (MIII = Fe, Ga, Y, Lu; MV = Nb, Ta, Sb) perovskite oxides. The MV = Nb, Ta oxides adopt disordered/partially ordered 3C perovskite structures, where all the MIII/Ti/MV metal-oxygen octahedra are corner-connected. In contrast, the MV = Sb oxides show a distinct preference for the 6H structure, where SbV/TiIV metal-oxygen octahedra share a common face, forming (Sb,Ti)O9 dimers, that are corner-connected to the MIIIO6 octahedra. Investigation of dielectric properties of MIII = Y/Lu, MV = Nb/Ta oxides reveals a normal low loss dielectric behaviour with ε = 30 – 50 in the temperature range 50 – 350 °C. The MIII = Fe, MV = Nb/Ta members show a dielectric behaviour similar to relaxor ferroelectric materials. Chapter 5 deals with a study of isomorphous substitution of several metal atoms in two Aurivillius structures, Bi5TiNbWO15 and Bi4Ti3O12, in an effort to probe structure-property correlations. These investigations have led to the synthesis of new derivatives, Bi4LnTiMWO15 (Ln, = La, Pr; M = Nb, Ta), as well as Bi4PbNb2WO15 and Bi3LaPbNb2WO15, that largely retain the Aurivillius intergrowth structure of the parent oxide Bi5TiNbWO15, but characteristically tend toward a centrosymmetric / tetragonal structure for the Ln-substituted derivatives. On the other hand, coupled substitution, 2TiIV Æ MV + FeIII in Bi4Ti3O12, yields new Aurivillius phases, Bi4Ti3-2xNbxFexO12 (x = 0.25, 0.50) and Bi4Ti3-2xTaxFexO12 (x = 0.25) that retain the orthorhombic noncentrosymmetric structure of the parent Bi4Ti3O12. Chapter 6 describes the design and synthesis of a new series of noncentrosymmetric oxides, R3Mn1.5CuV0.5O9 (R = Y, Ho, Er, Tm, Yb, Lu) possessing the YMnO3 structure. Investigation of the Lu-Mn-Cu-V-O system revealed the existence of an isostructural solid solution series, Lu3Mn3-3xCu2xVxO9 for 0 < x ≤ 0.75. Magnetic and dielectric properties of the oxides are consistent with a random distribution of Mn3+, Cu2+ and V5+ atoms that preserves the noncentrosymmetric RMnO3 structure. An exploratory investigation of the synthesis, structure and electronic properties of new ruthenium(IV) pyrochlore oxides and their manganese-substituted derivatives is presented in Chapter 7. The richness of the electronic properties of ruthenium-based metal oxides is affirmed by the results which revealed several novel electronic ground states : a metallic and Pauli paramagnetic state for BiPbRu2O6.5 that turns into a semiconducting ferromagnetic spin-glass state at 50 K for BiPbRuMnO6.5 ; a metallic state that likely shows a charge density wave (CDW) instability at 50-225 K for Bi1.50Zn0.50Ru2O6.75, that is suppressed by manganese substitution in Bi1.50Zn0.50Ru1.75Mn0.25O6.50, and a metallic ferromagnetic spin-glass-like state for Pb2Ru1.75Mn0.25O6.15. We describe the investigation of the structure and dielectric properties of rutile-based MTiTaO6 (M = Al, Cr, Fe) in Chapter 8. All the oxides possess disordered rutile structure. FeTiTaO6 shows a strong relaxor ferroelectric effect, while CrTiTaO6 shows a weaker relaxor ferroelectric behaviour. This work is significant for two reasons: the new material is lead-free and it is based on the rutile structure, unlike the conventional relaxors which are mostly derived from the perovskite structure. 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. She hopes that the studies reported here will constitute a worthwhile contribution to materials chemistry 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.

The physics of transition metal oxides is controlled by the combination and competition of several degrees of freedom, in particular the charge, the spin and the orbital state of the electrons. One important parameter responsible for the physical properties is the density of charge carriers which determines the oxidization state of the transition metal ions. The central objective in this work is the study of transition metal oxides in which the charge carrier density is adjusted and controlled via lithium intercalation/deintercalation using electrochemical methods. Lithium exchange can be achieved with a high degree of accuracy by electrochemical methods. The magnetic properties of various intermediate compounds are studied. Among the materials under study the mixed valent vanadium-oxide multiwall nanotubes represent a potentially technologically relevant material for lithium-ion batteries. Upon electron doping of VOx-NTs, the data confirm a higher number of magnetic V4+ sites. Interestingly, room temperature ferromagnetism evolves after electrochemical intercalation of Li, making VOx-NTs a novel type of self-assembled nanoscaled ferromagnets. The high temperature ferromagnetism was attributed to formation of nanosize interacting ferromagnetic spin clusters around the intercalated Li ions. This behavior was established by a complex experimental study with three different local spin probe techniques, namely, electron spin resonance (ESR), nuclear magnetic resonance (NMR) and muon spin relaxation spectroscopies. Sr2CuO2Br2 was another compound studied in this work. The material exhibits CuO4 layers isostructural to the hole-doped high-Tc superconductor La2-xSr2CuO4. Electron doping is realized by Li-intercalation and superconductivity was found below 9K. Electrochemical treatment hence allows the possibility of studying the electronic phase diagram of LixSr2CuO2Br2, a new electron doped superconductor. The effect of electrochemical lithium doping on the magnetic properties was also studied in tunnel-like alpha-MnO2 nanostructures. Upon lithium intercalation, Mn4+ present in alpha-MnO2 will be reduced to Mn3+, resulting in a Mn mixed valency in this compound. The mixed valency and different possible interactions arising between magnetic spins give a complexity to the magnetic properties of doped alpha-MnO2.