Thesis (doctoral)--Rheinisch-Westfälische Technische Hochschule Aachen, 2004. / Includes bibliographical references (p. 223-235).

Die vorliegende Dissertation "Struktur und Magnetotransport laserdeponierter Lanthanmanganat Dünnschichtsysteme" beschäftigt sich mit der Herstellung, den strukturellen Eigenschaften und dem Magnetotransport von ferromagnetisch-metallischen Lanthanmanganat-Schichten La0.7A0.3MnO3 (A=Sr, Ca) und Schichtsystemen. Die untersuchten Schichten und Schichtsysteme wurden mittels Laserablation in "off-axis" Geometrie auf einkristallinen oxidischen Substraten abgeschieden. An einer Serie von polykristallinen La0.7Sr0.3MnO3/Y:ZrO2(100) Schichten wurde der Korngrenzen-Magnetowiderstandseffekt ferromagnetisch-metallischer Manganate untersucht. Durch Variation der Substrattemperatur während der Abscheidung läßt sich die Textur graduell einstellen. Untersuchungen des quantitativen Verhaltens des Magnetowiderstandes zeigen eine klare Korrelation des Niederfeld-Magnetowiderstandes und des Hochfeld-Magnetowiderstandes. Durch Untersuchungen an einer nichttexturierten Schicht in hohen gepulsten Magnetfeldern konnte auf einen indirekten Tunnelprozeß der Elektronen durch die Korngrenze entsprechend einem Modell von Lee et al. geschlossen werden, wobei die magnetische Ordnung der Korngrenze antiferromagnetisch ist. An den epitaktischen Schichtserien La0.7Ca0.3MnO3/NdGaO3(110) und La0.7Sr0.3MnO3/SrTiO3(100) und an heteroepitaktischen Multilagen (La0.7Sr0.3MnO3/SrTiO3)n/SrTiO3(100) wurden die strukturellen, magnetischen und elektrische Eigenschaften in Abhängigkeit von der Schichtdicke und der Einfluß der Grenzflächeneigenschaften untersucht. Allgemein zeigte sich, daß die mechanische Verspannung und Mikrostruktur der Schichten einen großen Einfluß auf deren physikalischen Eigenschaften haben. Die beobachtete Reduzierung der Curie-Temperatur, der Metall-Isolator-Übergangstemperatur und der spontanen Magnetisierung kann auf den finite-size Effekt und auf die Ausbildung von Perkolationspfaden (metallische Cluster in nichtmetallischer Matrix) in den ultradünnen Schichen zurückgeführt werden.

Die vorliegende Dissertation "Struktur und Magnetotransport laserdeponierter Lanthanmanganat Dünnschichtsysteme" beschäftigt sich mit der Herstellung, den strukturellen Eigenschaften und dem Magnetotransport von ferromagnetisch-metallischen Lanthanmanganat-Schichten La0.7A0.3MnO3 (A=Sr, Ca) und Schichtsystemen. Die untersuchten Schichten und Schichtsysteme wurden mittels Laserablation in "off-axis" Geometrie auf einkristallinen oxidischen Substraten abgeschieden. An einer Serie von polykristallinen La0.7Sr0.3MnO3/Y:ZrO2(100) Schichten wurde der Korngrenzen-Magnetowiderstandseffekt ferromagnetisch-metallischer Manganate untersucht. Durch Variation der Substrattemperatur während der Abscheidung läßt sich die Textur graduell einstellen. Untersuchungen des quantitativen Verhaltens des Magnetowiderstandes zeigen eine klare Korrelation des Niederfeld-Magnetowiderstandes und des Hochfeld-Magnetowiderstandes. Durch Untersuchungen an einer nichttexturierten Schicht in hohen gepulsten Magnetfeldern konnte auf einen indirekten Tunnelprozeß der Elektronen durch die Korngrenze entsprechend einem Modell von Lee et al. geschlossen werden, wobei die magnetische Ordnung der Korngrenze antiferromagnetisch ist. An den epitaktischen Schichtserien La0.7Ca0.3MnO3/NdGaO3(110) und La0.7Sr0.3MnO3/SrTiO3(100) und an heteroepitaktischen Multilagen (La0.7Sr0.3MnO3/SrTiO3)n/SrTiO3(100) wurden die strukturellen, magnetischen und elektrische Eigenschaften in Abhängigkeit von der Schichtdicke und der Einfluß der Grenzflächeneigenschaften untersucht. Allgemein zeigte sich, daß die mechanische Verspannung und Mikrostruktur der Schichten einen großen Einfluß auf deren physikalischen Eigenschaften haben. Die beobachtete Reduzierung der Curie-Temperatur, der Metall-Isolator-Übergangstemperatur und der spontanen Magnetisierung kann auf den finite-size Effekt und auf die Ausbildung von Perkolationspfaden (metallische Cluster in nichtmetallischer Matrix) in den ultradünnen Schichen zurückgeführt werden.

Over the last decade progress towards step-wise structural transformations in solid state chemistry has been made using metal hydride reductants. Alkali and alkali-earth metal hydrides can effectively reduce transition metal oxides resulting frequently in novel oxygen defect structures. This provides access to control over cation oxidation states and magnetic exchange pathways, and thus electronic and magnetic properties. The goal for this research was to investigate a representative system that could be used both for exploration of novel oxygen defect phases and for investigating the fundamental parameters governing successful solid state reductions. The systems chosen for investigation were Sr2-xCaxMnO4 (0<x<2) and Sr2-xBaxMnO4 (x< 0.04). Detailed analysis of metal hydride reactivity with Sr2MnO4 is presented in addition to proof of the solid state reduction mechanism. As a result a number of novel oxygen defect phases have been produced, Sr2MnO4-x (0<x<0.37). The potential for producing novel lithium doped Sr2MnO4-x phases using a reduction/insertion approach with LiH has also been identified. Lastly as a test of application for metal hydrides as reductants the ability to topotactically reduce ScVO4 has been investigated.

Over the last decade progress towards step-wise structural transformations in solid state chemistry has been made using metal hydride reductants. Alkali and alkali-earth metal hydrides can effectively reduce transition metal oxides resulting frequently in novel oxygen defect structures. This provides access to control over cation oxidation states and magnetic exchange pathways, and thus electronic and magnetic properties. The goal for this research was to investigate a representative system that could be used both for exploration of novel oxygen defect phases and for investigating the fundamental parameters governing successful solid state reductions. The systems chosen for investigation were Sr2-xCaxMnO4 (0<x<2) and Sr2-xBaxMnO4 (x< 0.04). Detailed analysis of metal hydride reactivity with Sr2MnO4 is presented in addition to proof of the solid state reduction mechanism. As a result a number of novel oxygen defect phases have been produced, Sr2MnO4-x (0<x<0.37). The potential for producing novel lithium doped Sr2MnO4-x phases using a reduction/insertion approach with LiH has also been identified. Lastly as a test of application for metal hydrides as reductants the ability to topotactically reduce ScVO4 has been investigated.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / Esse trabalho consiste na obtenÃÃo de uma nova rota de sÃntese para o manganato de nÃquel (NiMn2O4) atravÃs do mÃtodo sol-gel protÃico, utilizando a gelatina comestÃvel como precursor orgÃnico, bem como uma caracterizaÃÃo do mesmo. A sÃntese das nanopartÃculas foi realizada atravÃs da diluiÃÃo de sais inorgÃnicos (NiCl2.6H2O, MnCl2.4H2O) e gelatina em Ãgua destilada com a adiÃÃo de hidrÃxido de sÃdio (NaOH) em soluÃÃo. Em seguida foi colocada em uma estufa com temperatura fixa de 100ÂC para que fosse seca. As amostras foram calcinadas numa faixa de temperatura de 600ÂC à 1000ÂC por um tempo prÃ-determinado. O forno utilizado na calcinaÃÃo possui um formato tubular com sistema rotativo e inclinaÃÃo ajustÃvel, cujo principal objetivo à a obtenÃÃo de uma maior homogeneizaÃÃo das partÃculas. Foi realizada uma caracterizaÃÃo microestrutural cujos parÃmetros calculados foram o tamanho e a microdeformaÃÃo das nanopartÃculas. As tÃcnicas empregadas para essa anÃlise foram: a difraÃÃo de raios-X com o uso do mÃtodo Rietveld de refinamento de estrutura; a fluorescÃncia de raios-X com o intuito de comprovar a estequiometria dos elementos presentes na sÃntese; medidas magnÃticas com o objetivo de encontrar propriedades magnÃticas do composto (NiMn2O4) e as anÃlises tÃrmicas TG e DSC para a determinaÃÃo das perdas de massa e energia de ativaÃÃo do material, durante o processo de sinterizaÃÃo. Todos os recursos e tÃcnicas aplicadas na obtenÃÃo desse composto tÃm como objetivo otimizar o processo de sua obtenÃÃo; com diminuiÃÃo de energia, tempo e custo / This work presents a new route for the synthesis of nickel manganate (NiMn2O4) through the sol-gel protein method, using gelatin as an organic precursor. The synthesis of nanoparticles was performed by dilution of inorganic salts (NiCl2.6H2O, MnCl2.4H2O) and gelatin in distilled water with the addition of sodium hydroxide (NaOH). This solution was then placed in an oven at a fixed temperature of 100ÂC to make it dry. The samples were calcined in a temperature range of 600ÂC to 1000ÂC for a predetermined time. The oven used in calcination has a tubular shape and is provided with rotation and adjustable tilt, whose main objective is to obtain a greater homogenization of the particles. Particle size and microstrain were calculated from the parameters obtained from the microstructural characterization. The technique used for this analysis ware: the X-ray diffraction using the Rietveld method of structure refinement; the technique of X-ray fluorescence was applied in order to prove the stoichiometry of the elements present in the synthesis; magnetic measurements in order to find the magnetic properties of the compound (NiMn2O4) and the thermal analysis TG and DSC were performed to determine the loss of mass and energy variation of the material during the sintering process. The technique used to obtain nickel manganate allowed the optimization of the process. Thus obtaining the desired material with lower energy consumption, shorter time and lower cost than other processes commonly employed

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In the present work, the magnetotransport measurement technique was developed and various materials, exhibiting resistances from 1 mOhm up to several tens of kOhm, were investigated in pulsed magnetic fields of up to 60 T. Phase diagrams of irreversibility and upper critical fields for pure and Zn-doped YBa2Cu3O_7-x high-temperature superconductors were measured. A high-field study of the electronic properties of the two semimetals LaBiPt and CeBiPt were presented. Magnetoresistance of La0.7Sr0.3MnO3 and La0.7Ca0.3MnO3 thin films were investigated.