Wai, Kwai Fong = 錳氧化物 - 鈮摻雜之鈦酸鍶異構結的電流電壓關係測量 / 韋桂芳. / "Sept 2007." / Thesis (M.Phil.)--Chinese University of Hong Kong, 2007. / Includes bibliographical references. / Text in English; abstracts in English and Chinese. / Wai, Kwai Fong = Meng yang hua wu - ni shan za zhi tai suan si yi gou jie de dian liu dian ya guan xi ce liang / Wei Guifang. / Acknowledgement / Abstract / 論文摘要 / Table of content / List of Figures / List of Tables / Appendix A / Chapter Chapter 1 --- Introduction / Chapter 1.1 --- Structure and properties of perovskite manganites / Chapter 1.2 --- Magnetoresistance (MR) / Chapter 1.3 --- Giant Magnetoresistance (GMR) / Chapter 1.4 --- Colossal Magnetoresistance (CMR) / Chapter 1.4.1 --- Exchange interaction and CMR / Chapter 1.5 --- p-n junction / Chapter 1.5.1 --- Fundamentals of a p-n homojunction / Chapter 1.5.2 --- Deviations from the Ideal Diode / Chapter 1.5.2.1 --- Zener breakdown / Chapter 1.5.2.2 --- Avalanche / Chapter 1.5.3 --- Heterojunction / Chapter 1.6 --- Research motivation / Chapter 1.7 --- Scope of the thesis / References / Chapter Chapter 2 --- Experimental details / Chapter 2.1 --- Thin film deposition / Chapter 2.1.1 --- Facing target sputtering / Chapter 2.1.2 --- Vacuum system / Chapter 2.1.3 --- Deposition procedure / Chapter 2.2 --- Oxygen annealing system / Chapter 2.3 --- Silver electrode coating apparatus / Chapter 2.4 --- Characterization / Chapter 2.4.1 --- Alpha-step profilometer / Chapter 2.4.2 --- X-ray diffractometer / Chapter 2.4.3 --- Electrical transport property measurement / Chapter 2.4.3.1 --- Measurement of resistance as a function of temperature (RT) / Chapter 2.4.3.2 --- Measurement of I-V characteristics of a junction / References / Chapter Chapter 3 --- Epitaxial LSMO/STON heterojunction / Chapter 3.1 --- Sample preparation / Chapter 3.2 --- Results and Analysis / Chapter 3.2.1 --- Structural analysis / Chapter 3.2.2 --- R-T measurement / Chapter 3.2.3 --- I-V measurement / Chapter 3.2.3.1 --- Analysis of diffusion voltage and breakdown voltage / Chapter 3.2.3.2 --- Construction of energy band diagram of LSMO/STON at room temperature / Chapter 3.2.3.3 --- Investigating how the energy band structure varies with the temperature / Chapter 3.2.3.4 --- Further development of the energy band analyzing method to wide-p/narrow-n heteroj unction / Chapter 3.2.3.5 --- Forward-biased deviations from ideal / Chapter 3.2.3.6 --- Discussion on the reasons for deviations from ideal / Chapter 3.2.4 --- MR determination / References / Chapter Chapter 4 --- Epitaxial [LSMO/PCMO] multilayers and p-n junction / Chapter 4.1 --- [LSMO/PCMO]/NGO multi-layered thin films / Chapter 4.1.1 --- Sample preparation / Chapter 4.1.2 --- Results and analysis / Chapter 4.1.2.1 --- Structural analysis / Chapter 4.1.2.2 --- R-T measurement / Chapter 4.2 --- [LSMO/PCMO]/STON multi-layered junction / Chapter 4.2.1 --- Sample preparation / Chapter 4.2.2 --- Results and analysis / Chapter 4.2.2.1 --- Structural analysis / Chapter 4.2.2.2 --- R-T measurement / Chapter 4.2.2.3 --- I-V measurement / Chapter 4.2.2.3.1 --- Analysis of diffusion voltage and breakdown voltage / Chapter 4.2.2.3.2 --- Investigating the energy band structure as a function of temperature / Chapter 4.2.2.3.3 --- Forward-biased deviations from an ideal junction diode / Chapter 4.2.2.3.4 --- Review on MR calculation / Chapter 4.2.2.3.5 --- Analysis of MR of [LSMO(8 A ) /PCMO(8 A)]/STON and LSMO/STON / References / Chapter Chapter 5 --- [La0 4Ca0.6MnO3/La0.8Ca0.2MnO3］p-n junction / Chapter 5.1 --- Sample preparation / Chapter 5.2 --- Result and analysis / Chapter 5.2.1 --- Structural analysis / Chapter 5.2.2 --- R-T measurement / Chapter 5.2.3 --- I-V measurement / Chapter 5.2.3.1 --- Analysis of diffusion voltage and breakdown voltage / Chapter 5.2.3.2 --- Investigating the energy band structure as a function of temperature / Chapter 5.2.3.3 --- Forward-biased deviations from ideal / Chapter 5.2.3.4 --- MR analysis / Chapter Chapter 6 --- Conclusion / Chapter 6.1 --- Conclusion / Chapter 6.2 --- Future outlook

In den Manganaten können kleine Änderungen von externen Feldern die elektronischen, magnetischen und strukturellen Eigenschaften drastisch beeinflussen. In dieser Arbeit wird der Einfluss von elektrischen Feldern und Licht auf den elektrischen Transport in Manganatschichten analysiert. Durch elektrische Feldern können die Widerstände des Manganats remanent und reversibel zwischen verschiedenen Widerstandsniveaus in Abhängigkeit von der Polarität und der Größe des elektrischen Feldes eingestellt werden. Dieser, auch als bipolares Widerstandsschalten bezeichnete Effekt, wird in nanokolumnaren Lanthan und Strontium dotierten Manganatschichten mittels leitfähiger Rasterkraftmikroskopie und in mittels Elektronenstrahllithographie präparierten Mikrostrukturen studiert. Des Weiteren wird der Einfluss von Laseranregungen auf die erste und dritte harmonische Spannung in einer Lanthan und Barium dotierten Manganatschicht untersucht.

Thesis (M.S.)--University of Texas at El Paso, 2007. / Title from title screen. Vita. CD-ROM. Includes bibliographical references. Also available online.

Thesis (Ph. D.)--University of Oregon, 2008. / Typescript. Includes vita and abstract. Includes bibliographical references (leaves 200-207). Also available online in ProQuest, free to University of Oregon users.

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

Thesis (Ph. D.)--University of Missouri-Columbia, 2005. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file viewed on (November 13, 2006) Vita. Includes bibliographical references.

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.

Mixed valence manganites with the perovskite structure R1-xAxMnO3 (where R = La, Nd, Pr and A = Ba, Ca, Sr, Pb) have been a popular subject of contemporary research because of their interesting physical properties such as competing magnetic orders, metal-insulator transitions and colossal magnetoresistance. A complex interplay between structure, electronic and magnetic properties results in rich phase diagrams involving various metallic, insulating and magnetic phases. A review of the literature related to rare-earth managnites clearly reveals that the systems with Pb as a divalent dopant are relatively less explored. This may be due to the volatile nature of lead based compounds which are used as precursors for preparing these systems. This has motivated us to take up research on Pb doped rare earth manganites. This thesis is divided into eight chapters. The first introductory chapter gives a brief review of the work on manganites which have already been reported in the literature following which the motivation for carying out the present investigation is given. The second chapter deals with technical details of various instruments used in the present reasearch work. The third chapter is related to growth of single crystals, their preliminary characterization, magnetization and resistivity studies. Single crystals of Pr1-xPbxMnO3 are grown by flux technique for different compositions. Crystals are characterized by energy dispersive x-ray analysis (EDAX) and inductively coupled plasma atomic emission spectroscopy (ICPAES) for compositional analysis. Magnetization and resistivity studies are carried out on Pr1-xPbxMnO3 for three compositions viz. x = 0.2, 0.23 and 0.3. The magnetization vs. temperature plots show that all the three compositions undergo a transition from paramagnetic to ferromagnetic state. The magnetization in the low temperature ferromagnetic region obeys Bloch`s law. The susceptibility in the paramagnetic region is fitted to Curie Weiss law. Deviation of susceptibilty from Curie Weiss law, a feature observed in all the three crystals has been attributed to formation of ferromagnetic clusters at ~ 250 K. The cluster formation has its implications on all other properties in the temperature range from TC to 250 K where TC is the magnetic transition temperature. Resistivity measurements are carried out on the same three compositions. The x = 0.2 and 0.23 compositions undergo a transition from paramagnetic insulating to ferromagnetic insulating phases. The x = 0.3 composition shows a metal – insulator transition at nearly 35 K above TC. Chapter 4 describes the critical behaviour of Pr1-xPbxMnO3 for two compositions, viz. x = 0.23 and 0.3. For critical studies, magnetization vs. field measurements are carried out in the temperature range TC ± 10 K. Using modified Arrott plots and Kouvel-Fisher method the critical exponents and precise value of TC are obtained. The x = 0.23 composition shows results which indicate a conventional second order phase transition shown by a 3D Heisenberg ferromagnet. It also obeys the universal scaling behaviour. However, the x = 0.3 composition shows deviation from this behaviour. Hence to probe further into the nature of magnetic transition of this compound the effective critical exponents are calculated as a function of reduced temperature ε (=(T-TC)/TC). Based on the behaviour of effective exponents the nature of the transition in the x = 0.3 composition is described in detail. The unconventional ordering is attributed to presence of possible magnetic frustration in the system. In chapter 5 the resistivity and magnetoresistance behaviour of the x = 0.23 and 0.3 crystals are discussed. Initially the nature of plots of temperature and field variation of resistivity are described for both the cases. Detailed measurements are carried out at the magnetic transition region. The analysis is carried out in terms of critical scattering behaviour at the transition region. The zero field resistivity is analyzed in terms of theory of Fisher and Langer, while the magnetoresistance is fitted to scaling theory at the critical region developed by Balberg and Helman. It is seen that the x = 0.23 crystal shows a critical behaviour in resistivity for zero field as well as in magnetoresistance close to TC. However, the behaviour of the x = 0.3 composition is more complex. A simpler critical scattering theory alone cannot explain its large negative magnetoresistance. Chapter 6 contains the EPR studies on the x = 0.23 and 0.3 compositions. Analysis is carried out in the paramagnetic region. The EPR signals are fitted to a modified Dysonian equation. The intensity, linewidth, and asymmetry parameter are obtained as a function of temperature from fitting. The parameters are obtained till 210 K for both compositions. The intensity is fitted to a Curie Weiss law. The linewidth shows a “bottleneck” mechanism and is proportional to conductivity. Hence it is fitted to activated behaviour. In addition, a secondary signal develops at low fields from 240 K and is present till 200 K in both the compositions. This is explained by means of phase separation. In chapter 7 the specific heat of the x = 0.23 and 0.3 compositions are discussed. The measurements are carried out from 2 to 300 K in zero field and also in the presence of 3 Tesla magnetic field. The analysis is carried out in two separate sections. The first section deals with the low temperature analysis from 2 to 80 K where apart from the usual lattice, electron and magnetic terms, presence of Schottky anomaly is also discussed. The Schottky peak occurs at a relatively higher temperature of around 40 K. Due to presence of higher order lattice terms the Schottky effect is not easily discernible. It is extracted only from fitting. In the second section, the specific heat associated with ferromagnetic – paramagnetic transition is extracted. The lattice term in the entire temperature range from 10 to 300 K except at the transition region is fitted to Einstein function. The magnetic specific heat is obtained by subtracting the Einstein specific heat from the total specific heat. The change in entropy due to magnetic transition is also calculated for both compositions. In chapter 8 the general conclusions derived from the work presented in this thesis are summarized along with the scope for future work in this system.

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 matériaux thermoélectriques (TE) permettent de convertir directement de la chaleur en électricité et vice-versa. Les objectifs de cette thèse étaient de tenter d'améliorer les performances TE de trois familles de matériaux et de mieux comprendre le lien entre les propriétés physiques (électriques, thermiques, magnétiques) généralement mesurées dans une large gamme de température (5–700 K) et les microstructures/compositions chimiques observées. Généralement, les matériaux ont été synthétisés par des techniques de métallurgie des poudres et densifiés par spark plasma sintering. La majeure partie de nos travaux a concerné la famille des matériaux tétraédrites, dérivés du minéral naturel (Cu,Ag)10(Zn,Fe)2(Sb,As)4S13, présentant des propriétés TE prometteuses, récemment mises en évidence. D’abord, les propriétés TE de huit tétraédrites naturelles de provenance différente ont été étudiées. Nous avons montré que leurs propriétés physiques sont plutôt prévisibles selon leur composition chimique et finalement peu différentes selon leur origine. Les propriétés TE de mélanges de tétraédrites naturelles et synthétiques obtenus par broyage mécanique ont ensuite été déterminées. Ce procédé fortement énergétique produit des particules de taille nanométrique des deux phases qui forment une solution solide pendant le frittage. Par contre, un broyage manuel conserve la présence des deux phases, ce qui conduit à de plus faibles performances TE. Ensuite, nous avons montré que la substitution Sb <-> As, usuelle dans les spécimens naturels, n’influence que faiblement les propriétés TE. Enfin, les propriétés TE de manganites de calcium et de polymères conducteurs ont également été étudiées / Thermoelectric (TE) materials allow direct conversion between heat and electricity. The aim of this thesis was to try to improve the thermoelectric performance of three different families of materials and to better understand the link between the various physical properties (electrical, thermal, magnetic) generally measured in a broad temperature range (5–700 K) and the observed microstructure/chemical composition. In general, the materials were synthesized by powder metallurgy techniques and densified by spark plasma sintering (SPS). The major part of our studies concerns the tetrahedrite family of materials, derived from the mineral tetrahedrite, (Cu,Ag)10(Zn,Fe)2(Sb,As)4S13, whose promising thermoelectric properties were only recently discovered. In a first approach, the TE properties of eight natural tetrahedrites of different geographic origin are studied. It is shown that they all behave rather predictably and uniformly. Next, the properties of ball milled mixtures of natural and synthetic tetrahedrites are investigated. This high-energy process yields nanoscale particles of the two phases, which form a solid solution during the sintering. Low-energy hand grinding preserves the two-phase nature and results in inferior TE performance. Because arsenic is a common substituent in natural specimens, several As-substituted tetrahedrites are synthesized and characterized. It is shown that the TE properties are only weakly influenced by the substitution of As for Sb. Besides tetrahedrites, calcium manganese oxides and conductive polymers are also studied