Metal oxide nanoparticles, both magnetic and nonmagnetic, have a multitude of applications in gas sensors, catalysts and catalyst supports, airborne trapping agents, biomedicines and drug delivery systems, fuel cells, laser diodes, and magnetic microwaves. Over the past decade, an inexpensive, simple, recyclable, and environmentally friendly large, scale synthesis method for the synthesis of these metal oxide nanoparticles has been sought. Many of the current techniques in use today, while good on the small, laboratory bench scale, suffer from drawbacks that make them unsuitable for the industrial scale. The aminolytic method, developed by Dr. Man Han while working for Dr. Zhang, fits industrial scale-up requirements. The aminolytic method involves a reaction between metal carboxylate(s) and oleylamine in a non-coordinating solvent. This system was shown to produce a range of spinel ferrites. Dr. Lisa Vaughan showed that this method can be recycled multiple times without degrading the quality of the produced nanoparticles. The purpose of this thesis is to test the versatility of the aminolytic method in the production of a wide range of metal oxides as well as various core/shell systems. Chapter 2 explores the effect of precursor carboxylates chain length on the aminolytic synthesis of cobalt ferrite, and manganese ferrite nanoparticles. In Chapter 3, a series of CuxMn1-xFe₂O₄, (x ranges from 0.0 to 0.2), nanoparticles were synthesized via the aminolytic method. This series allows for the investigation of the effects of orbital Jahn-Teller distortion as well as orbital angular momentum on the magnetic properties of this ferrite. The quantum couplings of magnetic ions in spinel ferrites govern their magnetic properties and responses. An understanding of the couplings between these metal ions allows for tailoring magnetic properties to obtain the desired response needed for various applications. Chapter 4 investigates the synthesis of MnO and Mn₃O₄ nanoparticles in pure single phase with high monodispersity. To the best of our knowledge, the range of sizes produced for MnO and Mn₃O₄ is the most extensive, and therefore a magnetic study of these systems shows some intriguing size dependent properties. The final part of this chapter investigates the applicability of the aminolytic method for building a MnO shell on a CoFe₂O₄ core. Chapter 5 explores the synthesis of another metal oxide, ZrO₂ in both the cubic and monoclinic phases with no impurities. The use of the aminolytic method here removes the need for dangerous/expensive precursors or equipment and eliminates the need for extensive high temperature heat treatments that destroy monodispersity which is required for most techniques. The creation of a core/shell system between CoFe₂O₄ and ZrO₂ using the aminolytic method was also tested. This core/shell system adds magnetic manipulation which is especially useful for the recovery of zirconia based photocatalyst. Chapter 6 studies the application of the aminolytic method in the synthesis of yttrium iron garnet (YIG) and yttrium iron perovskite (YIP) nanoparticles. Current synthesis techniques used to produce YIG and YIP nanoparticles often requires high temperatures, sensitive to contamination, which could be eliminated through the use of our method

In this investigation, the cation distribution in ferrites of spinel-type structure is spectroscopically investigated with respect to the observed magnetic behavior. The ferrite thin films were fabricated by pulsed laser deposition and consequently annealed at different temperatures as well as atmospheres. Structural properties were determined with various methods and the crystalline quality was examined. The dielectric function line-shape was parametrized based on empirical evidence and was found to be dominated by electronic transitions between d orbitals of Fe2+ cations as well as transitions from O 2p to 3d and 4s orbitals of iron and zinc cations. The strongest magneto-optical response was observed for transitions involving cations, which correspond to lattice disorder and inversion within the normal spinel structure. With the decrease in the substrate temperature during fabrication, a decrease in the magnetic response was observed. The diminishing ferrimagnetic order was directly correlated to the decrease in strength of the transitions, involving Fe3+ on tetrahedral lattice sites. After thermal treatment in argon atmosphere and at a temperature below the deposition temperature, the increase in the magnetic response was explained through the facilitation of oxygen vacancies. With the increase in treatment temperature, a decrease in ferrimagnetic order was related to the recrystallization of the disordered spinel structure toward a more stable normal configuration, evident in the dielectric function spectra. The cationic configuration distribution in the surface as well as the bulk region, as a function of Zn concentration, was determined from approximation of the XPS and the dielectric function spectra, respectively. The difference in the cation configuration distribution, in films of predominantly inverse configuration, was related to the weak magnetic response, as opposed to films of predominantly normal spinel configuration. Our results demonstrate that a defect-rich surface region could serve as a possible explanation for the ferrimagnetic order in a nominally non-magnetic normal spinel ZnFe2O4. In combination with structural property determination, the net magnetic behavior is explained through the local cationic disorder, determined from the parametrization of the dielectric function spectra in a wide spectral range.:1 Introduction 2 Theoretical background and fundamental considerations 2.1 Spinel ferrite crystal structure 2.2 Crystal field stabilization energy 2.3 Band structure description 2.4 Verwey transition 2.5 Magnetic exchange interactions 3 Sample preparation and modification 3.1 Macroscopic spinel film formation 3.2 Pulsed laser deposition 3.3 Thermal treatment 3.4 Sample overview 4 Methods and general properties 4.1 Structure characterization techniques 4.1.1 X-ray diffraction 4.1.2 X-ray reflectivity 4.1.3 Energy dispersive X-ray spectroscopy 4.1.4 Focused ion beam and scanning electron microscopy 4.1.5 Raman spectroscopy 4.2 Surface properties 4.2.1 Atomic force microscopy 4.2.2 X-ray photoelectron spectroscopy 4.3 Dielectric tensor properties 4.4 Spectroscopic ellipsometry 4.5 Magneto-optical Kerr effect 4.6 Magneto-static properties 5 Results and discussion 5.1 Magnetic and optical properties of Fe3O4 thin film and single crystal 5.2 Magneto-optical properties of ZnxFe3−xO4 thin films 5.3 Fabrication temperature dependent ferrimagnetic order 5.4 Thermally induced structural stabilization 5.5 Cation configuration in dependence on the Zn concentration 5.5.1 Structural property determination 5.5.2 Composition characterization 5.5.3 Magneto-static behavior 5.5.4 Section summary and discussion 6 Summary and outlook Bibliography List of article contributions Selbstständigkeitserklärung Acknowledgments