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Complex oxides represent an intersection of play grounds for the existence of exciting new fundamental physics and materials with potential technological implications. The realization of many exciting properties of these systems rely on the coupling of electronic, structural and magnetic degrees of freedom. Additionally, competing interactions within each type of coupling discussed previously lead to theoretically diverse ground states, which under the application of an external perturbation, can be tuned and probed. Ca3Co¬2-xMnxO6 represent a quasi-one dimensional Ising spin chain system oriented in an antiferromagnetic triangular lattice. The exotic behavior of the undoped compound Ca3Co2O6 has inspired work on continuing the fundamental understanding of frustrated magnetic systems. Through chemical doping of Manganese ions, the magnetic properties, namely the exotic spin glass like behavior can be enhanced for a modest doping range of x The effects of particle dimensionality were probed through the application of varied calcining conditions as to attempt to observe the altering of magnetic properties, mainly the out of equilibrium magnetization plateaus observed in Ca3Co1.75 Mn0.25O6. It appears that within the particle sizes studied the magnetic behavior is highly robust, even considering the inclusion of ionic disorder.

Research interest in complex oxides has resurged owing to progress in modern epitaxial techniques. Among such oxides, lead-titanate-based thin films such as PbTiO3 (PTO) and Pb(ZrxTi1−x)O3 (PZT) offer attractive advantages for a wide variety of applications. Moreover, integration between functional oxides with compound semiconductors has the potential to realize multi-functional devices which enjoy the properties from both groups of materials. Ferroelectric materials with a perovskite structure (ABO3) and semiconductors such as GaN with a hexagonal structure, require a careful choice of a bridge layer and suitable epitaxial technique. Molecular beam epitaxy (MBE) has been an established technique in providing epitaxial growth with high crystal perfection and precise control over material composition. Single-crystal oxides grown by molecular beam epitaxy (MBE) can in principle avoid grain boundaries and provide a sharp interface as well. In this dissertation, the MBE growth mechanism of PZT was investigated. In-situ RHEED patterns indicate that the growth of PTO and PZT occur in a two-dimensional, layer by layer mode, as confirmed by a streaky pattern. The crystal quality of PTO, PZO, and PZT thin films prepared by MBE are evaluated by X-ray diffraction (XRD), and have a full width at half maximum (FWHM) value of 4 arcmin for an 80nm thick layer. Optical properties of the PTO thin films have been characterized by variable angle spectroscopic ellipsometry (VASE), and well resolved dielectric functions are extracted. The refractive index is determined as 2.605 at 633 nm, and bandgap energy as 3.778eV. The electrical properties of the PTO and PZT are evaluated by the measurement of polarization-field hysteresis loops, give a remanent polarization of 83 μC/cm2 and a coercive field of 77 kV/cm. Lead oxide (PbO), titanium dioxide (TiO2), and zirconium dioxide (ZrO2), on GaN templates for potential PZT/GaN integration. The epitaxial growth of TiO2, PbO, and ZrO2 is realized on GaN templates for the first time by MBE. The PbO epitaxial layer was also used as a nucleation layer to enable single crystalline, perovskite PTO growth on GaN.

The emerging field of spintronics relies on the manipulation of electron spin in order to use it in spin-based electronics. Such a paradigm change has to tackle several challenges including finding materials with sufficiently long spin lifetimes and materials which are efficient in generating pure spin currents. This thesis predicts that two types of material families could be a solution to the aforementioned challenges: complex oxides and bismuth based materials. We derived a general approach for constructing an effective spin-orbit Hamiltonian which is applicable to all nonmagnetic materials. This formalism is useful for calculating spin-dependent properties near an arbitrary point in momentum space. We also verified this formalism through comparisons with other approaches for III-V semiconductors, and its general applicability is illustrated by deriving the spin-orbit interaction and predicting spin lifetimes for strained SrTiO3 and a two-dimensional electron gas in SrTiO3 (such as at the LaAIO3/SrTiO3 interface). Our results suggest robust spin coherence and spin transport properties in SrTiO3 related materials even at room temperature. In the second part of the study we calculated intrinsic spin Hall conductivities for bismuth-antimony Bi1-xSbx semimetals with strong spin-orbit couplings, from the Kubo formula and using Berry curvatures evaluated throughout the Brillouin zone from a tight-binding Hamiltonian. Nearly crossing bands with strong spin-orbit interaction generate giant spin Hall conductivities in these materials, ranging from 474 ((ћ/e)Ω-1cm-1) for bismuth to 96((ћ/e)Ω-1cm-1) for antimony; the value for bismuth is more than twice that of platinum. The large spin Hall conductivities persist for alloy compositions corresponding to a three-dimensional topological insulator state, such as Bi0.83Sb0.17. The spin Hall conductivity could be changed by a factor of 5 for doped Bi, or for Bi0.83Sb0.17, by changing the chemical potential by 0.5 eV, suggesting the potential for doping or voltage tuned spin Hall current. We have also calculated intrinsic spin Hall conductivities of Bi2Se3 and Bi2Te3 topological insulators from an effective tight-binding Hamiltonian including two nearest-neighbor interactions. We showed that both materials exhibit giant spin Hall conductivities calculated from the Kubo formula in linear response theory and the clean static limit. We conclude that bismuth-antimony alloys and bismuth chalcogenides are primary candidates for efficiently generating spin currents through the spin Hall effect.

High performance miniaturized passives are of great importance for advanced nanoelectronic packages for several applications including efficient power delivery. Low cost thin film capacitors fabricated directly on package (and/or on-chip) are an attractive approach towards realizing such devices. This thesis aims to explore fundamental frequency dependent dielectric and insulating properties of thin film high-k dielectric constant in the perovskite and perovskite-related complex oxides. Throughout this thesis, we have successfully observed the role of structure, strain and oxygen stoichiometry on the dielectric properties of thin film complex oxides, allowing a greater understanding of processing conditions and polarization mechanisms. In the first section of the thesis, we explore novel processing methods in the conventional ferroelectric, barium strontium titanate, \(Ba_{1-x}Sr_xTiO_3 (BST)\), using ultraviolet enhanced oxidation techniques in order to achieve improvements in the dielectric properties. Using this method, we also explore the growth of BST on inexpensive non-noble metals such as Ni which presents technical challenges due to the ability to oxidize at high temperatures. We observe a significant lowering of the dielectric loss while also lowering the process temperature which allows us to maintain an intimate interface between the dielectric layer and the metal electrode. The second section of this thesis explores the novel dielectric material, Lanthanum Strontium Nickelate, \(La_{2-x}Sr_xNiO_4 (LSNO)\), which exhibits a colossal dielectric response. For the first time, we report on the colossal dielectric properties of polycrystalline and epitaxial thin film LSNO. We observe a significant polarization dependence on the microstructure due to the grain/grain boundary interaction with charged carriers. We next grew epitaxial films on various insulating oxide substrates in order to decouple the grain boundary interaction. Here we observed substrate dependent dielectric properties associated with induced strain. We also observe, due to the p-type carriers in LSNO, pn junction formation when grown epitaxially on the conducting oxide degenerate n-type Nb-doped \(SrTiO_3\). Finally we explore the growth mechanism of epitaxial LSNO as a function of high oxygen content. Due to the ability for LSNO to take in interstitial oxygen, a reoriented growth is observed at a critical thickness, thereby allowing us to vary anisotropy as a function of deposition conditions. / Engineering and Applied Sciences

<p>The traditional semiconductor device scaling based on Moore’s law is reaching its physical limits. New materials hosting rich physical phenomena such as correlated electronic behavior may be essential to identify novel approaches for information processing. The tunable band structures in such systems enables the design of hardware for neuromorphic computing. Strongly correlated perovskite nickelates (ReNiO3) represent a class of quantum materials that possess exotic electronic properties such as metal-to-insulator transitions. In this thesis, detailed studies of NdNiO3 thin films from wafer-scale synthesis to structure characterization and to electronic device demonstration will be discussed.</p> <p>Atomic layer deposition (ALD) of correlated oxide thin films is essential for emerging electronic technologies and industry. We reported the scalable ALD growth of neodymium nickelate (NdNiO3) with high crystal quality using Nd(iPrCp)3, Ni(tBu2-amd)2 and ozone (O3) as precursors. By controlling various growth parameters such as precursor dose time and reactor temperature, we have optimized ALD condition for perovskite phase of NdNiO3­. We studied the structure and electrical properties of ALD NdNiO3 films epitaxially grown on LaAlO3 and confirmed their properties were comparable to those synthesized by physical vapor deposition methods. </p> <p>ReNiO3 undergoes a dramatic phase transition by hydrogen doping with catalytic electrodes independent of temperature. The electrons from hydrogen occupy Ni 3<em>d</em> orbitals and create strongly correlated insulating state with resistance changes up to eight orders of magnitudes. At room temperature, protons remain in the lattice locally near catalytic electrodes and can move by electrical fields due to its charge. The effect of high-speed voltage pulses on the migration of protons in NdNiO3 devices is discussed. After voltage pulses were applied with changing the voltage magnitude in nanosecond time scale, the resistance changes of the nickelate device were investigated. </p> <p>Reconfigurable perovskite nickelate devices were demonstrated and a single device can switch between multiple electronic functions such as neuron, synapse, resistor, and capacitor controlled by a single electrical pulse. Raman spectroscopy showed that differences in local proton distributions near the Pd electrode leads to different functions. This body of results motivates the search for novel materials where subtle compositional or structural differences can enable different gaps that can host neuromorphic functions.</p>

The layered iridates such as Sr2IrO4 and Sr3Ir2O7, have attracted substantial attention due to their novel electronic states originating from strong spin-orbit coupling and electron-correlation. Recent studies have revealed the possibilities of novel phases such as topological insulators, Weyl semimetals, and even a potential high-Tc superconducting state with a d-wave gap. However, there are still controversial issues regarding the fundamental electronic structure of these systems: the origin of the insulating gap is disputed as arising either from an antiferromagnetic ordering, i.e. Slater scheme or electron-correlation, i.e. Mott scheme. Moreover, it is a formidable task to unveil the physics of layered iridates due to the limited number of available materials for experimental characterizations. One way to overcome this limit and extend our investigation of the layered iridates is using metastable materials. These materials which are far from their equilibrium state, often have mechanical, electronic, and magnetic properties that different from their thermodynamically stable phases. However, these materials cannot be synthesized using thermodynamic equilibrium processes. One way to synthesize these materials is by using pulsed laser deposition (PLD). PLD is able to generate nonequilibrium material phases through the use of substrate strain and deposition conditions. Using this method, we have synthesized several thermodynamically metastable iridate thin-films and have investigated their electronic and optical properties. Synthesizing and investigating metastable iridates opens a path to expand the tunability further than the ability of the bulk methods. This thesis consists of four studies on metastable layered iridate thin film systems. In the first study, three-dimensional Mott variable-range hopping transport with decreased characteristic temperatures under lattice strain or isovalent doping has been observed in Sr2IrO4 thin films. Application of lattice strain or isovalent doping exerts metastable chemical pressure in the compounds, which changes both the bandwidth and electronic hopping. The variation of the characteristic temperature under lattice strain or isovalent doping implies that the density of states near the Fermi energy is reconstructed. The increased density of states in the Sr2IrO4 thin films with strain and isovalent doping could facilitate a condition to induce unprecedented electronic properties, opening a way for electronic device applications. In the second study, the effects of tuning the bandwidth via chemical pressure (i.e., Ca and Ba doping) on the optical properties of Sr2IrO4 epitaxial thin films has been investigated. Substitution of Sr by Ca and Ba ions exerts metastable chemical pressure in the system, which changes both the bandwidth and electronic hopping. The optical conductivity results of these thin films suggest that the two-peak-like optical conductivity spectra of the layered iridates originates from the overlap between the optically-forbidden spin-orbit exciton and the inter-site optical transitions within the Jeff = ½ band, which is consistent with the results obtained from a multi-orbital Hubbard model calculation. In the third study, thermodynamically metastable Ca2IrO4 thin- films have been synthesized. Since the perovskite structure of Ca2IrO4 is not thermodynamically stable, its bulk crystals do not exist in nature. We have synthesized the layered perovskite phase Ca2IrO4 thin- films from a polycrystalline hexagonal bulk crystal using an epitaxial stabilization technique. The smaller A-site in this compound compared to Sr2IrO4 and Ba2IrO4, increases the octahedral rotation and tilting, which enhance electron-correlation. The enhanced electron-correlation is consistent with the observation of increased gap energy in this compound. This study suggest that the epitaxial stabilization of metastable-phase thin-films can be used effectively for investigating complex-oxide systems. Finally, structural, transport, and optical properties of tensile strained (Sr1-xLax)3Ir2O7 (x = 0, 0.025, 0.05) thin-films have been investigated. While high-Tc superconductivity is predicted in the system, all of the samples are insulating. The insulating behavior of the La-doped Sr3Ir2O7 thin-films is presumably due to disorder-induced localization and ineffective electron-doping of La, which brings to light the intriguing difference between epitaxial thin films and bulk single crystals of the iridates. These studies thoroughly investigate a wide array of novel electronic and optical phenomena via tuning the relative strengths of electron correlation, electronic bandwidth, and spin-orbit coupling using perturbations such as chemical doping, and the stabilization of metastable phases in the layered iridates.

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Les mémoires vives à changement de résistance (ReRAM de l'anglais Resistive Random Access Memories) attirent fortement l'attention car elles sont considérées comme unes des plus prometteuses pour la prochaine génération de composants. Ceci est du à leurs basse consommation de puissance, leurs vitesse de commutation élevée et leurs potentiel pour devenir une mémoire à haute densité compatible avec la technologie CMOS. Ces mémoires se basent sur l'effet de commutation résistive (RS de l'anglais resistive switching) qui est un changement réversible de la résistivité contrôlé par un champ électrique externe. Il a été proposé que le RS soit couplé avec la migration de lacunes d'oxygène qui permet de générer, de façon réversible, un canal de conduction dans l'oxyde. Plusieurs expériences ont été menées pour élucider les mécanismes de la commutation pendant les dernières années sans aucune conclusion définitive sur le mécanisme sous jacent au RS. Le principal objectif de ce travail est de comprendre les mécanismes physiques qui contrôlent le RS et de pointer quels sont les paramètres clés qui pourraient améliorer la performance des dispositifs d'un point de vue technologique. Dans cette mémoire nous présentons des études de RS dans différentes interfaces métal/oxyde en utilisant de l'or, de l'argent et du platine comme métaux et des oxydes complexes : YBa2Cu3O7–δ (YBCO), La0.67Sr0.33MnO3 (LSMO) et La0.7Sr0.3CoO3 (LSCO). Ces oxydes ont été choisis car ce sont des systèmes à électrons fortement corrélés ayant des propriétés physiques qui dépendent fortement de la Stœchiométrie d'oxygène. Ils ont une structure similaire (type pérovskite) et une haute mobilité d'oxygène. Nous avons réalisé la validation du principe de fonctionnement pour chaque type de jonction et expliqué le RS en utilisant un modèle de diffusion de lacunes d'oxygène assisté par champ électrique. Nous avons caractérisé ensuite le mécanisme de conduction des jonctions qui suit une conduction dominé par un effet Poole-Frenkel dans YBCO et par un mécanisme type SCLC dans LSCO. La faisabilité des dispositifs de mémoire dans ces jonctions a été testée atteignant des répétitivités élevées avec une consommation de puissance optimale avec plus de 103 commutations RS réussies. Nous avons également étudié l'effet d'accumulation d'impulsions électriques cycliques d'amplitude croissante sur l'état de résistance de la mémoire non-volatile de la jonction. On a trouvé une relation entre l'amplitude du RS et le nombre d'impulsions appliquées pour une amplitude et une température fixées. Cette relation est similaire à l'équation de Basquin qui décrit la loi d'endommagement dans les essais mécaniques de fatigue reliant la contrainte appliquée au nombre de répétitions de la sollicitation (temps de vie). Ceci fait ressortir la similarité de la physique du RS et de la propagation de défauts dans les matériaux soumis à des contraintes mécaniques cycliques. Finalement, nous avons analysé l'évolution temporelle de l'état résistif rémanent dans l'interface oxyde-métal. Le temps de relaxation peut se décrire par une loi exponentielle étendue qui est caractérisée par un exposant d'étirement près de 0.5. Nous trouvons que les temps caractéristiques augmentent avec la température et la puissance appliquée ce qui veut dire que ce n'est pas un phénomène classique d'activation thermique. Les résultats mettent clairement en évidence la relation entre le RS et la diffusion de lacunes d'oxygène dans une surface avec une densité de pièges dépendante de la température et qui peut correspondre physiquement à la diffusion aux joints de grains. / Resistive Random Access Memories (RRAM) have attracted significant attention recently, as it is considered as one of the most promising candidates for the next generation of non-volatile memory devices. This is due to its low power consumption, fast switching speed and the ability to become a high density memory compatible with the conventional CMOS processes. The working principle of this kind of memories is the resistive switching (RS) which is simply the controlled reversible change in the resistivity of a junction generated by an external electric field. It has been proposed that the RS is coupled with the migration of oxygen vacancies generating a reversible conduction path inside the oxide. Many experiments have been done to address the switching mechanism during the last decade without any conclusive answer of what is the physical mechanism beneath the RS. The main goal of the present work it's to understand the physical mechanism that control the RS and to point out which are the key parameters that can help improve the performance of the memory devices from a technological point of view. In this dissertation we report on the studies of the RS in different interfaces metal/oxide where we have utilized gold, silver and platinum as metal and as complex oxides: YBa2Cu3O7–δ (YBCO), La0.67Sr0.33MnO3 (LSMO) y La0.7Sr0.3CoO3 (LSCO). This oxides have been chosen because all of them are strongly correlated compounds with physical properties strongly dependent of their oxygen stoichiometry. They also have a similar crystalline structure (perovskite type) and a high oxygen mobility. We realized the proof of concept for each type of junction successfully and explain the RS effect and explained the RS utilizing an electric assisted diffusion of oxygen vacancies model. We characterized them the conduction mechanism of the junctures with a conduction dominated by the Poole-Frenkel effect in the YBCO and by the SCLC mechanism in the LSCO. The feasibility of the memory devices in this junctions have been tested reaching high repeatability with optimize power consumption with more than 103 successful switching events. We have also studied the effects of accumulating cyclic electrical pulses of increasing amplitude on the non-volatile resistance state of the junctions. We have found a relation between the RS amplitude and the number of applied pulses, at a fixed amplitude and temperature. This relation remains very similar to the Basquin equation use to describe the stress-fatigue lifetime curves in mechanical tests. This points out to the similarity between the physics of the RS and the propagation of defects in materials subjected to repeated mechanical stress. This relation can be used as the basis to build an error correction scheme. Finally, we have analyzed the time evolution of the remnant resistive state in the oxide-metal interfaces. The time relaxation can be described by a stretched exponential law that is characterized by a power exponent close to 0.5. We found that the characteristic time increases with increasing temperature and applied power which means that this is not a standard thermally activated process. The results are a clear evidence of the relation between RS and the diffusion of oxygen vacancies on a two-dimensional surface with a temperature-dependent density of trapping centers, which may correspond, physically, to the diffusion along grain boundaries. / Las memorias resistivas están entre los principales candidatos a ser utilizados como elementos en una nueva generación de memorias no volátiles. Esto se debe a su bajo consumo energético, una alta velocidad de lectura/escritura y a la posibilidad de lograr memorias de alta densidad compatibles con los procesos de la tecnología CMOS actual (por sus siglas en inglés: Complementary Metal–Oxide–Semiconductor).El funcionamiento de estas memorias se basa en la conmutación resistiva (CR), que consiste en el cambio controlado de la resistencia de una interfase metal-óxido a través de estímulos eléctricos. Si bien hasta el presente no se ha podido determinar con certeza el mecanismo físico que controla la CR, se piensa que está basado en el movimiento de vacancias de oxígeno que formarían de manera reversible zonas de alta/baja conducción dentro del óxido.La presente tesis tiene como objetivo principal entender los mecanismos físicos que gobiernan a la CR y poner en evidencia algunos de los aspectos esenciales que pueden contribuir a lograr dispositivos útiles desde el punto de vista tecnológico.Para ello se han realizado estudios de las características principales de la CR para distintas interfases metal-óxido a distintas condiciones de temperatura. Se han utilizado Au, Pt y Ag como metales y los siguientes óxidos complejos YBa2Cu3O7–δ (YBCO), La0.67Sr0.33MnO3 (LSMO) y La0.7Sr0.3CoO3 (LSCO). Se han elegido estos óxidos complejos debido a que presentan características similares, como ser materiales fuertemente correlacionados con una estructura cristalina tipo perovskita y una alta movilidad de oxígenos, lo que afecta muchas de sus propiedades físicas, ya que dependen fuertemente de la estequiometría.Nuestros resultados han demostrado la existencia de una CR bipolar en todos estos sistemas. Ésta es explicada satisfactoriamente a través de un modelo de difusión de vacancias de oxígeno asistidas por campo eléctrico.Se han caracterizado las interfases como dispositivos de memoria, estudiando sus mecanismos de conducción, encontrándose una conducción dominada por un mecanismo del tipo Poole-Frenkel para la muestra de YBCO y una conducción del tipo SCLC para el LSCO y el LSMO. Adicionalmente, se ha conseguido una alta durabilidad y repetitividad en el funcionamiento de estas junturas como dispositivos de memoria,vgracias a la optimización en el protocolo utilizado para escribir/borrar, lográndose más de 103 conmutaciones consecutivas sin fallas en dispositivos bulk.También se ha estudiado el efecto de la acumulación de pulsos idénticos en las interfases obteniéndose una relación entre la amplitud de la CR y el número de pulsos aplicado a amplitud y temperatura fijas. Luego de someter la interfase a ciclos de fatiga eléctrica, se ha encontrado una similitud entre la evolución de la resistencia remanente en esta con la propagación de defectos en un metal sometido a pruebas de fatiga mecánica. Esta relación puede ser usada como base para generar un algoritmo de corrección de errores y para mejorar la efectividad y el consumo de energía de estos dispositivos de memoria.Finalmente, se han realizado estudios sobre la evolución temporal de cada estado de resistencia. Hemos demostrado que sigue una ley exponencial estirada con un exponente cercano a 0.5 y un tiempo característico dado, que depende tanto de la temperatura como de la potencia utilizada. Estos resultados implican que la evolución temporal no está dominada por un proceso estándar de difusión térmicamente activado. La difusión de vacancias de oxígeno ocurre en una superficie con una densidad de trampas que depende de la temperatura, donde dicha superficie correspondería físicamente a los bordes de grano del óxido.