Oxide interfaces have attracted considerable attention in recent years due to emerging novel properties that do not exist in the corresponding parent compounds. Furthermore, modern atomic-scale growth and probe techniques enable the formation and study of new artificial interface states distinct from the bulk state. A central issue in controlling the novel behavior in oxide heterostructures is to understand how various physical variables (spin, charge, lattice and/or orbital hybridization) interact with each other. In particular, density function theory (DFT) has provided significant insight into underlying physics of materials at the atomic level, giving quantitative results consistent with experiment. In this dissertation using density functional theory methods, we explore the electronic, magnetic and structural properties developed near the interface in SrTiO3/LaAlO3, EuO/LaAlO3, Fe/PbTiO3/Pt, Fe//BaTiO3/Pt and Cs/SrTiO3 heterostructures. We study the interplay between physical interactions, and quantify parameters that determine physical properties of hetetrostructures. These theoretical studies help understanding how physical variables couple with each other and how they determine new properties at oxide interfaces.

Novel phenomena and functionalities at epitaxial complex oxide heterostructures have been attracting huge scientific attention because of the intriguing fundamental physics as well as potential for technological applications that they embody. Essentially, charge and spin reconstruction at the interface can lead to exotic properties, which are completely different from those inherent to the individual materials, for example, a conductive interface between two insulating materials and interface ferromagnetism in the proximity of an antiferromagnet. The interplay between charge and spin degrees of freedom can be particularly intriguing, leading to a fascinating realm, called multiferroic. In this dissertation, a systematic study is performed on the electronic (charge) and magnetic (spin) interaction/reconstruction across the interface of an all-oxide model heterostructure system consisting of the ferromagnet (FM) La$_{0.7}$Sr$_{0.3}$MnO$_3$ (LSMO) and the multiferroic (ferroelectric and antiferromagnetic) BiFeO$_3$ (BFO). The study demonstrates two pathways of using these exotic interfacial properties to control bulk properties, both the ferroelectricity in BFO and ferromagnetism in LSMO. The journey starts with the growth of high-quality BFO/LSMO heterostructures with unit-cell precision control using reflection high-energy electron diffraction combined with pulsed-laser deposition, providing an important platform for the investigation of electronic and magnetic coupling phenomena across the interface. First, we have observed a novel consequence of the interface electronic interaction due to the so-called ``polar discontinuity'', namely, a built-in electrostatic potential accumulates across the heterointerface, and provides deterministic control of ferroelectric polarization states in thin films. This observation suggests a strong, delocalized effect with important implications for future electronics based on such materials. Secondly, we have revealed a strong magnetic coupling at this interface, manifested in the form of an enhanced coercive field as well as a significant exchange-bias coupling. Based on our x-ray magnetic circular dichroism studies, the origin of the exchange-bias coupling is attributed to a novel ferromagnetic state formed in the antiferromagnetic BFO sublattice at the interface with LSMO. Thirdly, using a field effect geometry, we have proposed a pathway to use an electric field to control the magnetism in LSMO in which the ground state of the interfacial ferromagnetic state is strongly correlated with the ferroelectric polarization. Magnetotransport measurements clearly demonstrate a reversible switch/control between two distinct exchange-bias states by isothermally switching the ferroelectric polarization of BFO. This is an important step towards controlling magnetization with the electric field, which may enable a new class of electrically controllable spintronic devices and provide a new basis for producing electrically controllable spin-polarized currents. Finally, combining experimental results with first-principle and phenomenological model calculations, a microscopic model has been proposed to understand the underlying physics of the magnetoelectric coupling, providing further insights on achieving the electric-field control of magnetism. In summary, our studies on the interfacial electronic and magnetic properties at BFO/LSMO heterointerfaces have revealed a strong interplay between the charge, spin, orbital and lattice degrees of freedom at the interface, which will have important implications for a new pathway to use the interface properties to control bulk functionalities (ferroelectric polarization and ferromagnetic magnetization in this study). Such couplings at the interface may be extended to other oxides and will bring into play remarkable physical concepts to this developing field of complex oxide heterointerfaces.

Transition metal oxides (TMOs) are an ideal arena for the study of electronic correlations because the s-electrons of the transition metal ions are removed and transferred to oxygen ions, and hence the strongly correlated d-electrons determine their physical properties such as electrical transport, magnetism, optical response, thermal conductivity, and superconductivity. These electron correlations prohibit the double occupancy of metal sites and induce a local entanglement of charge, spin, and orbital degrees of freedom. This gives rise to a variety of phenomena, e.g., Mott insulators, various charge/spin/orbital orderings, metal-insulator transitions, multiferroics, and superconductivity. In recent years, there has been a burst of activity to manipulate these phenomena, as well as create new ones, using oxide heterostructures. Most fundamental to understanding the physical properties of TMOs is the concept of symmetry of the order parameter. As Landau recognized, the essence of phase transitions is the change of the symmetry. For example, ferromagnetic ordering breaks the rotational symmetry in spin space, i.e., the ordered phase has lower symmetry than the Hamiltonian of the system. There are three most important symmetries to be considered here. (i) Spatial inversion (I), defined as r → -r. In the case of an insulator, breaking this symmetry can lead to spontaneous electric polarization, i.e. ferroelectricity, or pyroelectricity once the point group belongs to polar group symmetry. (ii) Time-reversal symmetry (T) defined as t → -t. In quantum mechanics, the time-evolution of the wave-function? is given by the phase factor e{sup -iEt/{h_bar}} with E being the energy, and hence time-reversal basically corresponds to taking the complex conjugate of the wave-function. Also the spin, which is induced by the 'spinning' of the particle, is reversed by time-reversal. Broken T-symmetry is most naturally associated with magnetism, since the spin operator changes sign with T-operation. (iii) Gauge symmetry (G), which is associated with a change in the phase of the wave-function as? → e{sup i{theta}}?. Gauge symmetry is connected to the law of charge conservation, and broken G-symmetry corresponds to superconductivity/superfluidity. To summarize, the interplay among these electronic degrees of freedom produces various forms of symmetry breaking patterns of I, T, and G, leading to novel emergent phenomena, which can appear only by the collective behavior of electrons and cannot be expected from individual electrons. Figure 1 shows this schematically by means of several representative phenomena. From this viewpoint, the interfaces of TMOs offer a unique and important laboratory because I is already broken by the structure itself, and the detailed form of broken I-symmetry can often be designed. Also, two-dimensionality usually enhances the effects of electron correlations by reducing their kinetic energy. These two features of oxide interfaces produce many novel effects and functions that cannot be attained in bulk form. Given that the electromagnetic responses are a major source of the physical properties of solids, and new gauge structures often appear in correlated electronic systems, we put 'emergent electromagnetism' at the center of Fig. 1.

Today, we live in the age of nanomaterials with discovery of novel properties at nanometer length scales. In this thesis, we focus on perovskite oxides at such length scales in the form of thin films and heterostructures, which represent rapidly emerging class of nanomaterials significant for a rich variety of emergent phenomena. Until now, research has mostly focused on using easily accessible in-plane experimental probes to study these systems. The goal of this thesis is to expand upon this approach by establishing a solid vertical device platform and to probe the dynamics of the strongly correlated electron systems therein. As part of this goal, we focus on the fabrication of vertical hot-electron transistors based on oxide heterostructures down to the two-dimensional limit with atomic-scale precision and then the study of non-equilibrium dynamics of hot electrons across phase transitions using these device platforms. Further, we probe the spectroscopic evolution of hot-electron dynamics in oxide heterostructures using internal photoemission spectroscopy. These studies open up new avenues for probing and utilizing emergent phenomena at oxide interfaces and heterostructures using vertical device geometry.

This book is devoted to the rapidly developing field of oxide thin-films and heterostructures. Oxide materials combined with atomic-scale precision in a heterostructure exhibit an abundance of macroscopic physical properties involving the strong coupling between the electronic, spin, and structural degrees of freedom, and the interplay between magnetism, ferroelectricity, and conductivity. Recent advances in thin-film deposition and characterization techniques made possible the experimental realization of such oxide heterostructures, promising novel functionalities and device concepts. The book consists of chapters on some of the key innovations in the field over recent years, including strongly correlated oxide heterostructures, magnetoelectric coupling and multiferroic materials, thermoelectric phenomena, and two-dimensional electron gases at oxide interfaces. The book covers the core principles, describes experimental approaches to fabricate and characterize oxide heterostructures, demonstrates new functional properties of these materials, and provides an overview of novel applications.

The discovery of a two dimensional electron gas (2DEG) at the interface of two insulating oxides (such as LaAlO3/SrTiO3) has attracted a significant amount of attention for novel oxide based electronics and fundamental physics studies. While most studies have been focused on LaAlO3/SrTiO3 heterostructures less attention has been given to other material systems. Here, we present recent results on a different material system, GdTiO3/SrTiO3. GdTiO3 is a ferrimagnetic Mott insulator with a polar (001)c surface, while SrTiO3 is a band insulator with a non-polar (001) surface. In this study, GdTiO3 and SrTiO3 layers were grown by hybrid molecular beam epitaxy. Electrical measurements showed the formation of a two-dimensional electron gas (2DEG) at the GdTiO3/SrTiO3 interface with total sheet carrier density of ~ 3×1014 cm-2 per interface. The staggered band alignment between GdTiO3 and SrTiO3 causes the 2DEG to be located on the SrTiO3 side of the interface. Shubnikov-de Haas oscillations of the longitudinal resistance in a quantizing magnetic field were observed, indicating two-dimensionality of the electron gas. Ferromagnetic behavior was observed in both GdTiO3/SrTiO3 (where SrTiO3 is doped by the interface) and La-doped SrTiO3 systems. We also discuss electron correlation effects in this system.