Orbital degrees of freedom play vital role in prompting novel phenomena in ruthenium based Ruddlesden-Popper compounds through coupling of orbits to spin and lattice. Physical properties are then particularly susceptible to small perturbations by external magnetic fields and/or slight structural changes. Current study pertains to the impact when a more-extended 4d Ruthenium ion is replaced by a less-extended 3d Chromium ion. Perovskite CaRuO3 (n=∞) is characterized by borderline magnetism and non- Fermi liquid behavior – common occurrences in quantum critical compounds. Remarkably, Cr substitution as low as x=0.05 abruptly drives CaRu1−xCrxO3 from a paramagnetic state to an itinerant ferromagnetic state (MS~0.4μB/f.u.), where TC=123K for x=0.22. The Cr-driven magnetism is highly anisotropic suggesting an important role of spin-orbit coupling. Unlike other chemical substitutions in the compound, Cr does not induce any Metal-Insulator transition that is expected to accompany the magnetic transition. The results indicate a coupling of Ru-4d and Cr-3d electrons that is unexpectedly favorable for itinerant ferromagnetism, which often exists delicately in the ruthenates. Bilayered Ca3Ru2O7 (n=2), an abode of huge anisotropy, exhibits a wide range of physical properties – Colossal Magnetoresistance occurring only when the spin polarized state is avoided, Antiferromagnetic-Metallic (AFM-M) state, Quantum Oscillations (periodic in 1/B and in B) that are highly angular dependent, to mention a few. Experimental results obtained so far provide a coherent picture illustrating that orbital order and its coupling to lattice and spin degrees of freedom drive the exotic electronic and magnetic properties in this Mott-like system. Transport and thermodynamic studies on Ca3(Ru1-xCrx)2O7 (0 ≤ x ≤ 0.20) reveal that AFM-M region is broadened with x that ultimately reaches 70K for x=0.20 (~8K for x=0). In this region, electron transport is enhanced and inhibited when B is applied along crystal’s respective axes, confirming an intrinsic half-metallic behavior. Moreover, the difference in coercivities of Ru and Cr magnetic ions pave way for the first-ever observation of a strong spin-valve effect in bulk material, a quantum phenomenon so far realized only in multilayer thin films or heterostructures. This discovery opens new avenues to understand the underlying physics of spin-valves and fully realize its potential in practical devices.

The layered transition metal oxide composition series of Li1+xV1-xO2 was synthesized using the solid state synthesis technique. X-ray diffraction was used to determine the dependence of structure on composition and clearly indicated a structural anomaly at x = 0 caused by the unusual magnetic ordering on the triangular lattice of the V3+ layer. To prevent magnetic frustration V3+ cations undergo orbital ordering and subsequent periodic displacent to form “trimers”. The periodicity of this phenomena results in a superlattice structure that can be observed as a faint peak in XRD spectra. The relationship between composition, superlattice peak intensity and lattice parameters was clearly documented for the first time. Li/Li1+xV1-xO2 cells were made and tested. Recent literature has shown that the transformation to 1T Li2VO2 upon lithiation is dependant on a nonzero x (ideally x = 0.07 for maximum capacity) to make a small number of tetrahedrally coordinated Li sites accessible. These sites then act as a trigger for shearing into the 1T phase. The cells described within this work intercalated significant amounts of lithium at a higher potential than the to 1T transition, possibly signifying occupation of a large number of the tetrahedral sites. LiVO2 is known to undergo delithiation even in ambient conditons and this can lead to cationic disorder. Cationic disorder is an inhibitor of anion sheet shearing and this suggests that sample handling could be a cause of the observed electrochemical behaviour. The effects of air and water exposure were investigated.

Neutron and x-ray diffraction has been used to study charge, orbital and magnetic ordering in some transition metal oxides. The long standing controversy regarding the nature of the ground state (Verwey structure) of the canonical charge ordered material magnetite (Fe3O4) has been resolved by x-ray single crystal diffraction studies on an almost single domain sample at 90 K. The Verwey structure is confirmed to have Cc symmetry with 56 unique sites in the asymmetric unit. Charge ordering is shown to be a useful first approximation to describe the nature of the ground state, and the conjecture that Verwey made in 1939 has finally been confirmed. However, three-site distortions which couple to the orbital ordering of the Fe2+ ordered states (trimerons) are shown to provide a more complete description of the low temperature structure. Trimerons explain the rather continuous distribution of the valence states observed in magnetite below Tv, anomalous shortening of Fe-Fe distances and the off-centre distortions resulting in ferroelectricity. DFT+U electronic structure calculations on the experimental coordinates support the conclusion of this crystallographic study, with the highest electron densities calculated for those Fe-Fe distances predicated to participate in the trimeron bonds. The 6H-perovskites of the type Ba3ARu2O9 have been reinvestigated by high resolution neutron and x-ray power diffraction. The charge ordered state of Ba3NaRu2O9 has been characterised at 110 K (P2/c, a =5.84001(2) Å, b = 10.22197(4) Å, c = 14.48497(6) Å, β = 90.2627(3) °) and shown to consist of a structure with near integer charge ordering of Ru5+ 2O9 / Ru6+ 2O9 dimers. The ground state has been shown to be very sensitive to external perturbations, with a novel melting of charge ordering observed under x-ray irradiation below 40 K (C2/c, a =5.84470(2) Å, b = 10.17706(3) Å, c = 14.45866(5) Å, β = 90.2151(3)-° at 10 K). High pressure studies reveal that the Ru-Ru intra-dimer distance may dictate the response of the system to pressure. Empirical trends in the Ba3ARu2O9 series of compounds have shown that change in ‘chemical pressure’ in these systems may be rationalised in terms of Coulomb’s law. In A = La and Y the magnetic ordering is shown to be FM within the Ru2O9 dimers (1.4(2) μB and 0.5(1) μB, respectively per Ru), representing the first case of intra dimer FM coupling reported in a system containing face-sharing RuO6 octahedra . The overall AFM coupling of the dimers implies an as yet unobserved breaking of the parent symmetry. In A = Nd, a complex competition between the crystal field effect of Nd3+ and the magnetic ordering of the Ru2O9 FM moments has been observed, leading first vi to FM order of Nd at 25 K (1.56(7) μB) followed by ordering of Ru moments (0.5(1) μB) and a spin reorientation transition of Nd moments at 18 K. In A = Ca, the formation of a singlet ground state is observed in Ru2O9 rather than the expected AFM coupling and below 100 K Ba3CaRu2O9 is diamagnetic. All five systems indicate that the Ru2O9 dimer is the physically significant unit in these systems when considering structural trends and the ordering of charge, spin and orbital degrees of freedom.

xxv, 207 p. ; ill. (some col.) A print copy of this title is available from the UO Libraries, under the call number: SCIENCE QD172.T6 T87 2008 / A growing interest in the physics of complex systems such as in the transition-metal oxide family has exploded recently, especially in the last 20 years or so. One notable effect is the change in electrical resistivity of a system by orders of magnitude in an applied magnetic field, coined the "colossal magnetoresistance effect". In efforts to understand these types of effects, there has been an unveiling of a rich variety of phenomena in the field of strongly correlated electron physics that has come to dominate the current scientific times. Most notable is the competition of myriad types of order: magnetic, lattice, charge and orbital all self-organize to display a fascinating array of phases on a variety of length scales. Furthermore, it has become apparent that new probes are needed to grasp some of this physics that transcends current condensed matter theory, where much of the behavior of these types of systems has remained unexplored. We have developed a new technique to gain more information about the system than with conventional x-ray diffraction. By scattering highly coherent, low energy x-rays, we can measure manganite speckle: a "fingerprint' of the microscopic structure in the bulk. The coherence of the x-rays can further be used to elucidate new insight into the dynamics of these phases. We describe here a number of novel effects near the orbital order phase transition in a half-doped manganite. We observe a small fluctuating component in the scattered signal that is correlated with three effects: both a rapidly decreasing total signal and orbital domain size, as well as an abrupt onset of a broad background intensity that we attribute to the thermal production of correlated polarons. Our results suggest that the transition is characterized by a competition between a pinned orbital domain topology that remains static, and mobile domain boundaries that exhibit slow, spatiotemporal fluctuations. This study opens up a new chapter to the study of manganite physics as coherent x-ray scattering offers a new direction to understand the strange and exotic behavior demonstrated in the multifaceted manganites. / Adviser: Stephen Kevan

Ca2RuO4 is a structurally-driven Mott insulator with a metal-insulator (MI) transition at TMI = 357K, followed by a well-separated antiferromagnetic order at TN = 110 K. Slightly substituting Ru with a 3d transition metal ion M effectively shifts TMI and induces exotic magnetic behavior below TN. Moreover, M doping for Ru produces negative thermal expansion in Ca2Ru1-xMxO4 (M = Cr, Mn, Fe or Cu); the lattice volume expands on cooling with a total volume expansion ratio reaching as high as 1%. The onset of the negative thermal expansion closely tracks TMI and TN, sharply contrasting classic negative thermal expansion that shows no relevance to electronic properties. In addition, the observed negative thermal expansion occurs near room temperature and extends over a wide temperature interval. These findings underscores new physics driven by a complex interplay between orbital, spin and lattice degrees of freedom. These materials constitute a new class of Negative Thermal Expansion (NTE) materials with novel electronic and magnetic functions.