The work presented herein focuses on the synthesis and characterization of new cyanide bridged molecular magnetic materials that form discrete molecules as well as three dimensional networks. This research is inspired by the recognition that the Prussian blue (PB) family exhibits a wide range of interesting magnetic properties such as photomagnetism, spin crossover, and high TC magnets owing to the presence of the cyanide bridge that promotes magnetic communication between adjacent metal spins. An underexplored facet of this research is the systematic development of the topic with anisotropic metal ions research that was undertaken as part of this dissertation. The resulting discoveries are materials that exhibit a wide range of bistable magnetic properties, including photomagnetism, long range magnetic ordering, SMM, and exchange-biased SMM behavior. New Prussian Blue analogs are presented in Chapter II of this thesis that are based on the nearly unexplored hexacyanoosmate(III) ion. A family of CoII PB derivatives of OsIII were found to exhibit photomagnetic and charge transfer induced spin transition (CTIST) behavior and a study of alkali metal cation dependence revealed marked differences in both the photomagnetic and CTIST properties, with the highest ordering temperature being observed for the K+ analog which exhibits a TC of 28.5 K. The phenomenon of linkage isomerism reported for PB analogs and other molecular materials that incorporate the [Cr(CN)6]3- ion wherein the CN ligand reverses its binding mode between the two metal centers was studied in detail as described in Chapter III. Small molecule models that incorporate [Cr(CN)6]3- and CoII ions were investigated by single crystal X-ray crystallography, magnetism, and solution IR studies and the data led to useful mechanistic information about the nature of the cyanide reversal process. The use of the anisotropic hexacyanoosmate(III) anion to form a trinuclear species with MnIII was undertaken in the study described in Chapter IV. The first SMM based on the hexacyanoosmate(III) ion was discovered and found to exhibit a very rare exchange biased SMM phenomena in one of its crystal forms. In Chapter V new building blocks with the pentadentate MPPA ligand are described which are ideally suited for the preparation of a range of model compounds of the dinuclear and trinuclear variety.

Clusters of metal ions that possess large numbers of magnetically coupled unpaired electrons have attracted much interest in recent years due to their fascinating magnetic behavior. With an appreciable component of magnetic anisotropy, these large-spin paramagnetic molecules can exhibit an energy barrier to inversion of their magnetic dipole, leading to spontaneous magnetization and magnetic hysteresis below a critical temperature. Since this behavior is a property of an individual clusters rather than a collection of molecules, this phenomenon has been dubbed ??Single Molecule Magnetism??. Our approach to the study of new high-spin systems has been to exert a measure of synthetic control in the preparation of clusters. Specifically we are employing highly anisotropic metal ions with the anticipation that these ions would engender large overall magnetic anisotropy in the resulting clusters. The first step in this process was the development of the chemistry of two new d5 ReII (S = ??) complexes, namely [ReII(triphos)(CH3CN)3][PF6]2 and [Et4N][ReII(triphos)(CN)3]. The magnetic, optical and electrochemical properties were studied and theoretical models were developed to describe the origin of the large temperature independent paramagnetism that was observed. Next, we successfully employed transition metal cyanide chemistry using the ReII building blocks to prepare a family of isostructural, cubic clusters of the general formula {[MCl]4[Re(triphos)(CN)3]4} M = Mn, Fe, Co, Ni, Cu, Zn whose 3d ions adopt local tetrahedral geometries. Within the clusters, magnetic exchange is observed between the paramagnetic ions, which has been modeled using an Ising exchange model to account for the dominating anisotropy of the ReII ion. Despite the high pseudo-symmetry of the clusters (Td), this work has yielded a rare example of a metal-cyanide single molecule magnet, {[MCl]4[Re(triphos)(CN)3]4} with an S = 8 ground state, D = -0.39 cm-1 and an effective energy barrier for magnetization reversal of Ueff = 8.8 cm-1. The elucidation of this family of isostructural clusters has also allowed us to pursue fundamental work on the structure/property relationships of the exotic, paramagnetic ReII ion. As the clusters are soluble, stable compounds, the future of this chemistry lies in the development of a true building-block approach to ??super-clusters?? that exhibit very high ground state spin values.

Order-disorder phenomena in geometrical frustrated systems are the attractive topics because of the intrinsic fluctuation. Among the geometrical frustrated systems, the material with spinel structure (AB2X4) is one of the appropriate candidates to investigate the long range ordering behavior. Corner sharing of tetrahedron and edge sharing of octahedron in the unique structural network of spinel structure are the characteristics for geometrical frustration. Hence, to study the 3d transition metal substituted in spinel system which leads to fruitful physical behavior becomes rapidly attractive. In this dissertation, long range ordering behavior in spin frustrated systems including three interesting materials LiTi2O4, NaxCoO2¡DyH2O, and CdCr2S4 were investigated. LiTi2O4 was found to show the highest superconducting transition temperature (Tc ~ 11 K) while first hydrated superconductor NaxCoO2¡DyH2O (Tc~ 4.5 K) was discovered in 2003. Superconductivity of LiTi2O4 and NaxCoO2¡DyH2O had been measured and analyzed by low temperature specific heat under magnetic field. According to the analyses of specific-heat results, isotropic (s-wave) and nodal (d-wave) gaps of superconducting pairing symmetry were proposed for LiTi2O4 and NaxCoO2¡DyH2O, respectively. Finally, LiTi2O4 was confirmed to be a typical BCS-like, fully gapped, and electron-phonon moderate-coupling type-II superconductor. Not like the case of LiTi2O4, the superconducting parameters of NaxCoO2¡DyH2O, such as Tc, HC2 and pairing symmetry, were strongly dependent on synthesized conditions. However, the evidence of nodal gap was found to be an intrinsic feature in this peculiar material NaxCoO2¡DyH2O. In the ferromagnetic insulator CdCr2S4, we first found several interesting features induced by external electric field in dielectric and magnetization measurements. Exchangestriction was proposed to be associated with the colossal change of dielectric constant value and suppression of magnetization under external electric and magnetic field in CdCr2S4. Therefore, our results supported that CdCr2S4 was a typical multiferroic material. In a conclusion, the intrinsic fluctuation of spin frustrated systems wasnecessary to pay more attention in the near future due to its fruitful physical properties and behind theoretical description.

Magnetic oxides exhibit rich complexity in their fundamental physical properties determined by the intricate interplay between structural, electronic and magnetic degrees of freedom. The common themes that are often present in these systems are the phase coexistence, strong magnetostructural coupling, and possible spin frustration induced by lattice geometry. While a complete understanding of the ground state magnetic properties and cooperative phenomena in this class of compounds is key to manipulating their functionality for applications, it remains among the most challenging problems facing condensed-matter physics today. To address these outstanding issues, it is essential to employ experimental methods that allow for detailed investigations of the temperature and magnetic field response of the different phases. In this PhD dissertation, I will demonstrate the relatively unconventional experimental methods of magnetocaloric effect (MCE) and radio-frequency transverse susceptibility (TS) as powerful probes of multiple magnetic transitions, glassy phenomena, and ground state magnetic properties in a large class of complex magnetic oxides, including La0.7Ca0.3-xSrxMnO3 (x = 0, 0.05, 0.1, 0.2 and 0.25), Pr0.5Sr0.5MnO3, Pr1-xSrxCoO3 (x = 0.3, 0.35, 0.4 and 0.5), La5/8−xPrxCa3/8MnO3 (x = 0.275 and 0.375), and Ca3Co2O6. First, the influences of strain and grain boundaries, via chemical substitution and reduced dimensionality, were studied via MCE in La0.7Ca0.3-xSrxMnO3. Polycrystalline, single crystalline, and thin-film La0.7Ca0.3-xSrxMnO3 samples show a paramagnetic to ferromagnetic transition at a wide variety of temperatures as well as an observed change in the fundamental nature of the transition (i.e. first-order magnetic transition to second order magnetic transition) that is dependent on the chemical concentration and dimensionality. Systematic TS and MCE experiments on Pr0.5Sr0.5MnO3 and Pr0.5Sr0.5CoO3 have uncovered the different nature of low-temperature magnetic phases and demonstrate the importance of coupled structural/magnetocrystalline anisotropy in these half-doped perovskite systems. These findings point to the existence of a distinct class of phenomena in transition-metal oxide materials due to the unique interplay between structure and magnetic anisotropy, and provide evidence for the interplay of spin and orbital order as the origin of intrinsic phase separation in manganites. While Pr0.5Sr0.5MnO3 provides important insights into the influence of first- and second-order transitions on the MCE and refrigerant capacity (RC) in a single material, giving a good guidance on the development of magnetocaloric materials for active magnetic refrigeration, Pr1-xSrxCoO3 provides an excellent system for determining the structural entropy change and its contribution to the MCE in magnetocaloric materials. We have demonstrated that the structural entropy contributes significantly to the total entropy change and the structurally coupled magnetocrystalline anisotropy plays a crucial role in tailoring the magnetocaloric properties for active magnetic refrigeration technology. In the case of La5/8−xPrxCa3/8MnO3, whose bulk form is comprised of micron-sized regions of ferromagnetic (FM), paramagnetic (PM), and charge-ordered (CO) phases, TS and MCE experiments have evidenced the dominance of low-temperature FM and high-temperature CO phases. The "dynamic" strain liquid state is strongly dependent on magnetic field, while the "frozen" strain-glass state is almost magnetic field independent. The sharp changes in the magnetization, electrical resistivity, and magnetic entropy just below the Curie temperature occur via the growth of FM domains already present in the material, even in zero magnetic field. The subtle balance of coexisting phases and kinetic arrest are also probed by MCE and TS experiments, leading to a new and more comprehensive magnetic phase diagram. A geometrically frustrated spin chain compound Ca3Co2O6 provides an interesting case study for understanding the cooperative phenomena of low-dimensional magnetism and topological magnetic frustration in a single material. Our MCE studies have yielded new insights into the nature of switching between multi-states and competing interactions within spin chains and between them, leading to a more comprehensive magnetic phase diagram.

Multifunctional polymer nanocomposites (PNCs) are attractive for the design of tunable RF and microwave components such as flexible electronics, attenuators, and antennas due to cost-effectiveness and durability of polymeric matrices. In this work, three separate PNCs were synthesized. Magnetite (Fe3O4) and cobalt ferrite (CFO) nanoparticles, synthesized by thermal decomposition, were used as PNC fillers. Polymers used in this work were a commercial polymer provided by the Rogers Corporation (RP) and polyvinylidene fluoride (PVDF). PNCs in this thesis consist of Fe3O4 in RP, CFO in RP, and Fe3O4 in PVDF. Characterization techniques for determining morphology of the nanoparticles, and their resulting PNCs, include x-ray diffraction, transmission electron microscopy and magnetometry. All magnetometry measurements were taken using a Quantum Design Physical Property Measurement System with a superconducting magnet. Temperature and external magnetic field magnetization measurements revealed that all samples exhibit superparamagnetic behavior at room temperature. Blocking temperature, coercivity and reduced remnant magnetization do not vary with concentration. Tunable saturation magnetization, based on nanoparticle loading, was observed across all PNCs, regardless of polymer or nanoparticle choice, indicating that this is an inherent property in all similar PNC materials. Tunability studies of the magneto-dielectric PNCs were carried out by adding the PNC to cavity and microstrip linear resonator devices, and passing frequencies of 1-6 GHz through them in the presence of transverse external magnetic fields of up to 4.5 kOe, provided by an electromagnet. Microwave characteristics were extracted from scattering parameters of the PNCs. In all cases, losses were reduced, quality factor was increased, and tunability of the resonance frequency was demonstrated. Strong magnetic field dependence was observed across all samples measured in this study.

This work set out to investigate two questions: 1) what is the state of qualitative understanding of magnetism at various stages of expertise? 2) What approaches to problem-solving are used across the spectrum of expertise? I studied three groups: ten novices (university students who had completed one introductory course in electricity and magnetism), ten experts-in-training (upper division and graduate students) and 11 experts (physics professors and researchers). Data collection involved structured interviews during which participants solved a series of non-standard problems in magnetism while thinking out loud. The problems were designed to test for conceptual understanding. The interviews were audio taped, transcribed, and analyzed using a grounded theory approach. None of the novices and only a few of the experts in training showed a strong understanding of inductance, magnetic energy, and magnetic pressure; and for the most part they tended not to approach problems visually. Novices frequently described gist memories of demonstrations, text book problems, and rules (heuristics). However, these fragmentary mental models were not complete enough to allow them to reason productively. Experts-in-training were able to solve problems that the novices were not able to solve, many times simply because they had greater recall of the material, and therefore more confidence in their facts. Much of their thinking was concrete, based on mentally manipulating objects. Three, however, exhibited traits of experts, albeit not consistently. The experts solved most of the problems in ways that were both effective and efficient. Part of the efficiency derived from their ability to visualize and thus reason in terms of field lines. / text

The purpose of this study was to investigate the effects of two perturbations, the application of an external magnetic field and randomised chemical pressure through Ti4+/Sn4+ substitution, on the dynamic spin ice state in Pr2Sn2O7. We show through magnetometry, heat capacity and powder neutron diffraction that the dynamic spin ice state in Pr2Sn2O7 is extremely fragile, requiring an external field of approximately 0.5 T to induce a transition into a long range ordered antiferromagnetic state, in accordance with the recorded behaviour of other spin ice materials. Similarly, the dynamic spin ice state in Pr2Sn2O7 only required a doping percentage of less than 2.5% to induce a transition away from the spin ice state. But instead of the predicted spin glass state, Pr2Sn2O7 assumes a cluster-type magnetic structure with extremely weak intercluster antiferromagnetic interactions, a magnetic structure that persists even to the highest doping level of 30%. The results of this thesis reveals that careful attention must be taken when selecting and placing the tetravalent cation in the 16c Wyckoff site in the pyrochlore structure, if one desires to have a spin ice state. / October 2015

When the thickness of a magnetic layer is comparable to (or smaller than) the electron mean free path, the interface between magnetic and non-magnetic layers becomes very important factor to determine magnetic properties of the ultra-thin films. The quality of interface can enhance (or reduce) the desired properties. Several interesting physical phenomena were studied using these interface effects. The magnetic anisotropy of ultra-thin Co films is studied as function of non-magnetic underlayer thickness and non-magnetic overlayer materials using ex situ Brillouin light scattering (BLS). I observed that perpendicular magnetic anisotropy (PMA) increases with underlayer thickness and saturates after 5 ML. This saturation can be understood as a relaxation of the in-plane lattice parameter of Au(111) on top of Cu(111) to its bulk value. For the overlayer study, Cu, Al, and Au are used. An Au overlayer gives the largest PMA due to the largest in-plane lattice mismatch between Co and Au. An unusual effect was found by adding an additional layer on top of the Au overlayer. An additional Al capping layer on top of the Au overlayer reduces the PMA significantly. The possible explanation is that the misfit strain at the interface between the Al and the Au can be propagated through the Au layer to affect the magnetic properties of Co even though the in-plane lattice mismatch is less than 1%. Another interesting problem in interface interdiffusion and thermal stability in magnetic tunnel junction (MTJ) structures is studied using X-ray photoelectron spectroscopy (XPS). Since XPS is a very chemically sensitive technique, it allows us to monitor interface interdiffusion of the MTJ structures as-deposited and during post-deposition processing. For the plasma-oxidized samples, Fe only participates in the oxidation reduction process. In contrast to plasma-oxidized samples, there were no noticeable chemical shifts as-deposited and during post-deposition processing in air-oxidized samples. However, peak intensity variations were observed due to interface interdiffusion.

Kyoto University (京都大学) / 0048 / 新制・課程博士 / 博士(工学) / 甲第18988号 / 工博第4030号 / 新制||工||1620 / 31939 / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 中村 裕之, 教授 安田 秀幸, 教授 吉村 一良 / 学位規則第4条第1項該当

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.