The thermodynamics of disorder have been studied for hundreds of years, with physicists using entropy to quantitatively connect the macroscopic properties of a system to its microscopic multiplicity (disorder). Here, we consider the effect of disorder in magnetic materials. The pyrochlore oxides (A2B2O7), comprised of a bipartite lattice of corner-sharing tetrahedra, have been central to the study of geometric frustration for the past several decades. Pyrochlores, in which the A-site is occupied by the magnetic cation dysprosium, tend to exhibit spin ice ordering down to low temperatures, in spite of chemical perturbations to the B-site lattice. With the motivation of this study being the investigation of how adding B-site disorder to the traditional Dy2ScNbO7 form of Dy-pyrochlores, a stoichiometric mixture of Sc-3+ and Nb-5+ was used to synthesize Dy2ScNbO7, the pyrochlore material that is central to this thesis work. We show using magnetometry, heat capacity, muon spin relaxation, and inelastic neutron scattering that the mixed B-site pyrochlore Dy2ScNbO7, does not adopt the spin ice ground state. The low temperature spin dynamics are much faster than other analogous dysprosium pyrochlores, the residual entropy is significantly smaller than that predicted for a spin ice and there are low-lying crystal field excitations. These results all indicate that the B-site disorder appears to destroy the predicted Ising anisotropy of dysprosium. / Thesis / Master of Science (MSc)

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24437号 / 理博第4936号 / 新制||理||1705(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)教授 谷村 吉隆, 教授 林 重彦, 教授 鈴木 俊法 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

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The rare earth pyrochlore oxides, with formula R2B2O7, are a chemically versatile family of materials that exhibit a diverse array of magnetic phenomena. In this structure the R and B site cations each form a corner-sharing tetrahedral network, a motif that is prone to intense geometric magnetic frustration. As a consequence of their magnetic frustration, rare earth pyrochlores are observed to host a number of remarkable states such as spin ice and spin liquid states. In this thesis we endeavor to explore the phase diagrams of the rare earth pyrochlores through the lens of chemical pressure. Chemical pressure is applied by varying the ionic radius of the non-magnetic B site cation, which either expands or contracts the lattice, in analogy to externally applied pressure. We apply positive chemical pressure by substituting germanium at the B site and negative chemical pressure by substituting lead at the B site. We also consider the effect of platinum substitution, which has nominally negligible chemical pressure effects. In the ytterbium pyrochlores, we find that positive chemical pressure tunes the magnetic ground state from ferromagnetic to antiferromagnetic. Remarkably, we also find that the ytterbium pyrochlores share a ubiquitous form to their low temperature spin dynamics despite their disparate ordered states. In the terbium pyrochlores, we find that positive chemical pressure promotes ferromagnetic correlations - the opposite effect of externally applied pressure. Our studies of platinum pyrochlores reveal that platinum, while non-magnetic, is able to facilitate superexchange pathways. Thus, the magnetic ground states of the platinum pyrochlores are significantly altered from their titanate analogs. The work in this thesis highlights the delicate balance of interactions inherent to rare earth pyrochlore magnetism and shows that chemical pressure is a powerful tool for navigating their phase spaces. / Thesis / Doctor of Philosophy (PhD) / Rare earth pyrochlores have the chemical formula R2B2O7, where R is a magnetic rare earth element and B is a non-magnetic element. Materials of this type are widely studied because they have a propensity to exhibit exotic magnetic properties. In this thesis, we study the effect of varying the size of the non-magnetic B site atom, which is termed chemical pressure. As B is made larger or smaller, the crystal lattice expands or contracts, mimicking the effect of externally applied pressure. High-pressure synthesis techniques were used to prepare R2B2O7 compounds with B site cations that are typically too small (germanium), too large (lead), or too unstable (platinum) under ambient pressure conditions. Our characterizations of these high-pressure materials have revealed that their magnetism is remarkably sensitive to the application of chemical pressure.

This dissertation aims to investigate and correlate structure, dynamics and transport properties of several novel soft materials systems using multiple Nuclear Magnetic Resonance (NMR) methodologies, including solid-state NMR (SSNMR), diffusometry, and imaging, and with the help of X-ray scattering. First, we report the investigation of structure and dynamics of three polymeric membranes: hydroxyalkyl-containing imidazolium homopolymers, poly(arylene ether sulfone) segmented copolymers, and disulfonated poly(arylene ether sulfone) random copolymers using a wide array of SSNMR techniques, including: 1) ¹³C cross-polarization magic angle spinning (CPMAS) with varying cross-polarization (CP) contact time, 2) ¹³C single-pulse magic angle spinning (MAS) with varying delay time, 3) ²³Na single-pulse MAS, 4) two dimensional phaseadjusted spinning sideband (2D PASS), 5) proton spin−lattice relaxation (T₁), 6) rotating frame spin−lattice relaxation (T₁ρ), and 7) center-band-only detection of exchange (CODEX). These various types of SSNMR spectroscopic methods provide a wealth of structural and dynamic information over a wide range of time scales from a few nanoseconds to seconds. We further present a picture of rich structural and transport behaviors in supramolecular assemblies formed by amphiphilic wedge molecules using a combination of ²³Na solid-state NMR, ¹H/²H PFG NMR diffusion, relaxation and grazing-incidence small-angle X-ray scattering. Our results show that the liquid crystalline domains in these materials undergo a transition from columnar to bicontinuous cubic phases with a simple increase in humidity, while the amorphous domain boundaries consist of individual wedge molecules with a significant fraction (~ 10%) of total wedge molecules. Multiple-component diffusion of both wedges and water further confirms the structural and dynamic heterogeneity, with the bicontinous cubic phase being able to facilitate much faster water and ion transport than the columnar phase. We then develop a quantitative approach to probe the migration of two novel “theranostic” polymeric agents (combining “therapeutic” and “diagnostic” functions) into bulk hydrogels using two distinct time-resolved magnetic resonance imaging (MRI) methods. To the best of our knowledge, this is the first work that combines time-resolved MRI experiments to reliably quantify diffusivity of paramagnetic and superparamagnetic nanoparticles in bulk biological media. Our results agree closely with those obtained from fluorescence techniques, yet the capability of our approach allows the analysis of actual nanoparticles diffusion through biogels on mm to cm scales during a range of time periods. Finally, we employ a combination of NMR techniques to obtain a comprehensive understanding of ion clustering and transport behaviors of ionic liquids inside the benchmark ionic polymer Nafion. Spin relaxation shows that anion relaxation is more influenced by the fixed sulfonate groups than cation relaxation. 2D ¹H-¹⁹F heteronuclear Overhauser effect spectroscopy (HOESY) and 1D ¹⁹F¹⁹F selective nuclear Overhauser effect (NOE) spectroscopy confirm our assumption of the formation of ion clusters at low water content in the ionomer. While we observe non-restricted diffusion behavior for cations, anion diffusion is strongly restricted both between domain boundaries and within domains in the absence of water. The restricted anion diffusion can serve as a reliable probe for detailed multiscale structures of the ionomer. / Ph. D.

As the switching rates in electronic and optoelectronic devices are pushed to even higher frequencies, it is crucial to probe carrier dynamics in semiconductors on femtosecond timescales. Time resolved spectroscopy is an excellent tool to probe the relaxation dynamics of photoexcited carriers; where after the initial photoexcitation, the nonequilibrium population of electrons and holes relax by a series of scattering processes including carrier-carrier and carrier-phonon scattering. Probing carrier and spin relaxation dynamics in InAs and InSb based narrow-gap semiconductors is crucial to understand the different scattering mechanisms related to the systems. Similar studies in InSb quantum wells are also intriguing, especially for their scientifically unique features (such as small effective mass, large g-factor etc). Our time resolved techniques demonstrated tunability of carrier and spin dynamics which might be important for charge and spin based devices. The samples studied in this work were provided by the groups of Prof. Wessels (Northwestern University) and Prof. Santos (University of Oklahoma). Theoretical calculations were performed by the group of Prof. Stanton (University of Florida). The THz measurements were performed at Wright State University in collaboration with Prof. Jason Deibel. This work has been supported by the National Science Foundation through grants Career Award DMR-0846834, AFOSR Young Investigator Program 06NE231. A portion of this work was performed at the National High Magnetic Field Laboratory (in collaboration with Dr. Stephen McGill), which is supported by National Science Foundation Cooperative Agreement No. DMR-0654118, the State of Florida, and the U.S. Department of Energy. / Ph. D.

Electron spin relaxation and carrier recombination were investigated in gallium indium nitride arsenide (GaInNAs) multiple quantum wells, using picosecond optical pulses. Pump-probe experiments were carried out at room temperature, using pulses produced by a Ti:sapphire pumped optical parametric oscillator. The peak wavelengths of the excitonic resonances for the quantum well samples were identified using linear absorption measurements, and were found to be in the range 1.25µm-1.29µm. Carrier recombination times were measured for three samples of varying nitrogen content, and were observed to decrease from 548 to 180ps as nitrogen molar fractions were increased in the range 0.45-1.24%. Carrier recombination times were also measured for samples which had undergone a post-growth annealing process, and were found to be signicantly shorter compared to times measured for as-grown samples. Electron spin relaxation time was investigated for samples with quantum well widths in the range 5.8-8nm, and was found to increase with increasing well width, (i.e. decreasing quantum confinement energy), a trend predicted by both D'Yakonov-Kachorovskii and Elliott-Yafet models of spin relaxation in quantum wells. In a further study, longer spin relaxation times were exhibited by samples containing higher molar fractions of nitrogen, but having nominally constant quantum well width. Spin relaxation times increased from 47ps to 115ps for samples containing nitrogen concentrations in the range 0.45-1.24%. Decreases in spin relaxation time were observed in the case of those samples which had been annealed post-growth, compared to as-grown samples. Finally, all-optical polarisation switching based on spin relaxation of optically generated carriers in GaInNAs multiple quantum wells was demonstrated.

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