Relative Orientation of EFG Tensors of Half-integer Quadupolar Nuclei Studied by 3D MQMAS Spin Diffusion Spectroscopy

This thesis is an experimental study of spin dependent transport in nanoscale ferromagnetic tunnel junction arrays and lateral multi-terminal devices with normal metal and superconducting spin transport channels. Two-, three-, and five-junction arrays have been fabricated in the form of lateral circuits and characterized using variable temperature magneto-transport measurements. The smallest inter-junction separation achieved was 65 nm. No significant enhancement in the sequential magneto-resistance (MR) was observed, which is attributed to the combined effect of short spin diffusion length in the ferromagnetic electrodes and high resistance of the tunnel barriers used. A substantially weaker bias dependence of the MR is observed for double junctions than for single junctions, consistent with the theoretical expectations. Spin diffusion and relaxation in one-dimensional normal metal channels is studied using a novel multi-terminal device. The device has multiple ferromagnetic detector electrodes for an in-situ determination of the spin transport parameters. Such configuration has a great advantage as it eliminates sample-to-sample uncertainties in the physical properties studied. A three terminal device having a pair of detector electrodes placed symmetrically about the injection point is used to directly demonstrate decoupling of spin and charge current in nanostructures. Furthermore, by varying the thickness of the normal metal channel on the scale of the mean free path the surface contribution to spin relaxation is measured and compared to the bulk spin scattering rate. It is found that for Al surface scattering makes a weak contribution to the overall spin relaxation rate, the result that should be important for a number of proposed thin film spin-based devices. The interplay between non-equilibrium magnetism and superconductivity is studied in a ferromagnetic/superconductor single electron transistor. Spin imbalance in the base is controlled by the bias voltage applied to the magnetic emitter/collector as well as the relative orientation of their magnetic moments. A strong magneto-transport effect is observed and attributed to a suppression of the superconducting gap in the center electrode by the spin imbalance in the antiparallel state of the device. The intrinsic spin relaxation parameters for the center electrode, important for interpreting the data are studied in a separate experiment using spin injection into a one-dimensional superconducting channel. It is found that the spin accumulation increases substantially on transition into the superconducting state while the spin diffusion length is reduced. These results represent a new way of combining magnetism and superconductivity on the nano-scale. / QC 20100924

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Depuis 1949, date à laquelle Bloembergen en introduisit le concept, la diffusion de spin nucléaire suscite un vif intérêt en résonance magnétique. La diffusion de spin, qui peut être définie comme le transfert de polarisation de spin induit par l’interaction dipolaire, est un mécanisme omniprésent dans les solides. Les mesures expérimentales de ce phénomène contiennent des informations sur la structure du système étudié. La diffusion de spin est cependant un problème quantique à N corps, ce qui rend sa description ab initio relativement difficile. L’objectif principal de cette thèse est d’obtenir une description quantitative et ab initio de la diffusion de spin, en modélisant de manière adéquate la dynamique à N corps sous-jacente. Tout d’abord, nous exploitons une approche existante, reposant sur l’utilisation d’une équation maître pour les polarisations, dans le cas de la diffusion de spin entre carbones permise par les protons (PDSD). Ensuite, nous introduisons une méthode permettant de simuler l’évolution temporelle d’un ensemble d’observables pour un système de spins nucléaires fortement couplés, en utilisant les corrélations de petit ordre dans l’espace de Liouville (LCL). Le modèle LCL fournit une description précise du transfert de polarisation pour les systèmes polycristallins soumis à la rotation à l’angle magique. Après avoir décrit le modèle, nous analysons plus en détail la réduction de l’espace de Liouville pour les solides, afin d’identifier les conditions dans lesquelles l’approximation LCL est valide. Enfin, nous effectuons des simulations de la diffusion de spin entre pro- tons (PSD) et entre carbones (PDSD), à partir de la structure des cristaux étudiés et sans aucun paramètre libre, et nous constatons pour des solides organiques polycristallins que leur accord avec les mesures expérimentales est excellent. / Since its introduction by Bloembergen in 1949, nuclear spin diffusion has been a topic of significant interest in magnetic resonance. Spin diffusion, which can be defined as the transfer of spin polarisation induced by the dipolar interaction, is a ubiquitous transport mechanism in solids. Experimental observations of spin diffusion contain structural information. However, the many-body nature of the problem makes it difficult to describe from first principles. The central goal of this thesis is to obtain a quantitative description of the spin diffusion phenomenon from first-principles, through the development of suitable models of the underlying many-body dynamics. To that end we first consider an extension of an existing approach that relies on a master equation to describe the polarisations, for the case of proton-driven carbon-13 spin diffusion (PDSD). Second, a novel approach is introduced for the simulation of the time evolution of selected observables for large strongly coupled nuclear spin systems, using low-order correlations in Liouville space (LCL). Following the introduction of this new simulation method, Liouville-space reduction in solids is analysed in more detail, in order to identify the conditions under which the LCL approximation is valid. Finally, using the LCL model, simulations of proton spin diffusion (PSD) and PDSD are performed, directly from crystal geometry and with no adjustable parameters, and are found to be in excellent agreement with experimental measurements for polycrystalline organic solids.

O objetivo desta dissertação é a utilização de metodologias de RMN para caracterizar a separação de fases e, em algum grau, a dinâmica de segmentos moleculares em copolímeros em bloco. Na primeira parte do trabalho, técnicas de RMN de Difusão de Spins, cujo fenômeno envolvido traz informações sobre a formação de domínios de segmentos moleculares, foram exploradas no sentido de avaliar seu desempenho assim como as principais dificuldades experimentais. Para isso, foi usado como referência o copolímero tri-bloco SEBS (Estireno-EtilenoButileno-Estireno), cuja morfologia é bem conhecida. Os testes experimentais foram realizados em equipamentos de RMN com campo magnético de 0.5 T e 9.4 T, sendo que em baixo campo uma proposta alternativa de tratamento dos dados foi utilizada. Como já apontado na literatura, os resultados indicaram que embora seja possível realizar tais experimentos em baixo campo a análise dos dados se torna mais complexa devido aos tempos de relaxação T1 mais curtos, tornando necessário o uso de simulações numéricas, que fazem a análise mais dependente de modelos específicos. A segunda parte do trabalho foi dedicada ao estudo de copolímeros em bloco compostos por polióxidoetileno (POE) ou Polietileno Glicol (PEG - POE de baixo peso molecular) e poliestireno (PS) e atambém copolimeros a base de PS e acrilatos ramificados com POE (PMAPEG - do inglês Poly Methyl Acrilate Polyethylene Glicol). Nesses estudos, técnicas de RMN de 1H e 13C como função da temperatura foram usadas para estudar as principais transições dinâmicas das cadeias de POE. Foi demonstrado que, embora o comportamento dinâmico das cadeias de POE seja similar em todos os copolímeros estudados, nas amostras de copolímeros com PMAPEG o grau de heterogeneidade dos movimentos das cadeias de POE é consideravelmente menor, o que foi atribuído ao empacotamento local semelhante e mais regular nos segmentos PMAPEG. Experimentos de RMN de Difusão de Spins foram utilizados nos estudos de morfologia, sendo demonstrada a separação de fases com formação de domínios em todas as amostras, com a regularidade desses domínios dependendo da composição. As dimensões médias dos domínios foram estimadas e os resultados correlacionados com os aspectos dinâmicos. / The main objective of this dissertation is the use of NMR methods to characterize the phase separation and, to some extent, the dynamics of the molecular segments in block copolymers. In the first part, NMR Spin Diffusion methods were explored in order to evaluate their performance as well as the main experimental difficulties. For that, a reference tri-block polymer SEBS (styrene-block-butadiene-block-styrene), which had a well known morphology, was used. The experimental tests were carried out in NMR equipments with magnetic field of 0.47 T and 9.4 T and at low filed an alternative proposal for data analysis was used. A already shown in the literature, the results indicated that , despite being possible to accomplish these experiments in low field, the data analysis become more intricate due to the shorter T1 values at this magnetic field, requiring the use of numerical simulations, which make the method more model dependent. The second part was dedicated to the study of copolymers consisting of Polyoxyethylene (PEO) or Polyethylene Glycol (PEG-low molecular weight PEO) and polystyrene (PS) as well as copolymers based on PS and Poly acrylates with PEO branches (PMAPEG -Poly Methyl Acrylate Polyethylene Glicol). In these studies, 1H and 13C NMR methods as function of temperature were used to characterize the main dynamic transitions in the PEO chains. It was shown that, despite similar dynamic behavior was observed in all samples, the PS-PMAPEG copolymers present a smaller degree of motional heterogeneity, which was attributed to the similar local packing of the PMAPEG chains. Using Spin diffusion NMR information about the morphology of the samples were obtained, showing evidences of phase separation and domain formation in all samples, being the regularity of the domain related with the sample composition. The average domain sizes were estimated.

In recent years, Spin Seebeck effect (SSE) emerges as one of the efficient and easiest ways to generate pure spin current for spintronics devices. In this dissertation, we have systematically studied the SSE and related phenomena like spin Hall magneto-resistance (SMR), anomalous Nernst effect (ANE) in functional magnetic oxides for both fundamental understanding of their origins and practical ways to apply into technological devices. The research has been performed on three different systems of topical interest: (i) Y3Fe5O12 (YIG)/Pt and YIG/C60/Pt, (ii) CoFe2O4 (CFO)/Pt and CFO/C60/Pt, and (iii) Nd0.6Sr0.4MnO3 (NSMO). In case of the YIG/Pt structure, we have achieved a new consensus regarding the temperature dependence of the longitudinal SSE (LSSE). For the first time, we have demonstrated the temperature dependence of LSSE in association with the magnetocrystalline anisotropy (HK) and surface perpendicular magnetic anisotropy field (HKS) of YIG in the same YIG/Pt system. We show that on lowering temperature, the sharp drop in LSSE signal (VLSSE) and the sudden increases in HK and HKS at ~175 K are associated with the spin reorientation due to single ion anisotropy of Fe2+ ions. The VLSSE peak at ~75 K is attributed to the HKS and MS (saturation magnetization) whose peaks also occur at the same temperature. The effects of surface and bulk magnetic anisotropies are corroborated with those of thermally excited magnon number and magnon propagation length to satisfactorily explain the temperature dependence of LSSE in the Pt/YIG system. As a new way to reduce conductivity mismatch, promote spin transport, and tune the spin mixing conductance (G) at the YIG/Pt interface, we have deposited an organic semiconductor (OSC), C60, between ferrimagnetic material (FM) and Pt. Transverse susceptibility study on YIG/C60/Pt has shown that the deposition of C60 has reduced HKS at the surface of YIG significantly, due to the hybridization between the dz2 orbital in Fe and C atoms, leading to the overall increase in spin moments and G and consequently the LSSE. Upon lowering temperature from 300 K, we have observed an exponential increase in LSSE at low temperature (a ~800% increment at 150 K) in this system, which is attributed to the exponential increase in the spin diffusion length of C60 at low temperature. On the other hand, similar experiments on CoFe2O4 (CFO)/C60/Pt show a reduction in the LSSE signal at room temperature, due to the hybridization between the dz2 orbital in Co and C atoms that results in the increased magnetic anisotropy. Upon decreasing the temperature below 150 K, we have interestingly observed that LSSE signal from CFO/C60/Pt exceeds that of CFO/Pt and increases remarkably with temperature. This finding confirms the important role played by the spin diffusion length of C60 in enhancing the LSSE. A systematic study of SMR, SSE, and HKS on the YIG/Pt system using the same YIG single crystal has revealed a low-temperature peak at the same temperature (~75 K) for all the phenomena. Given the distinct origins of the SSE and SMR, our observation points to the difference in spin states between the bulk and surface of YIG as the main reason for such a low-temperature peak, and suggests that the ‘magnon phonon drag’ theory developed to explain the temperature-dependent SSE behavior should be adjusted to include this important effect. SSE and ANE studies on NSMO films have revealed the dominance of ANE over SSE in this class of perovskite-structured materials. The substrate-dependent study of the films shows that compressive strain developed due to the large lattice mismatch from LAO gives rise to the enhanced ANE signal. On the same substrate, ANE signal strength increases as the thickness increases. A sign change in ANE has been observed at a particular temperature, which explains that the Anomalous Hall effect (AHE) and ANE in these systems arise due to intrinsic scattering mechanisms. Overall, we have performed the SSE and related studies on the three important classes of functional magnetic oxide materials. We demonstrate the important role of magnetic anisotropy in manipulating the SSE in these systems. With this knowledge, we have been able to design the novel YIG/C60/Pt and CFO/C60/Pt heterostructures that exhibit the giant SSEs. The organic semiconductor C60 has been explored for the first time as a means of controlling pure spin current in inorganic magnetic oxide/metal heterostructures, paying the way for future spintronic materials and devices.

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Since its introduction by Bloembergen in 1949, nuclear spin diffusion has been a topic of significant interest in magnetic resonance. Spin diffusion, which can be defined as the transfer of spin polarisation induced by the dipolar interaction, is a ubiquitous transport mechanism in solids. Experimental observations of spin diffusion contain structural information. However, the many-body nature of the problem makes it difficult to describe from first principles. The central goal of this thesis is to obtain a quantitative description of the spin diffusion phenomenon from first-principles, through the development of suitable models of the underlying many-body dynamics. To that end we first consider an extension of an existing approach that relies on a master equation to describe the polarisations, for the case of proton-driven carbon-13 spin diffusion (PDSD). Second, a novel approach is introduced for the simulation of the time evolution of selected observables for large strongly coupled nuclear spin systems, using low-order correlations in Liouville space (LCL). Following the introduction of this new simulation method, Liouville-space reduction in solids is analysed in more detail, in order to identify the conditions under which the LCL approximation is valid. Finally, using the LCL model, simulations of proton spin diffusion (PSD) and PDSD are performed, directly from crystal geometry and with no adjustable parameters, and are found to be in excellent agreement with experimental measurements for polycrystalline organic solids.

O objetivo desta dissertação é a utilização de metodologias de RMN para caracterizar a separação de fases e, em algum grau, a dinâmica de segmentos moleculares em copolímeros em bloco. Na primeira parte do trabalho, técnicas de RMN de Difusão de Spins, cujo fenômeno envolvido traz informações sobre a formação de domínios de segmentos moleculares, foram exploradas no sentido de avaliar seu desempenho assim como as principais dificuldades experimentais. Para isso, foi usado como referência o copolímero tri-bloco SEBS (Estireno-EtilenoButileno-Estireno), cuja morfologia é bem conhecida. Os testes experimentais foram realizados em equipamentos de RMN com campo magnético de 0.5 T e 9.4 T, sendo que em baixo campo uma proposta alternativa de tratamento dos dados foi utilizada. Como já apontado na literatura, os resultados indicaram que embora seja possível realizar tais experimentos em baixo campo a análise dos dados se torna mais complexa devido aos tempos de relaxação T1 mais curtos, tornando necessário o uso de simulações numéricas, que fazem a análise mais dependente de modelos específicos. A segunda parte do trabalho foi dedicada ao estudo de copolímeros em bloco compostos por polióxidoetileno (POE) ou Polietileno Glicol (PEG - POE de baixo peso molecular) e poliestireno (PS) e atambém copolimeros a base de PS e acrilatos ramificados com POE (PMAPEG - do inglês Poly Methyl Acrilate Polyethylene Glicol). Nesses estudos, técnicas de RMN de 1H e 13C como função da temperatura foram usadas para estudar as principais transições dinâmicas das cadeias de POE. Foi demonstrado que, embora o comportamento dinâmico das cadeias de POE seja similar em todos os copolímeros estudados, nas amostras de copolímeros com PMAPEG o grau de heterogeneidade dos movimentos das cadeias de POE é consideravelmente menor, o que foi atribuído ao empacotamento local semelhante e mais regular nos segmentos PMAPEG. Experimentos de RMN de Difusão de Spins foram utilizados nos estudos de morfologia, sendo demonstrada a separação de fases com formação de domínios em todas as amostras, com a regularidade desses domínios dependendo da composição. As dimensões médias dos domínios foram estimadas e os resultados correlacionados com os aspectos dinâmicos. / The main objective of this dissertation is the use of NMR methods to characterize the phase separation and, to some extent, the dynamics of the molecular segments in block copolymers. In the first part, NMR Spin Diffusion methods were explored in order to evaluate their performance as well as the main experimental difficulties. For that, a reference tri-block polymer SEBS (styrene-block-butadiene-block-styrene), which had a well known morphology, was used. The experimental tests were carried out in NMR equipments with magnetic field of 0.47 T and 9.4 T and at low filed an alternative proposal for data analysis was used. A already shown in the literature, the results indicated that , despite being possible to accomplish these experiments in low field, the data analysis become more intricate due to the shorter T1 values at this magnetic field, requiring the use of numerical simulations, which make the method more model dependent. The second part was dedicated to the study of copolymers consisting of Polyoxyethylene (PEO) or Polyethylene Glycol (PEG-low molecular weight PEO) and polystyrene (PS) as well as copolymers based on PS and Poly acrylates with PEO branches (PMAPEG -Poly Methyl Acrylate Polyethylene Glicol). In these studies, 1H and 13C NMR methods as function of temperature were used to characterize the main dynamic transitions in the PEO chains. It was shown that, despite similar dynamic behavior was observed in all samples, the PS-PMAPEG copolymers present a smaller degree of motional heterogeneity, which was attributed to the similar local packing of the PMAPEG chains. Using Spin diffusion NMR information about the morphology of the samples were obtained, showing evidences of phase separation and domain formation in all samples, being the regularity of the domain related with the sample composition. The average domain sizes were estimated.

京都大学 / 新制・課程博士 / 博士(理学) / 甲第24871号 / 理博第4981号 / 新制||理||1711(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)准教授 武田 和行, 教授 堀毛 悟史, 教授 北川 宏 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM